OPIUM
=Botanical Origin=—Papaver somniferum L., see preceding article.
=History=[186]—The medicinal properties of the milky juice of the poppy have been known from a remote period. Theophrastus who lived in the beginning of the 3rd century B.C. was acquainted with the substance in question, under the name of Μηκώνιον. The investigations of Unger (1857; see Capsulæ Papaveris,) have failed to trace any acquaintance of ancient Egypt with opium.
Scribonius Largus in his Compositiones Medicamentorum[187] (circa A.D. 40) notices the method of procuring opium, and points out that the true drug is derived from the capsules, and not from the foliage of the plant.
[186] For more particulars see Dr. Rice’s learned notes in New Remedies, New York, 1876, 229, reprinted in Pharm. Journ. vii. (2 Dec. 1876; 23 June 1877), pp. 452 and 1041.
[187] Ed. Bernhold, Argent. 1786, c. iii. sect. 22.
About the year 77 of the same century, Dioscorides[188] plainly distinguished the juice of the capsules under the name of ὀπός from an extract of the entire plant, μηκώνειον, which he regarded as much less active. He described exactly how the capsules should be incised, the performing of which operation he designated by the verb ὀπίζειν. We may infer from these statements of Dioscorides that the collection of opium was at that early period a branch of industry in Asia Minor. The same authority alludes to the adulteration of the drug with the milky juices of Glaucium and Lactuca, and with gum.
Pliny[189] devotes some space to an account of Opion, of which he describes the medicinal use. The drug is repeatedly mentioned as Lacrima papaveris by Celsus in the 1st century, and more or less particularly by numerous later Latin authors. During the classical period of the Roman Empire as well as in the early middle ages, the only sort of opium known was that of Asia Minor.
The use of the drug was transmitted by the Arabs to the nations of the East, and in the first instance to the Persians. From the Greek word ὀπός, juice, was formed the Arabic word Afyun, which has found its way into many Asiatic languages.[190]
The introduction of opium into India seems to have been connected with the spread of Islamism, and may have been favoured by the Mahommedan prohibition of wine. The earliest mention of it as a production of that country occurs in the travels of Barbosa[191] who visited Calicut on the Malabar coast in 1511. Among the more valuable drugs the prices of which he quotes, opium occupies a prominent place. It was either imported from Aden or Cambay, that from the latter place being the cheaper, yet worth three or four times as much as camphor or benzoin.
Pyres[192] in his letter about Indian drugs to Manuel, king of Portugal, written from Cochin in 1516, speaks of the opium of Egypt, that of Cambay and of the kingdom of Coûs (Kus Bahár, S.W. of Bhotan) in Bengal. He adds that it is a great article of merchandize in these parts and fetches a good price;—that the kings and lords eat of it, and even the common people, though not so much because it costs dear.
Garçia d’Orta[193] informs us that the opium of Cambay in the middle of the 16th century was chiefly collected in Malwa, and that it is soft and yellowish. That from Aden and other places near the Erythrean Sea is black and hard. A superior kind was imported from Cairo, agreeing as Garçia supposed with the opium of the ancient Thebaïd, a district of Upper Egypt near the modern Karnak and Luksor.
[188] Lib. iv. c. 65.
[189] Lib. xx. c. 76.
[190] There are no ancient Chinese or Sanskrit names for opium. In the former language the drug is called O-fu-yung from the Arabic. Two other names Ya-pien and O-pien are adaptations to the Chinese idiom of our word opium. There are several other designations which may be translated Smoking dirt, Foreign poison, Black commodity, &c.
[191] Coasts of East Africa and Malabar (Hakluyt Soc.), Lond. 1866. 206, 223.
[192] Journ. de Soc. Pharm. Lusit. ii. (1838) 36. Pires, or Pyres, was the first ambassador from Europe to China: Abel Rémusat, Nouv. mélanges asiatiques, ii. (1829) 203. See also Pedro José da Silva, Elogio historico e noticia completa de Thomé Pires, pharmaceutico e primeiro naturalista da India, Lisboa, 1866 (Library of the Pharm. Soc., London, Pamphlets, No. 30).
[193] Aromatum ... Historia, edit Clusius, Antv. 1574. lib. i. c. 4.
In India the Mogul Government uniformly sold the opium monopoly, and the East India Company followed their example, reserving to itself the sole right of cultivating the poppy and selling the opium.
Opium thebaïcum was mentioned by Simon Januensis,[194] physician to Pope Nicolas IV. (A.D. 1288-92), who also alludes to meconium as the dried juice of the pounded capsules and leaves. Prosper Alpinus,[195] who visited Egypt in 1580-83, states that opium or meconium was in his time prepared in the Thebaïd from the expressed juice of poppy heads.
The German traveller Kämpfer, who visited Persia in 1685, describes the various kinds of opium prepared in that country. The best sorts were flavoured with nutmeg, cardamom, cinnamon and mace, or simply with saffron and ambergris. Such compositions were called Theriaka, and were held in great estimation during the middle ages, and probably supplied to a large extent the place of pure opium. It was not uncommon for the sultans of Egypt of the 15th century to send presents of Theriaka to the doges of Venice and the sovereigns of Cyprus.[196]
In Europe opium seems in later times not to have been reckoned among the more costly drugs; in the 16th century we find it quoted at the same price as benzoin, and much cheaper than camphor, rhubarb, or manna.[197]
With regard to China it is supposed that opium was first brought thither by the Arabians, who are known to have traded with the southern ports of the empire as early as the 9th century. More recently, at least until the 18th century, the Chinese imported the drug in their junks as a return cargo from India. At this period it was used almost exclusively as a remedy for dysentery, and the whole quantity imported was very small. It was not until 1767 that the importation reached 1,000 chests, at which rate it continued for some years, most of the trade being in the hands of the Portuguese. The East India Company made a small adventure in 1773; and seven years later an opium depôt of two small vessels was established by the English in Lark’s Bay, south of Macao.
The Chinese authorities began to complain of these two ships in 1793, but the traffic still increased, and without serious interruption until 1820, when an edict was issued forbidding any vessel having opium on board to enter the Canton river. This led to a system of contraband trade with the connivance of the Chinese officials, which towards the expiration of the East India Company’s charter in 1834 had assumed a regular character. The political difficulties between England and China that ensued shortly after this event, and the so-called Opium War, culminated in the Treaty of Nanking (1842), by which five ports of China were opened to foreign trade, and opium was in 1858 admitted as a legal article of commerce.[198]
[194] Clavis Sanationis, Venet. 1510. 46.
[195] De Medicina Ægyptiorum, Lugd. Bat. 1719. 261.
[196] De Mas Latrie, Hist. de Chypre, iii. 406. 483; Muratori, Rerum Italic. Scriptores, xxii. 1170; Amari, I diplomi Arabi del archivio Fiorentino, Firenze, 1863. 358.
[197] Fontanon, Edicts et ordonnances des roys de France, ii. (1585) 347.
[198] For more ample particulars on these momentous events, see S. Wells Williams’s Middle Kingdom, vol. ii. (1848); British Almanac Companion for 1844, p. 77.
The vice of opium-smoking began to prevail in China in the second half of the 17th century,[199] and in another hundred years had spread like a plague over the gigantic empire. The first edict against the practice was issued in 1796, since which there have been innumerable enactments and memorials,[200] but all powerless to arrest the evil which is still increasing in an alarming ratio. Mr. Hughes, Commissioner of Customs at Amoy, thus wrote on this subject in his official Trade Report[201] for the year 1870:—“Opium-smoking appears here as elsewhere in China to be becoming yearly a more recognized habit,—almost a necessity of the people. Those who use the drug now do so openly, and native public opinion attaches no odium to its use, so long as it is not carried to excess.... In the city of Amoy, and in adjacent cities and towns, the proportion of opium-smokers is estimated to be from 15 to 20 per cent. of the adult population.... In the country the proportion is stated to be from 5 to 10 per cent....”
=Production=—The poppy in whatever region it may grow always contains a milky juice possessing the same properties; and the collection of opium is possible in all temperate and subtropical countries where the rainfall is not excessive. But the production of the drug is limited by other conditions than soil and climate, among which the value of land and labour stands pre-eminent.
At the present day opium is produced on an important scale in Asia Minor, Persia, India, and China; to a small extent in Egypt. The drug has also been collected in Europe, Algeria,[202] North America,[203] and Australia[204] but more for the sake of experiment than as an object of commerce.
We shall describe the production of the different kinds under their several names.
1. Opium of Asia Minor; Turkey, Smyrna, or Constantinople Opium[205]—The poppy from which this most important kind of opium is obtained is Papaver somniferum, var. β. glabrum Boissier. The flowers are commonly purplish, but sometimes white, and the seeds vary from white to dark violet.
The cultivation is carried on throughout Asia Minor, both on the more elevated and the lower lands, the cultivators being mostly small peasant proprietors. The plant requires a naturally rich and moist soil, further improved by manure, not to mention much care and attention on the part of the grower. Spring frosts, drought, or locusts sometimes effect its complete destruction. The sowing takes place at intervals from November to March, partly to insure against risk of total failure, and partly in order that the plants may not all come to perfection at the same time.
[199] Bretschneider, Study of Chinese Bot. Works, 1870. 48.
[200] Chinese Repository, vol. v. (1837) vi &c.
[201] Addressed to the Inspector-General of Customs, Pekin, and published at Shanghai, 1871
[202] Pharm. Journ. xv. (1856) 348.
[203] Am. Journ. of Phar. xviii. (1870) 124; Journ. of Soc. of Arts, Dec. 1, 1871.
[204] Pharm. Journ. Oct. 1, 1870. 272.
[205] Much information under this head has been derived from a paper On the production of Opium in Asia Minor by S. H. Maltass (Pharm. Journ. xiv. 1855. 396), and one On the Culture and Commerce in Opium in Asia Minor, by E. R. Heffler, of Smyrna (Pharm. Journ. x. 1869. 434).
The plants flower between May and July according to the elevation of the land. A few days after the fall of the petals the poppy head being about an inch and a half in diameter is ready for incision. The incision is made with a knife transversely, about half-way up the capsule, and extends over about two-thirds the circumference, or is carried spirally to beyond its starting point. Great nicety is required not to cut too deep so as to penetrate the capsule, as in that case some of the juice would flow inside and be lost. The incisions are generally made in the afternoon and the next morning are found covered with exuded juice. This is scraped off with a knife, the gatherer transferring it to a poppy leaf which he holds in his left hand. At every alternate scraping, the knife is wetted with saliva by drawing it through the mouth, the object being to prevent the adhesion of the juice to the blade. Each poppy-head is, as a rule, cut only once; but as a plant produces several heads all of which are not of proper age at the same time, the operation of incising and gathering has to be gone over two or three times on the same plot of ground.
As soon as a sufficient quantity of the half-dried juice has been collected to form a cake or lump, it is wrapped in poppy leaves and put for a short time to dry in the shade. There is no given size for cakes of opium, and they vary in weight from a few ounces to more than two pounds. In some villages it is the practice to make the masses larger than in others. Before the opium is ready for the market, a meeting of buyers and sellers is held in each district, at which the price to be asked is discussed and settled,—the peasants being most of them in debt to the buyers or merchants.
To the latter the opium is sold in a very soft but natural state. These dealers sometimes manipulate the soft drug with a wooden pestle into larger masses which they envelope in poppy leaves and pack in cotton bags sealed at the mouth for transport to Smyrna. According to another account, the opium as obtained from the grower is at once packed in bags together with a quantity of the little chaffy fruits of a dock (Rumex sp.) to prevent the lumps from sticking together, and so brought in baskets to Smyrna, or ports farther north.
The opium remains in the baskets (placed in cool warehouses to avoid loss of weight) till sold, and it is only on reaching the buyer’s warehouse that the seals are broken and the contents of the bags exposed. This is done in the presence of the buyer, seller, and a public examiner, the last of whom goes through the process of inspecting the drug piece by piece, throwing aside any of suspicions quality. Heffler of Smyrna asserts that the drug is divided into three qualities, viz.—the prime, which is not so much a selected quality as the opium of some esteemed districts,—the current, which is the mercantile quality and constitutes the great bulk of the crop,—and lastly the inferior or chiqinti.[206] The opium of very bad quality or wholly spurious he would place in a fourth category. Maltass applies the name chiqinti (or chicantee) to opium of every degree of badness.
The examination of opium by the official expert is not conducted in any scientific method. His opinion of the drug is based on colour, odour, appearance and weight, and appears to be generally very correct. Fayk Bey (1867) has recommended the Turkish government to adopt the more certain method of assaying opium by chemical means.
[206] Probably signifying refuse,—that which comes out.
In Asia Minor the largest quantities of opium are now produced in the north-western districts of Karahissar Sahib, Balahissar, Kutaya, and Kiwa (or Geiveh), the last on the river Sakariyeh which runs into the Black Sea. These centres of large production of opium send a superior quality of the drug to Constantinople by way of Izmid; the best apparently from Bogaditch and Balikesri, near the Susurlu river. Angora and Amasia are other places in the north of Asia Minor whence opium is obtained.
In the centre of the peninsula Afium Karahissar (literally opium-black-castle) and Ushak are important localities for opium, which is also the case with Isbarta, Buldur and Hamid farther south. The product of these districts finds its way to Smyrna, in the immediate neighbourhood of which but little opium is produced. The export from Smyrna in 1871, in which year the crop was very large, was 5650 cases, valued at £784,500.[207]
Turkey Opium, as it is generally called in English trade, occurs in the form of rounded masses which according to their softness become more or less flattened or many-sided, or irregular by mutual pressure in the cases in which they are packed. There appears to be no rule as to their weight[208] which varies from an ounce up to more than 6 lb.; from ½ lb. to 2 lb. is however the most usual. The exterior is covered with the remains of poppy leaves strewn over with the Rumex chaff before alluded to, which together make the lumps sufficiently dry to be easily handled. The consistence is such that the drug can be readily cut with a knife, or moulded between the fingers. The interior is moist and coarsely granular, varying in tint from a light chestnut to a blackish brown. Fine shreds of the epidermis of the poppy capsule are perceptible even to the naked eye, but are still more evident if the residue of opium washed with water, is moistened with dilute chromic acid (1 to 100). The odour of Turkey opium is peculiar, and though commonly described as narcotic and unpleasant, is to many persons far from disagreeable. The taste is bitter.
The substances alleged to be used for adulterating Turkey opium are sand, pounded poppy capsules, pulp of apricots or figs, gum tragacanth or even turpentine. Bits of lead are sometimes found in the lumps, also stones and masses of clay.
2. Egyptian Opium,—though not abundant little as formerly is still met with in European commerce. It usually occurs in hard, flattish cakes about 4 inches in diameter covered with the remnants of a poppy leaf, but not strewn over with rumex-fruits. We have also seen it (1873) as freshly imported, in a soft and plastic state. The fractured surface of this opium (when hard) is finely porous, of a dark liver-colour, shining here and there from imbedded particles of quartz or gum, and reddish-yellow points (of resin?). Under the microscope an abundance of starch granules is sometimes visible. The morphine in a sample from Merck amounted to 6 per cent.
[207] Consul Cumberbatch, Trade Report for 1871, presented to Parliament.
[208] The largest lump I have seen weighed 6 lb. 6 oz., being part of 65 packages which I examined 2nd July, 1873.—D. H.
According to Von Kremer who wrote in 1863,[209] there were then in Upper Egypt near Esneh, Kenneh, and Siout, as much as 10,000 feddan (equal to about the same number of English acres) of land cultivated with the poppy from which opium was obtained in March, and seed in April. Hartmann[210] states that the cultivation is carried on by the government, and solely for the requirement of the sanitary establishments.
S. Stafford Allen in 1861 witnessed the collection of opium at Kenneh in Upper Egypt,[211] from a white-flowered poppy. An incision is made in the capsule by running a knife twice round it transversely, and the juice scraped off the following day with a sort of scoop-knife. The gatherings are collected on a leaf and placed in the sun to harden. The produce appeared extremely small and was said to be wholly used in the country.
Gastinel, director of the Experimental Garden at Cairo, and government inspector of pharmaceutical stores, has shown (1865) that the poppy in Egypt might yield a very good product containing 10 to 12 per cent. of morphine, and that the present bad quality of Egyptian opium is due to an over-moist soil, and a too early scarification of the capsule, whereby (not to mention wilful adulteration) the proportion of morphine is reduced to 3 or 4 per cent.
In 1872, 9636 lb. of opium, value £5023, were imported into the United Kingdom from Egypt.
3. Persian Opium.—Persia, probably the original home of the baneful practice of opium-eating, cultivates the drug chiefly in the central provinces where, according to Boissier, the plant grown to furnish it is Papaver somniferum, var. γ album (P. officinale Gm.) having ovate roundish capsules. Poppy heads from Persia which we saw at the Paris Exhibition in 1867, had vertical incisions and contained white seeds.
The strongest opium called in Persia Teriak-e-Arabistani is obtained in the neighbourhood of Dizful and Shuster, east of the Lower Tigris. Good opium is likewise produced about Sari and Balfarush in the province of Mazanderan, and in the southern province of Kerman. The lowest quality which is mixed with starch and other matters, is sold in light brown sticks; it is made at Shahabdulazim, Kashan, and Kum.[212] A large quantity of opium appears to be produced in Khokan and Turkestan.
[209] Aegypten, Forschungen über Land und Volk während eines 10 zehnjährigen Aufenthalts, Leipzig, 1863.
[210] Naturgeschichtl. medicin. Skizze der Nilländer, Berlin, 1866. 353.
[211] Pharm. Journ. iv. (1863) 199.
[212] Polak, Persien, ii. (1865) 248, &c.
Persian opium is carried overland to China through Bokhara, Khokan and Kashgar;[213] but since 1864 it has also been extensively conveyed thither by sea, and it is now quoted in trade reports like that of Malwa, Patna, and Benares.[214] It is exported by way of Trebizond to Constantinople where it used to be worked up to imitate the opium of Asia Minor, and at the same time adulterated.[215] Since 1870, Persian opium which was previously rarely seen as such in Europe, has been imported in considerable quantity, being shipped now from Bushire and Bunder Abbas, in the Persian Gulf, to London or to the Straits Settlements and China. It occurs in various forms, the most typical being a short rounded cone weighing 6 to 10 ounces. We have also seen it in flat circular cakes, 1¼ lb. in weight. In both forms the drug was of firm consistence, a good opium-smell, and internally brown of a comparatively light tint. The surface was strewn over with remnants of stalks and leaves. Some of it had been collected with the use of oil as in Malwa (see p. 51), which was apparent from the greasiness of the cone, and the globules of oil visible when the drug was cut. The best samples of this drug as recently imported, have yielded 8 to 10·75 per cent. of morphine, reckoned on the opium in its moist state.[216]
[213] Powell, Economic Products of the Punjab, i. (1868) 294.
[214] Thus in the Trade Report for Foochow, for 1870, addressed to Mr. Hart, Inspector-General of Customs, Pekin, is the following table:
Malwa. Patna. Benares. Persian. Imports of Opium in 1867 chests 2327 1673 724 300 ” ” 1868 ” 2460 1257 377 544 ” ” 1869 ” 2201 1340 410 493 ” ” 1870 ” 1849 1283 245 630
[215] Letter from Mr. Merck to Dr. F. 1863.
[216] Information kindly given us (9th June, 1873) by Mr. W. Dillworth Howard, of the firm of Howard and Sons, Stratford. A morphine manufacturer has no particular interest in ascertaining the amount of water in the opium he purchases. All he requires to know is the percentage of morphine which the drug contains. It is otherwise with the pharmaceutist, whose preparations have to be made with dried opium.
Carles,[217] from a specimen which seems to have been adulterated with sugar, obtained 8·40 per cent. of morphine, and 3·60 of narcotine, the drug not having been previously dried.
Inferior qualities of Persian opium have also been imported. Some that was soft black and extractiform afforded undried only 3 to ½ per cent. of morphine (Howard); while some of very pale hue in small sticks, each wrapped in paper, yielded no more than 0·2 per cent.! (Howard). For further details, see p. 61.
In Turkestan an aqueous extract of poppy heads collected before maturity is prepared; it seems to be rich in alkaloids.[218]
4. European Opium—From numerous experiments made during the present century in Greece, Italy, France, Switzerland, Germany, England, and even in Sweden, it has been shown that in all these countries a very rich opium, not inferior to that of the East, can be produced.
The most numerous attempts at opium-growing in Europe have been made in France. But although the cultivation was recommended in the strongest terms by Guibourt,[219] who found in French opium the highest percentage of morphine yet observed (22·8 per cent.), it has never become a serious branch of industry.
Aubergier of Clermont-Ferrand has carried on the cultivation with great perseverance since 1844, and has succeeded in producing a very pure inspissated juice which he calls Affium, and which is said to contain uniformly[220] 10 per cent. of morphine. It is made up in cakes of 50 grammes, but is scarcely an article of wholesale commerce.[221]
Some careful and interesting scientific investigations relating to the production of opium in the neighbourhood of Amiens, were made by Decharme in 1855 to 1862.[222] He found 14,725 capsules incised within 6 days to afford 431 grammes of milky juice, yielding 205 grammes (= 47·6 per cent.) of dry opium containing 16 per cent. of morphine. Another sample of dried opium afforded 20 per cent. of morphine. Decharme observed that the amount of morphine diminished when the juice is very slowly dried,—a point of great importance deserving attention in India. The peculiar odour of opium as observable in the oriental drug, is developed, according to the same authority, by a kind of fermentation.[223] Adrian even suggests that morphine is formed only by a similar process, inasmuch as he could obtain none by exhausting fresh poppy capsules with acidulated alcohol, while capsules of the same crop yielded an opium rich in morphine.
[217] Journ. de Pharm. xvii (1873) 427.
[218] Fedschenko’s Catalogue of the Moscow Exhibition, Turkestan department, in Buchner’s Repertorium für Pharmacie, xxii. (1873) 221.
[219] Journ. de Pharm. xli. (1862) 184, 201.
[220] How this uniformity is insured we know not.
[221] Dorvault, Officine, éd. 8. 1872. 648.
[222] They are recorded in several pamphlets, for which we are indebted to the author, reprinted from the Mém. de l’Acad. du déartement de la Somme and the Mém. de l’Académie Stanislas.
[223] Journ. de Pharm. vi. (1867) 222.
5. =East Indian Opium=—The principal region of British India distinguished for the production of opium is the central tract of the Ganges, comprising an area of about 600 miles in length, by 200 miles in width. It reaches from Dinajpur in the east, to Hazaribagh in the south, and Gorakhpur in the north, and extends westward to Agra, thus including the flat and thickly-populated districts of Behar and Benares. The amount of land here actually under poppy cultivation was estimated in 1871-72 as 560,000 acres.
The region second in importance for the culture of opium consists of the broad table-lands of Malwa, and the slopes of the Vindhya Hills, in the dominions of the Holkar.
Beyond these vast districts, the area under poppy cultivation is comparatively small,[224] yet it appears to be on the increase. Stewart[225] reports (1869) that the plant is grown (principally for opium) throughout the plains of the Punjab, but less commonly in the north-west. In the valley of the Biās, east of Lahore, it is cultivated up to nearly 7500 feet above the sea-level.
The manufacture of opium in these parts of India is not under any restriction as in Hindustan. Most districts, says Powell (1868),[226] cultivate the poppy to a certain extent, and produce a small quantity of indifferent opium for local consumption. The drug, however, is prepared in the Hill States, and the opium of Kūlū (E. of Lahore), is of excellent quality, and forms a staple article of trade in that region. Opium is also produced in Nepal, Basāhīr and Rāmpūr, and at Doda Kashtwar in the Jammū territory.[227] It is exported from these districts to Yarkand, Khutan, Aksu, and other Chinese provinces,—to the extent in 1862 of 210 maunds (= 16,800 lb.). The Madras Presidency exports no opium at all.
The opium districts of Bengal[228] are divided into two agencies, those of Behar and Benares, which are under the control of officials residing respectively at Patna and Ghazipur. The opium is a government monopoly—that is to say, the cultivators are under an obligation to sell their produce to the government at a price agreed on beforehand; at the same time it is wholly optional with them, whether to enter on the cultivation or not.
[224] So we may infer from the fact that of the 39,225 chests which paid duty to Government at Bombay in 1872, 37,979 were Malwa opium, the remaining 1,246 being reckoned as from Guzerat.—Statement of the Trade and Nav. of Bombay for 1871-72, p. xv.
[225] Punjab Plants, Lahore, 1869. 10.
[226] Op. cit. i. 294.
[227] At the base of the Himalaya, S. and S.E. of Kashmir.
[228] Much of what follows respecting Bengal opium is derived from a paper by Eatwell, formerly First Assistant and Opium Examiner in the Government Factory at Ghazipur.—Pharm. Journ. xi. (1852) 269, &c.
The variety of poppy cultivated is the same as in Persia, namely, P. somniferum, var. γ album. As in Asia Minor, a moist and fertile soil is indispensable.[229] The plant is liable to injury by insects, excessive rain, hail, or the growth on its roots of a species of Orobanche.
In Behar the sowing takes place at the beginning of November, and the capsules are sacrificed in February or March (March or April in Malwa). This operation is performed with a peculiar instrument, called a nushtur, having three or four two-pointed blades, bound together with cotton thread.[230] In using the nushtur, only one set of points is brought into use at a time, the capsule being scarified vertically from base to summit. This scarification is repeated on different sides of the capsule at intervals of a few days, from two to six times. In many districts of Bengal, transverse cuts are made in the poppy-head as in Asia Minor.
The milky juice is scraped off early on the following morning with an iron scoop, which as it becomes filled is emptied into an earthen pot carried by the collector’s side. In Malwa a flat scraper is used which, as well as the fingers of the gatherer, is wetted from time to time with linseed oil to prevent the adhesion of the glutinous juice. All accounts represent the juice to be in a very moist state by reason of dew, which sometimes even washes it away; but so little is this moisture of the juice thought detrimental that, as Butter states,[231] the collectors in some places actually wash their scrapers in water, and add the washings to the collection of the morning!
The juice when brought home is a wet granular mass of pinkish colour; and in the bottom of the vessel in which it is contained, there collects a dark fluid resembling infusion of coffee, which is called pasēwā. The recent juice strongly reddens litmus, and blackens metallic iron. It is placed in a shallow earthen vessel, which is tilted in such a manner that the pasēwā may drain off as long as there is any of it to be separated. This liquor is set aside in a covered vessel. The residual mass is now exposed to the air, though never to the sun, and turned over every few days to promote its attaining the proper degree of dryness, which according to the Benares regulations, allows of 30 per cent. of moisture. This drying operation occupies three or four weeks.
The drug is then taken to the Government factory for sale; previous to being sold it is examined for adulteration by a native expert, and its proportion of water is also carefully determined. Having been received into stock, it undergoes but little treatment beyond a thorough mixing, until it is required to be formed into globular cakes. This is effected in a somewhat complicated manner, the opium being strictly of standard consistence. First the quantity of opium is weighed out, and having been formed into a ball is enveloped in a crust of dried poppy petals, skilfully agglutinated one over the other by means of a liquid called lēwā. This consists partly of good opium, partly of pasēwā, and partly of opium of inferior quality, all being mixed with the washings of the various pots and vessels which have contained opium, and then evaporated to a thick fluid, 100 grains of which should afford 53 of dry residue. These various things are used to form a ball of opium in the following proportions:—
[229] It is said (1873) that the ground devoted to poppy-culture in Bengal is becoming impoverished, and that the plant no longer attains its usual dimensions.
[230] For figures of the instrument, see Pharm. Journ. xi. (1862) 207.
[231] Pharm. Journ. xi. (1852) 209.
seers. chittaks. Opium of standard consistence 1 7·50 ” contained in lēwā 3·75 Poppy petals 5·43 Fine trash 0·50 ----------- 2 1·18 = about 4 lb. 3½ oz. avoirdupois. -----------
The finished balls usually termed cakes, which are quite spherical and have a diameter of 6 inches, are rolled in poppy trash which is the name given to the coarsely powdered stalks, capsules and leaves of the plant; they are then placed in small dishes and exposed to the direct influence of the sun. Should any become distended, it is at once opened, the gas allowed to escape, and the cake made up again. After three days the cakes are placed, by the end of July, in frames in the factory where the air is allowed to circulate. They still however require constant watching and turning, as they are liable to contract mildew which has to be removed by rubbing in poppy trash. By October the cakes have become perfectly dry externally and quite hard, and are in condition to be packed in cases (40 cakes in each) for the China market which consumes the great bulk of the manufacture.
For consumption in India the drug is prepared in a different shape. It is inspissated by solar heat till it contains only 10 per cent. of moisture, in which state it is formed into square cages of 2 lb. each which are wrapped in oil paper, or it is made into flat square tablets. Such a drug is known as Abkāri Opium.
The Government opium factories in Bengal are conducted on the most orderly system. The care bestowed in selecting the drug, and in excluding any that is damaged or adulterated is such that the merchants who purchase the commodity rarely require to examine it, although permission is freely accorded to open at each sale any number of chests or cakes they may desire. In the year 1871-72 the number of chests sold was 49,695, the price being £139 per chest, which is £26 higher than the average of the preceding year. The net profit on each chest was £90.[232]
In Malwa the manufacture of opium is left entirely to private enterprise, the profit to Government being derived from an export duty of 600 rupees (£60) per chest.[233] As may readily be supposed, the drug is of much less uniform quality than that which has passed through the Bengal agencies, and having no guarantee as to purity it commands less confidence.
[232] Statement exhibiting the moral and material progress and condition of India during the year 1871-72,—Blue Book ordered to be printed 29th July, 1873. p. 10.
[233] The revenue by this duty upon opium exported from Bombay in the year 1871-72, was £2,353,500.
Malwa opium is not made into balls, but into rectangular masses, or bricks which are not cased in poppy petals; it contains as much as 95 per cent. of dry opium. Some opium sold in London as Malwa Opium in 1870 had the form of rounded masses covered with vegetable remains. It was of firm consistence, dark colour, and rather smoky odour. W. D. Howard obtained from it (undried) 9 per cent. of morphine. Other importations afforded the same chemist 4·8 and 6 per cent. respectively.
The chests of Patna opium hold 120 catties or 160 lb. Those of Malwa opium 1 pecul or 133⅓ lb.
The quantity of opium produced in India cannot be ascertained, but the amount exported[234] is accurately known. Thus from British India the exports in the year ending March 31, 1872, were 93,364 chests valued at £13,365,228. Of this quantity Bengal furnished 49,455 chests, Bombay 43,909 chests: they were exported thus:—
To China 85,470 chests. The Straits Settlements 7,845 ” Ceylon, Java, Mauritius and Bourbon 38 ” The United Kingdom 4 ” Other countries 7 ” ------ Total 93,364 ” ------
The net revenue to the Government of India from opium in the year 1871-72 was £7,657,213.
6. =Chinese Opium=—China consumes not only nine-tenths of the opium exported from India, and a considerable quantity of that produced in Asia Minor, but the whole of what is raised in her own provinces. How large is this last quantity we shall endeavour to show.
The drug is mentioned as a production of Yunnan in a history of that province, of which the latest edition appeared in 1736. But it is only very recently that its cultivation in China has assumed such large proportions as to threaten serious competition with that in India.[235]
In a Report upon the Trade of Hankow for 1869, addressed to Mr. Hart, Inspector-General of Customs, Pekin, we find Notes of a journey through the opium districts of Szechuen, undertaken for the special purpose of obtaining information about the drug.[236] From these notes it appears that the estimated crop of the province for 1869 was 4235 peculs (= 564,666 lb.). This was considered small, and the Szechuen opium merchants asserted that 6000 peculs was a fair average. The same authorities estimated the annual yield of the province of Kweichow at 15,000, and of Yunnan at 20,000 peculs, making a total of 41,000 peculs or 5,466,666 lb. In 1869 also, Sir R. Alcock reported that about two-thirds of the province of Szechuen and one-third of that of Yunnan were devoted to opium.[237]
Mr. Consul Markham states[238] that the province of Shensi likewise furnishes important supplies. Mr. Edkins the well-known missionary has lately pointed out from personal observation[238] the extensive cultivation of the poppy in the north-eastern province of Shantung.
[234] Annual Statement of the Trade and Navigation of British India with foreign countries, published by order of the Governor-General, Calcutta, 1872. 52.
[235] In the Report on the Trade of Hankow for 1869 addressed to Mr. Hart, Inspector-General of Customs, Pekin, it is stated—“The importation of opium is considerably short for the last two seasons, but this is not to be wondered at now that each opium-shopkeeper in this and the surrounding districts advertises native drug for sale.”
W. H. Medhurst, British Consul at Shanghai, says—“The drug is now being so extensively produced by the Chinese upon their own soil as sensibly to affect the demand for the India-grown commodity.”—Foreigner in Far Cathay, Lond. 1872. 20.
The quantity of opium exported from Bombay in 1871-72 was less by 1719 chests than that exported in 1870-71, the decrease being attributed to the present large cultivation in China.—Statement of the Trade and Nav. of Bombay for 1871-72, pp. xii. xvi.
[236] According to the French missionaries, the cultivation of the poppy in the great province of Szechuen was hardly known even so recently as 1840.
[237] Calcutta Blue Book, p. 205.
[238] Journ. of Soc. of Arts, Sept. (1872) 6, p. 338.
Opium of very fair quality is now produced about Ninguta (lat. 44°) in north-eastern Manchuria, a region having a rigorous winter climate. Consul Adkins of Newchwang who visited this district in 1871, reports that the opium is inspissated in the sun until hard enough to be wrapped in poppy leaves, and that its price on the spot is equal to about 1s. per ounce.[239]
Shensi opium is said to be the best, then that of Yunnan. But Chinese consumers mostly regard home-grown opium as inferior in strength and flavour, and only fit for use when mixed with the Indian drug.[240]
It must not be supposed that the growing of opium in China has passed unnoticed by the Chinese Government. Whatever may be the nature of the sanction now accorded to this branch of industry, it was “rigorously” prohibited, at least in some provinces, about ten years ago, the effect of the prohibition being to stimulate the foreign importations. Thus at Shanghai in 1865, the importation of Benares opium was 2637 peculs,[241] being more than double that of the previous year, and Persian opium, very rarely seen before, was imported to the extent of 533 peculs, besides about 70 peculs of Turkish.[242]
Of the growth of the trade in opium between India and China, the following figures[243] will give some idea: value of exports in
1852-53—£6,470,915. 1861-62—£9,704,972. 1871-72—£11,605,577.
and[244]
In 1872 1873 1874 1875 1876 Chests opium, 93,364 82,908 88,727 94,746 88,350 Value, £13,365,228 11,426,280 11,341,857 11,956,972 11,148,426
In 1877 the imports of opium in Hong Kong were stated to consist of 6818 peculs, valued at 2,380,665 taels, coming from Patna (2158 peculs), Benares (3596 peculs), Persia (1041 peculs), Malwa (10 peculs), Turkey (3⅓ peculs). In the same year 4043 peculs of opium were imported in Amoy.
Poppy cultivation in the south-west of China has been briefly described by Thorel,[245] from whose remarks it would appear to be exactly like that of India. The poppy is white-flowered; the head is wounded with a three-bladed knife, in a series of 3 to 5 vertical incisions, and the exuded juice is scraped off and transferred to a small pot suspended at the waist. How the drug is finished off we know not. A Chinese account states simply that the best opium is sun-dried. But little is known of its physical and chemical properties. Thorel speaks of it as a soft substance resembling an extract. Dr. R. A. Jamieson[246] describes a sample submitted to him as a flat cake enveloped in the sheathing petiole of bamboo; externally it was a blackish-brown, glutinous substance, dry and brittle on the outside. It lost by drying 18 per cent. of water, and afforded upon incineration 7·5 per cent. of ash. In 100 grains of the (undried) drug, there were found 5·9 of morphine, and 7·5 of narcotine. (See also p. 62.)
[239] North China Herald, June 28, 1873.
[240] Reports of H.M. Consuls in China, 1871 (No. 3, 1872), 1874 (No. 5, 1875), p. 4, 23.
[241] One pecul = 133⅓ lb.
[242] Reports on the Trade at the Treaty Ports in China for 1865. 125.
[243] Taken from the Annual Statement of the Trade and Navigation of British India with foreign countries, published by order of the Governor-General, Calcutta, 1872—199.
[244] Statistical Abstract relating to British India from 1866-67 to 1875-76. London, 1877, pp. 51, 53.
[245] Notes médicales du voyage d’exploration du Mékong et de Cochinchine, Paris, 1870. 23.
[246] Report on the Trade of Hankow, before quoted.
The Chinese who prepare opium for use by converting it into an aqueous extract which they smoke, do not estimate the value of the drug according to its richness in morphine, but by peculiarities of aroma and degree of solubility. In China the preparation of opium for smoking is a special business, not beneath the notice even of Europeans.[247]
7. =Zambezi= or =Mozambik Opium=—From a notice in Pharm. Journal viii. (1878) 1007, it would appear that the Portuguese have formed in 1877 a large company called the “Mozambique Opium Cultivating and Trading Company.”
=Description=—The leading characteristics of each kind of opium have been already noticed. The following remarks bear chiefly on the microscopic appearances of the drug.
As will be presently shown, a more or less considerable part of the drug consists of peculiar substances which are mostly crystallizable and are many of them present in a crystalline state in the drug itself. All kinds of opium appear more or less crystalline when a little in a dry state is triturated with benzol and examined under the microscope. The forms are various: opium from Asia Minor exhibits needles and short imperfect crystals usually not in large quantity, whereas Indian and still more Persian opium is not only highly crystalline but shows a variety of forms which become beautifully evident when seen by polarized light. In several kinds large crystals occur which are doubtless sugar, either intentionally mixed or naturally present. The crystals seen in opium are not however sufficiently developed to warrant positive conclusions as to their nature, besides which the opium constituents when pure are capable under slightly varied circumstances of assuming very different forms. Hence the attempt to obtain from solutions crystals which shall be comparable with those of the same substances in a state of purity often fails. Some interesting observations in this direction were made by Deane and Brady in 1864-5.[248]
All opium has a peculiar narcotic odour and a sharp bitter taste.
=Chemical Composition=—Poppy-juice like analogous vegetable fluids is a mixture of several substances in variable proportion. With the commoner substances which constitute the great bulk of the drug we are not yet sufficiently acquainted.
[247] In 1870, a British firm at Amoy opened an establishment for preparing opium for the supply of the Chinese in California and Australia—Pall Mall Gazette, Nov. 7th, 1878, p. 7, announces: “The monopoly of preparing and selling opium in the 14 districts of Kwang-chow-fu, has been leased to a Hong at Canton for 3 years, ... innovation on former practice.... Opium shops are henceforth to be licensed, and the Exchequer will receive the yearly sum of 140,000 dollars—a welcome addition to the revenue.”
[248] Pharm. Journ. vi. 234; vii. 183. with 4 beautiful plates representing the crystallizations from extract and tincture of opium as well as from the pure opium constituents. When the juice of the poppy is prevented from rapid drying by the addition of a little glycerin, crystals are developed in it.
In the first place (independently of water) there is found mucilage distinct from that of gum arabic, also pectic matter,[249] and albumin. These bodies, together with unavoidable fragments of the poppy capsules, probably amount on an average to more than half the weight of the opium.[250]
In addition to these substances, the juice also contains sugar in solution,—in French opium to the extent of 6½ to 8 per cent.: according to Decharme it is uncrystallizable. Sugar also exists in other opium, but whether always naturally has not been determined.
Fresh poppy-juice contains in the form of emulsion, wax, pectin, albumin and insoluble calcareous salts. When good Turkey opium is treated with water these substances remain in the residue to the extent of 6 to 10 per cent.
Hesse (1870) has isolated the wax by exhausting the refuse of opium with boiling alcohol and a little lime. He thus obtained a crystalline mass from which he separated by chloroform Palmitate and Cerotate of Cerotyl, the former in the larger proportion.
The presence of Caoutchouc has also been pointed out; Procter[251] found opium produced in Vermont to contain about 11 per cent. of that substance, together with a little fatty matter and resin.
Respecting the colouring matter and an extremely small quantity of a volatile body with pepper-like odour, we know but little. After the colouring matter has been precipitated from an aqueous solution of opium by lead acetate, the liquid becomes again coloured by exposure to the air. As to the volatile body, it may be removed by acetone or benzol, but has not yet been isolated.
The salts of inorganic bases, chiefly of calcium, magnesium and potassium, contain partly the ordinary acids such as phosphoric and sulphuric, and partly an acid peculiar to the poppy.
Good opium of Asia Minor dried at 100° C. yields 4 to 8 per cent. of ash.
Poppy-juice contains neither starch nor tannic acid, the absence of which easily detected substances affords one criterion for judging of the purity of the drug.
The proportion of water in opium is very variable. In drying Turkey opium previous to pulverization and for other pharmaceutical purposes, the average loss is about 12½ per cent.[252] Bengal opium, which resembles a soft black extract, is manufactured so as to contain 30 per cent. of water.
[249] We had the opportunity of examining very good specimens of pectic matter and caoutchouc from opium, with which we were presented (1879) by Messrs. J. F. Macfarlane & Co., of London and Edinburgh.
[250] Flückiger, in Pharm. Journ. x. (1869) 208.
[251] American Journ. of Pharm., 1870. 124.
[252] From the laboratory accounts of Messrs. Allen and Hanburys, London, by which it appears that 200 lb. of Turkey opium dried at various times in the course of 10 years lost in weight 25¼ lb.
As the active constituents of opium, or at all events the morphine, can be completely extracted by cold water, the proportion of soluble matter is of practical importance. In good opium of Asia Minor previously dried, the extract (dried at 100° C.) always amounts to between 55 and 66 per cent.,—generally to more than 60, thus affording in many instances a test of the pureness of the drug. Dried Indian opium yields from 60 to 68 per cent. of matter soluble in cold water.[253]
The peculiar constituents of opium are of basic, acid, or neutral nature. Some of these substances were observed in opium as early as the 17th and 18th century, and designated Magisterium Opii. Bucholz in 1802 vainly endeavoured to obtain a salt from the extract by crystallization. In 1803, however, Charles Derosne, an apothecary of Paris, in diluting a syrupy aqueous extract of opium, observed crystals of the substance now called Narcotine, which he prepared pure. He believed that the same body was obtained by precipitating the mother liquor with an alkali, but what he so got was morphine. It is needless to pursue the further researches of Derosne. Ingenious as they were, it was reserved for Friedrich Wilhelm Adam Sertürner, apothecary of Einbeck in Hanover (nat. 1783, ob. 1841) to discover their true interpretation.
Sertürner had been engaged since 1805 with the chemical investigation of opium, and in 1816 he summarized his results in the statement that he had enriched science (we now translate his own words[254])—“not only with the knowledge of a remarkable new vegetable acid [Mekonsäure (meconic acid) which he had made known as Opiumsäure in 1806], but also with the discovery of a new alkaline salifiable base, Morphium, one of the most remarkable substances, and apparently related to ammonia.” Sertürner in fact distinctly recognised the basic nature and the organic constitution of morphium (now called Morphine, Morphia, or Morphinum), and prepared a number of its crystalline salts. He likewise demonstrated the poisonous nature of these substances by experiments on himself and others. Lastly, he pointed out, though very incorrectly, the difference between morphine and the so-called Opium-salt (Narcotine) of Derosne. It is possible that this latter chemist may have had morphine in his hands at the same time as Sertürner, or even earlier. This honour is also due to Séguin, whose paper “Sur l’Opium” read at the Institute, December 24, 1804, was, strange to say, not published till 1814.[255] To Sertürner, however, undoubtedly belongs the merit of first making known the existence of organic alkalis in the vegetable kingdom,[256]—a series of bodies practically interminable. As to opium, it still remains after nearly seventy years a nidus of new substances.
Solutions of morphine in acids or in alkalis rotate the plane of polarization to the left.
The morphine in opium is combined with meconic acid, and is therefore easily soluble in water.[257] The Narcotine is present in the free state, and can be extracted by chloroform, boiling alcohol, benzol, ether, or volatile oils,[258] but not by water. It dissolves in 3 parts of chloroform, in 20 of boiling alcohol, in 21 of benzol, in 40 of boiling ether. Its alkaline properties are very weak, and it does not affect vegetable colours. If we examine opium by the microscope we cannot at once detect the presence of narcotine, but if first moistened with glycerin, numerous large crystals may generally be found after the lapse of some days. If the opium has been previously exhausted with benzol or ether, in order to remove the narcotine, no such crystals will be formed. Hence it follows that narcotine pre-exists in an amorphous state.
[253] Calculated from official statements given by Eatwell in the paper quoted at p. 50.
[254] Gilbert’s Annalen der Physik, lv. (1817) 57.
[255] Annales de Chimie, xcii (1814) 225.
[256] The Institut de France on the 27th June, 1831, awarded to Sertürner a prize of 2000 francs—“pour avoir reconnu la nature alcaline de la morphine, et avoir ainsi ouvert une voie qui produit de grandes découvertes médicales.”
[257] There are exceptional cases in which it is asserted that water does not take up the whole amount of morphine.
[258] In large crystals by means of oil of turpentine.
By decomposition with sulphuric acid, narcotine yields Cotarnine, an undoubted base, together with Opianic Acid, and certain derivatives of the latter.
The discovery of another base, Codeine, was made in 1832 by Robiquet. It dissolves in 17 parts of boiling water, forming a highly alkaline solution which perfectly saturates acids, and exhibits in polarized light a levogyre power. Codeine is also readily soluble at ordinary temperatures in 7 parts amylic alcohol, and in 11 of benzol.
The codeine of commerce is in very large crystals containing 2 atoms = 5·66 per cent. of water. By crystallization from ether the alkaloid may be obtained in small anhydrous crystals.
Since 1832 other alkaloids have been found in opium, as may be seen in the following table, which includes all the 17 now known.[259]
A very large number of derivatives of several among them have been prepared, of which we point out a few in smaller type. The molecular constitution of these opium alkaloids being not yet thoroughly settled, we add only their empirical formulæ, which however exhibit unmistakeable connections.
Papaverosine discovered by Deschamps in poppy heads (p. 42) can hardly be absent from opium. In some points it appears to resemble cryptopine.
Among the peculiar non-basic constituents of opium, the first to call for notice is Meconic Acid, C₇H₄O₇, discovered, as already observed, by Sertürner in 1805. It is distinguished by the red colour which it produces with ferric salts, the same as that of ferric sulphocyanate; but the latter only dissolves in ether. Meconic acid is soluble in 4 parts of boiling water, but immediately gives off CO₂, and the remaining solution instead of depositing micaceous crystalline scales of meconic acid, yields on cooling (but best after boiling with hydrochloric acid) hard granular crystals of Comenic Acid, C₆H₄O₅.
Lactic Acid was discovered by T. and H. Smith in the opium-liquors produced in the manufacture of morphine. These chemists regarded it as a peculiar body, and under the name of Thebolactic Acid, exhibited it together with its copper and morphine salts at the London International Exhibition of 1862. Its identity with ordinary lactic acid was ascertained by Stenhouse (whose experiments have not been published) and also by J. Y. Buchanan.[260] T. and H. Smith consider it to be a regular constituent of Turkey opium; they obtained it as a calcium salt to the amount of about 2 per cent., and have prepared it in this form and in a pure state to the extent of over 100 lb. In our opinion it is not an original constituent of poppy-juice.
[259] In 1851 Hinterberger described as a peculiar alkaloid, Opianine; Dr. Hesse has examined Hinterberger’s specimen of this body, and found (1875) it to consist of impure narcotine.
[260] Berichte d. Deutsch. Chem. Gesellsch. zu Berlin, iii. (1870) 182.
NATURAL ALKALOIDS OF OPIUM
and a few of their Artificial Derivatives.
---------------+---------------------------------+----+----+----+--- DISCOVERED BY | | =C=| =H=| =N=| =O= | | | | | Wöhler, 1844 | Cotarnine | 12 | 13 | 1 | 3 |Formed by oxidizing narcotine; | | | | | soluble in water. | | | | Hesse, 1871 | =1. HYDROCOTARNINE= | 12 | 15 | 1 | 3 |Crystallizable, alkaline, | | | | | volatile at 100°. | | | | Matthiessen | APOMORPHINE | 17 | 17 | 1 | 2 and Wright, |From morphine, by hydrochloric | | | | 1869 | acid. Colourless, amorphous, | | | | | turning green by exposure to | | | | | air; emetic. | | | | | | | | | Wright, 1871 | DESOXYMORPHINE | 17 | 19 | 1 | 2 | | | | | Sertürner, | =2. MORPHINE= | 17 | 19 | 1 | 3 1816 |Crystallizable, alkaline, | | | | | levogyre. | | | | Pelletier and | =3. PSEUDOMORPHINE= | 17 | 19 | 1 | 4 Thibouméry, |Crystallizes with H₂O; does not | | | | 1835 | unite even with acetic acid. | | | | | | | | | Matthiessen | APOCODEINE | 18 | 19 | 1 | 2 and Burnside, |From codeine by chloride of zinc;| | | | 1871 | amorphous, emetic. | | | | | | | | | Wright, 1871 | DESOXYCODEINE | 18 | 21 | 1 | 2 | | | | | Robiquet, 1832 | =4. CODEINE= | 18 | 21 | 1 | 3 |Crystallizable, alkaline, soluble| | | | | in water. | | | | | | | | | Matthiessen | NORNARCOTINE | 19 | 17 | 1 | 7 and Foster, | | | | | 1868 | | | | | | | | | | Thibouméry, | =5. THEBAINE= | 19 | 21 | 1 | 3 1835 |Crystallizable, alkaline, | | | | | isomeric with buxine. | | | | | | | | | Hesse, 1870 | THEBENINE | 19 | 21 | 1 | 3 | | | | | Hesse, 1870 | THEBAICINE | 19 | 21 | 1 | 3 |From thebaine or thebenine by | | | | | hydrochloric acid. | | | | | | | | | Hesse 1871 | =6. PROTOPINE= | 20 | 19 | 1 | 5 |Crystallizable, alkaline. | | | | | | | | | Matthiessen | METHYLNORNARCOTINE | 20 | 19 | 1 | 7 and Foster, | | | | | 1868 | | | | | | | | | | Hesse, 1871 | DEUTEROPINE | 20 | 21 | 1 | 5 |Not yet isolated. | | | | | | | | | Hesse, 1870 | =7. LAUDANINE= | 20 | 25 | 1 | 4 |An alkaloid which, as well as its| | | | | salts, forms large crystals; | | | | | turns orange by hydrochloric | | | | | acid. | | | | | | | | | Hesse, 1878 | =8. CODAMINE= | 20 | 25 | 1 | 4 |Crystallizable, alkaline; can be | | | | | sublimed; becomes green by | | | | | nitric acid. | | | | | | | | | Merck, 1848 | =9. PAPAVERINE= | 21 | 21 | 1 | 4 |Crystallizable, also its | | | | | hydrochlorate; sulphate in | | | | | sulphuric acid precipitated by | | | | | water. | | | | | | | | | Hesse, 1865 | =10. RHŒADINE= | 21 | 21 | 1 | 6 |Crystallizable, not distinctly | | | | | alkaline; can be sublimed; | | | | | occurs also in Papaver | | | | | Rhœas. | | | | | | | | | Hesse, 1865 | RHŒAGENINE | 21 | 21 | 1 | 6 |From rhœadine; Crystallizable, | | | | | alkaline. | | | | | | | | | Armstrong, 1871| DIMETHYLNORNARCOTINE | 21 | 21 | 1 | 7 | | | | | Hesse, 1870 | =11. MECONIDINE= | 21 | 23 | 1 | 4 |Amorphous, alkaline, melts at | | | | | 58°, not stable, the salts also | | | | | easily altered. | | | | | | | | | T. & H. Smith, | =12. CRYPTOPINE= | 21 | 23 | 1 | 5 1864 |Crystallizable, alkaline; salts | | | | | tend to gelatinize; | | | | | hydrochlorate crystallizes | | | | | in tufts. | | | | | | | | | Hesse, 1871 | =13. LAUDANOSINE= | 21 | 27 | 1 | 4 |Crystallizable, alkaline. | | | | | | | | | Derosne, 1803 | =14. NARCOTINE= | 22 | 23 | 1 | 7 |Crystallizable, not alkaline; | | | | | salts not stable. | | | | | | | | | Hesse, 1870 | =15. LANTHOPINE= | 23 | 25 | 1 | 4 |Microscopic crystals not | | | | | alkaline, sparingly soluble in | | | | | hot or cold spirit of wine, | | | | | ether or benzol. | | | | | | | | | Pelletier, 1832| =16. NARCEINE= | 23 | 29 | 1 | 9 |Crystallizable (as a hydrate), | | | | | readily soluble in boiling water| | | | | or in alkalis, levogyre. | | | | | | | | | T. & H. Smith, | =17. GNOSCOPINE= | 34 | 36 | 2 | 11 1868 |Crystallizable, melts at 233°, | | | | | soluble in chloroform and | | | | | bisulphide of carbon, slightly | | | | | so in benzol, not in ether. The | | | | | salts have an acid reaction. | | | | ---------------+---------------------------------+----+----+----+
In the year 1826, Dublanc[261] observed in opium a peculiar substance having neither basic nor acid properties which was afterwards (1832) prepared in a state of purity by Couerbe. It has been called Opianyl or (by Couerbe) Meconine. It has the composition C₁₀H₁₀O₄ = C₆H₂·CH₂·O·CO(OCH₃)₂. Meconin forms prisms which fuse under water at 77° C. or per se at 110°, and distil at 155°; it dissolves in about 20 parts of boiling water, from which it may be readily crystallized. Meconin may be formed by heating narcotine with nitric acid.
An analogous substance Meconoiosin C₈H₁₀O₂ = C₆H₂·(OH)₂·(CH₃)₂, has been discovered in 1878 by T. and H. Smith. Meconoiosin is readily soluble in 27 parts of cold water, and melts at 88° C. When heated with slightly diluted sulphuric acid, and when the evaporation has reached a certain point, meconoiosin produces a deep red; with meconin the coloration is a beautiful green.
=Proportion of peculiar constituents=—The substances described in the foregoing section exist in opium in very variable proportion; and as it is on their presence, but especially that of morphine, that the value of the drug depends, the importance of exact estimation is evident.
Opium whether required for analysis or for pharmaceutical preparations has to be taken exclusively in the dry state. The amount of water it contains is so uncertain that the drug must be reduced to a fixed standard by complete desiccation at 100° C., before any given weight is taken.
=Morphine=—Guibourt[262] who analysed a large number of samples of opium, and whose skill and care in such research are not disputed, obtained from a sample of French opium produced near Amiens, 22·88 per cent. of morphine crystallized from spirit of wine. This percentage has not to our knowledge been ever exceeded. From another specimen produced in the same district he got 21·23 per cent., from a third 20·67. The lowest percentage from a French opium was 14·96,—in each case reckoned on material previously dried.
Chevallier extracted from opium grown by Aubergier at Clermont in the centre of France, 17·50 per cent. of morphine. Decharmes from a French opium obtained 17·6 per cent., and Biltz from a German opium 20 per cent. Opium produced in Württemberg sent to the Vienna Exhibition of 1873 afforded Hesse 12 to 15 per cent. of morphine; and opium from Silesia 9 to 10 per cent.[263]
A pure American opium collected in the State of Vermont yielded Proctor 15·75 per cent. of morphine and 2 percent of narcotine.[264]
The opium of Asia Minor furnishes very nearly the same proportions of morphine as that of Europe. The maximum recorded by Guibourt is 21·46 per cent. obtained from a Smyrna opium sold in Paris. The mean yield of 8 samples of opium sent by Della Sudda of Constantinople to the Paris Exhibition of 1855 was 14·78 per cent. The mean percentage of morphine afforded by 12 other samples of Turkey opium obtained from various sources was 14·66.
[261] Annales de Chimie et de Physique, xlix. (1832) 5-20.—The paper was read before the Acad. de Méd., 13th May, 1826.
[262] Mémoire sur le dosage de l’Opium et sur la quantité de morphine que l’opium doit contenir, Paris, 1862.
[263] Schroff, Ausstellungsbericht, Arzneiwaaren, p. 31.
[264] Am. Journ. of Pharm. xviii. (1870) 124.
Chevallier[265] states that Smyrna opium, of which several cases were received by Merck of Darmstadt in 1845, afforded 12 to 13 per cent. of pure morphine reckoned upon the drug in its fresh and moist state.
Fayk Bey[266] analysed 92 samples of opium of Asia Minor, and found that half the number yielded more than 10 per cent. of morphine. The richest afforded 17·2 per cent.
From the foregoing statements we are warranted in assuming that good Smyrna opium deprived of water ought to afford 12 to 15 per cent. of morphine, and that if the percentage is less than 10, adulteration may be suspected.
Egyptian opium has usually been found very much weaker in morphine than that of Asia Minor. A sample sent to the Paris Exhibition of 1865 and presented to one of us by Figari Bey of Cairo, afforded us 5·8 per cent. of morphine and 8·7 of narcotine.
Persian opium appears extremely variable, probably in consequence of the practice of combining it with sugar and other substances. It is however sometimes very good. Séput[267] obtained from four samples the respective percentages of 13·47, 11·52, 10·12, 10·08 of morphine, the opium being free from water. Mr. Howard as already stated (p. 49) extracted from Persian opium, not previously dried, from 8 to 10·75 per cent. of morphine.
East Indian opium is remarkable for its low percentage of morphine, a circumstance which we think is attributable in part to climate and in part to a method of collection radically defective. It is scarcely conceivable that the long period during which the juice remains in a wet state,—always three to four weeks,—does not exercise a destructive action on its constituents.
According to Eatwell[268] the percentage of morphine in the samples of Benares opium officially submitted for analysis gave the following averages.—
1845-46 1846-47 1847-48 1848-49 2·48 2·38 2·20 3·21
The same observer has recorded the results of the examination of freshly collected poppy-juice, which in three instances afforded respectively 1·4, 3·06, and 2·89 per cent. of morphine, reckoned on the material deprived of water; but the conditions under which the experiments were made appear open to great objection.[269]
Such very low results are not always obtained from East Indian opium. In a sample from Khandesh furnished by the Indian Museum, we found 6·07 of morphine. Solly from the same kind obtained about 7 per cent.
Patna Garden Opium which is the sort prepared exclusively for medicinal use, afforded us 8·6 per cent. of purified morphine and 4 per cent. of narcotine.[270] Guibourt obtained from such an opium 7·72 per cent. Christison from a sample sent to Duncan of Edinburgh in 1830,[271] 9·50 per cent. of hydrochlorate of morphine.
[265] Notice historique sur l’opium indigène, Paris, 1852.
[266] Monographie des Opiums de l’Empire Ottoman envoyés à l’Exposition de Paris, 1867.
[267] Journ. de Pharm. xxxix. (1861) 163.
[268] Pharm. Journ. xi. (1852) 361.
[269] In one case the juice was allowed to stand in a basin from 23rd Feb. to 7th May, being “occasionally stirred”!
[270] This drug made in 1838 came from the Apothecary-General, Calcutta, and was presented by Christison to the Kew Museum. It is in rectangular tablets 2½ inches square and ¾ of an inch thick, cased in wax.
[271] The actual specimen is in the Kew Museum.
Samples from the Indian Museum placed at our disposal by Dr. J. Forbes Watson gave[272] us the following percentages of morphine:—Medical (Indian) Opium, 1852-53, portion of a square brick, 4·3; Garden Behar Opium, 4·6; Abkāri Provision Opium, Patna, No. 5380, 3·5; Sind Opium, No. 28, 3·8; Opium, Hyderabad, Sind, 3·2 (and 5·4 of narcotine); Malwa Opium, 6·1.
With regard to the percentage of morphine in Chinese Opium, the following data have been obligingly furnished to us by Mr. T. W. Sheppard, F.C.S., Opium Examiner to the Benares Opium Agency, of analyses made by himself from samples of the drug procured in China by Sir R. Alcock:—Szechuen opium, 2·2; Kweichow, 2·5; Yunnan, 4·1; Kansu, 5·1 per cent. Mr. S. informs us that Dr. Eatwell obtained in 1852 from Szechuen opium 3·3, and from Kweichow opium 6·1[273] per cent.—the opium in all instances being reckoned as dry. The samples examined by Mr. S. contained 86 to 95 per cent. of dry opium, and yielded (undried) 36 to 53 per cent. of extract soluble in cold water. The proportion of morphine in the sample of Chinese opium analysed by Dr. Jamieson (p. 55) was nearly 7·2 per cent. calculated on the dry drug.
Pseudomorphine—occurs only in very small quantities. Hesse found it in some sorts of opium to the extent of 0·02 per cent.—in others still less.
Codeine—has been found in Smyrna, French and Indian opium, but only to the extent of ⅕ to ⅖ per cent. T. and H. Smith give the proportion in Turkey opium as 0·3 per cent.[274]
=Thebaine=—which has likewise been obtained from French opium, amounts in Turkey opium according to Merck to about 1 per cent. In the latter sort T. and H. Smith found only about 8·15 per cent., but of
Papaverine—in the same drug, 1 per cent.
Narcotine—exists in opium in widely different proportions and often in considerable abundance. Thus Schindler obtained in 1834 from a Smyrna opium yielding 10·30 per cent. of morphine, 1·30 per cent. of narcotine. Biltz (1831) analysed an oriental opium which afforded 9·25 per cent. of morphine and 7·50 of narcotine. Reveil (1860) obtained from Persian opium not rich in morphine, from half as much to twice as much narcotine as morphine. The utmost of narcotine was 9·90 per cent. We have found in German opium of undubitable purity[275] 10·9 per cent. of narcotine.
East Indian opium was found by Eatwell (1850) always to afford more narcotine than morphine,—frequently twice as much. The sample from Khandesh referred to on the opposite page, afforded us 7·7 per cent. of pure narcotine.
French opium collected from the Pavot œillette sometimes affords neither narcotine, thebaine, nor narceine.[276]
[272] Pharm. Journ. v. (1875) 845.
[273] This sample, the richest of all in morphine, is noted as of “2nd quality.”
[274] Pharm. Journ. vii. (1866) 183.
[275] Collected in 1829 by Biltz and obligingly placed in 1867 at my disposal by his son.—F. A. F.
[276] The statement of Biltz (1831) that an opium collected by himself from poppies grown in 1829 at Erfurt afforded 33 per cent. of narcotine is contrary to the experience of all other chemists. The same must be said of Mulder’s assertion respecting an opium giving 6 to 13 per cent. of narceine.
Narceine—Of this substance Couerbe found in opium 0·1 per cent.; T. and H. Smith 0·02 and Schindler 0·71.
Cryptopine—exists in opium in very small proportion. T. and H. Smith state that since the alkaloid first came under their notice, they have collected of it altogether about 5 ounces in the form of hydrochlorate, and this small quantity in operating on many thousands of pounds of opium. But they by no means assert that the whole of the cryptopine was obtained.
Rhœadine—is also found only in exceedingly minute quantity.
Meconic Acid—If the average amount of morphine in opium be estimated at 15 per cent., and the alkaloid be supposed to exist as a tribasic meconate, it would require for saturation 3·4 per cent. of meconic acid. Wittstein obtained rather more than 3 per cent., T. and H. Smith 4 per cent., and Decharmes 4·33. Opium produced in Vermont yielded, according to Proctor (1870) 5·25 per cent. of meconic acid. The quantity of acid required to unite with the other bases assuming them to exist as salts can be but extremely small.
=Estimation of Morphine in Opium=—The practical valuation of opium turns in the first instance upon the estimation of the water present in the drug, and in the second upon the proportion which the latter contains of morphine.[277]
The first question is determined by exposing a known quantity of the drug divided into small slices or fragments to the heat of a water-bath until it cease to lose weight.
For the estimation of the morphine many processes have been devised, but none is perfectly satisfactory.[278] That which we recommend is thus performed:—Take of opium previously dried at 100° C., as above stated, and powdered, 10 grammes; shake it with 100 grammes alcohol 0·950 sp. gr., and filter after a day or two. The weight of the liquid should be made equal to 100 grammes. Add to it 50 grammes of ether and 2 grammes of ammonia water 0·960 sp. gr.; collect the crystals of opium which separate slowly, after a day or two, dry them at 100° C., and weigh them.—On applying this method to Indian opium, we were but little satisfied with it.
=Commerce=—By official statistics it appears that the quantity of opium imported into the United Kingdom in 1872 was 356,211 lb., valued at £361,503. The imports from Asiatic and European Turkey are stated in the same tables thus:—
1868 1870 1872 1874 317,133 lb. 276,691 lb. 325,572 lb. 514,000 lb.
It is thus evident that the drug used in Great Britain is chiefly Turkish. The import of opium from Persia has been very irregular. In 1871, 21,894 lb. are reported as received from that country; in 1872, none.
[277] In selecting a sample for analysis, care should be taken that it fairly represents the bulk of the drug. We prefer to take a little piece from each of several lumps, mix them in a mortar, and weigh from the mixed sample the required quantity.
[278] See also Proctor, Pharm. Journ. vii. (1876) 244, and Yearbook of Pharm. 1877. 528.
Except that a little Malwa opium has occasionally been imported, it may be asserted the opium of India is entirely unknown in the English market, and that none of it is to be found even in London in the warehouse of any druggist.
As to other countries, we may point out that in 1876 the import of opium (prepared) into the colony of Victoria was valued at £104,557.
=Uses=—Opium possesses sedative powers which are universally known. In the words of Pereira, it is the most important and valuable medicine of the whole Materia Medica; and we may add, the source by its judicious employment of more happiness and by its abuse of more misery[279] than any other drug employed by mankind.
=Adulteration=—The manifold falsifications of opium have been already noticed, and the method by which its more important alkaloid may be estimated has been pointed out. Moreover as already stated, neither tannic acid nor starch ever occur in genuine opium; and the proportion of ash left upon the incineration of a good opium does not exceed 4 to 8 per cent. of the dried drug. Another criterion is afforded by the amount soluble in cold water which ought to exceed 55 per cent. reckoned on dry opium. Finally, if we are correct, the gum contained in pure opium is distinct from gum arabic, being precipitable by neutral acetate of lead. If we exhaust with water opium falsified with gum arabic, the mucilage peculiar to opium will be precipitated by neutral acetate of lead, the liquid separated from the precipitate will still contain the gum arabic which may be thrown down by alcohol. If gum is present to some extent, an abundant precipitate is produced.
CRUCIFERÆ
SEMEN SINAPIS NIGRÆ.
Black, Brown or Red Mustard; F. Moutarde noire ou grise; G. Schwarzer Senf.
=Botanical Origin=—Brassica nigra Koch (Sinapis nigra L.). Black Mustard is found wild over the whole of Europe excepting the extreme north. It also occurs in Northern Africa, Asia Minor, Mesopotamia, the Caucasian region, Western India, as well as in Southern Siberia and China. By cultivation, which is conducted on a large scale in many countries (as Alsace, Bohemia, Holland, England and Italy), it has doubtless been diffused through regions where it did not anciently exist. It has now become naturalized both in North and South America.
=History=—Mustard was well known to the ancients. Theophrastus mentions it as Νάπμ,—Dioscorides as Νάπμ or Σίνηπι. Pliny notices three kinds which have been referred by Fée[280] to Brassica nigra Koch, B. alba Hook. f. et Th., and to a South European species, Diplotaxis erucoides DC. (Sinapis erucoides L.). The use of mustard seems up to this period to have been more medicinal than dietetic. But from an edict of Diocletian, A.D. 301[281] in which it is mentioned along with alimentary substances, we must suppose it was then regarded as a condiment at least in the eastern parts of the Roman Empire.
[279] See Tingling, J. F. B., The poppy-plague and England’s crime, London, 1876 (192 p.); Turner, F. S. (Secretary of the Anglo-Oriental Society for the Suppression of the Opium Trade), British Opium Policy and its results to India and China. London, 1876 (308 pages); Sir Edw. Fry, England, China, and Opium, 1878 (61 p.).
[280] Botanique et Matière Méd. de Pline, ii. (1833) 446.
[281] Mommsen in Berichte der sächs. Gesellsch. der Wissenschaften zu Leipzig, 1851. 1-80.
In Europe during the middle ages mustard was a valued accompaniment to food, especially to the salted meat which constituted a large portion of the diet of our ancestors during the winter.[282] In the Welsh “Meddygon Myddvai,” of the 13th century, a paragraph is devoted to the “Virtues of Mustard.” In household accounts of the 13th and 14th centuries, mustard under the name of Senapium is of constant occurrence.
Mustard was then cultivated in England, but not as it would seem very extensively. The price of the seed between A.D. 1285 and 1395 varied from 1_s._ 3_d._ to 6_s._ 8_d._ per quarter, but in 1347 and 1376 it was as high as 15_s._ and 16_s._[283] In the accounts of the abbey of St. Germain-des-Prés in Paris, commencing A.D. 800, mustard is specifically mentioned as a regular part of the revenue of the convent lands.[284]
The essential oil of mustard was, apparently, noticed about the year 1660 by Nicolas Le Febvre (see in the article Rad. Inulae), more distinctly in 1732 by Boerhaave. Its acridity and high specific gravity were pointed out by Murray.[285] Thibierge in 1819 observed that sulphur was one of the constituents of the oil, and Guibourt[286] stated that it is not pre-existing in the seed.
=Production=—Mustard is grown in England only on the richest alluvial soils, and chiefly in the counties of Lincolnshire and Yorkshire. Very good seed is produced in Holland.
=Description=—The pod of Brassica nigra is smooth, erect, and closely pressed against the axis of the long slender raceme. It has a strong nerve on each of its two valves and contains in each cell from 4 to 6 spherical or slightly oval seeds. The seeds are about ¹/₂₅ of an inch in diameter and ¹/₅₀ of a grain in weight; they are of a dark reddish-brown. The surface is reticulated with minute pits, and often more or less covered with a whitish pellicle which gives to some seeds a grey colour.[287] The testa which is thin, brittle and translucent encloses an exalbuminous embryo having two short cotyledons folded together longitudinally and forming a sort of trough in which the radicle lies bent up. The embryo thus coiled into a ball completely fills the testa; the outer cotyledon is thicker than the inner, which viewed in transverse section seems to hold the radicle as a pair of forceps. The seeds when pulverized have a greenish yellow hue. Masticated they have for an instant a bitterish taste which however quickly becomes pungent. When triturated with water they afford a yellowish emulsion emitting a pungent acrid vapour which affects the eyes, and has a strong acid reaction. The seeds powdered dry have no such pungency. When the seeds are triturated with solution of potash, the pungent odour is not evolved; nor when they are boiled in water. Neither is the acridity developed on triturating them with alcohol, dilute mineral acids, or solution of tannin, or even with water when they have been kept in powder for a long time.
[282] Enclosed pasture land in England was rare, and there was but scanty provision for preserving stock through the winter, root crops being unknown. Hence in November there was a general slaughtering of sheep and oxen, the flesh of which was salted for winter use.—See also Pharm. Journ. viii. (1876, April 27) 862.
[283] Rogers, Hist. of Agriculture and Prices in England, i. (1866) 223.
[284] Guérard, Polyptique de l’Abbé Irminon, Paris, i. (1844) 715.
[285] Apparatus medicaminum, ii. (1794) 399.
[286] Journ. de Pharm. xvii. (1831) 360.
[287] The grey colour of the seed, which is attributed to rain during the ripening, is very detrimental to its value. The great aim of the grower is to produce seed of a bright reddish-brown, with no grey seed intermixed.
=Microscopic Structure=—The whitish pellicle already mentioned, which covers the seed, is made up of hexagonal tabular cells. The epidermis consists of one row of densely packed brown cells, radially elongated and having strong lateral and inner walls. Their outer walls on the other hand are thin and not coloured; they are not clearly obvious when seen under oil, but swell up very considerably in presence of water, emitting mucilage.[288] Seeds immersed in water become therefore covered with a glossy envelope, levelling down the superficial inequalities, so that the wet seed appears smooth. The tissue of the cotyledons exhibits large drops of fatty oil and granules of albumin.
=Chemical Composition=—By distilling brown mustard with water, the seed having been previously macerated, the pungent principle, Essential Oil of Mustard, is obtained.
The oil, which has the composition SCN(C₃H⁵), (allyl isosulphocyanate), boils at 148° C.; it has a sp. gr. of 1·017, no rotatory power, and is soluble without coloration or turbidity in three times its weight or more of cold strong sulphuric acid. To this oil is due the pungent smell and taste of mustard and its inflammatory action on the skin. As already pointed out, mustard oil is not present in the dry seeds, but is produced only after they have been comminuted and mixed with water, the temperature of which should not exceed 50° C.
The remarkable reaction which gives rise to the formation of mustard oil was explained by Will and Körner in 1863. They obtained from mustard a crystallizable substance, then termed Myronate of potassium, now called Sinigrin. It is to be regarded, according to the admirable investigations of these chemists, as a compound of
Isosulphocyanate of allyl or mustard oil C₄ H₆ NS Bisulphate of potassium H KS O₄ Sugar (dextro-glucose) C₆ H₁₂ O₆ ----------------- so that the formula C₁₀ H₁₈ KNS₂ O₁₀
is that of sinigrin. It does in fact split into the above-mentioned three substances when dissolved in water and brought into contact with Myrosin.
[288] Most minutely described and figured by F. von Höhnel, in Haberlandt’s Untersuchungen auf dem Gebiete des Pflanzenbaues, i. (Vienna, 1875) 171-202.
This albuminous body discovered by Bussy in 1839, but the composition of which has not been made out, likewise undergoes a certain decomposition under these circumstances. Sinigrin may likewise be decomposed by alkalis and, according to Ludwig and Lange, by silver nitrate. These chemists obtained sinigrin from the seeds in the proportion of 0·5 per cent.; Will and Körner got 0·5 to 0·6 per cent. The extraction of the substance is therefore attended with great loss, as the minimum yield of volatile oil, 0·42 per cent. indicates 2·36 of potassium myronate.
The aqueous solution of myrosin coagulates at 60° C. and then becomes inactive: hence mustard seed which has been heated to 100° C. or has been roasted yields no volatile oil, nor does it yield any if powdered and introduced at once into boiling water. The proportion of myrosin in mustard has not been exactly determined. The total amount of nitrogen in the seed is 2·9 per cent. (Hoffmann) which would correspond to 18 per cent. of myrosin, supposing the proportion of nitrogen in that substance to be the same as in albumin, and the total quantity of nitrogen to belong to it. Sometimes black mustard contains so little of it, that an emulsion of white mustard requires to be added in order to develop all the volatile oil it is capable of yielding.
An emulsion of mustard or a solution of pure sinigrin brought into contact with myrosin, frequently deposits sulphur by decomposition of the allyl sulphocyanide, hence crude oil of mustard sometimes contains a considerable proportion (even half) of Allyl cyanide, C₄H₅N, distinguished by its lower sp. gr. (0·839) and lower boiling point (118° C.).
The seeds, roots, or herbaceous part of many other plants of the order Cruciferæ yield a volatile oil composed in part of mustard oil and in part of allyl sulphide
C₂H₅} C₆H₁₀S = } S, C₃H₅}
which latter is likewise obtainable from the bulbs of garlic. Many Cruciferæ afford from their roots or seeds chiefly or solely oil of mustard, and from their leaves oil of garlic. As to other plants, the roots of Reseda lutea L. and R. luteola L. have been shown by Volhard (1871) to afford oil of mustard.[289] The strong smell given off by the crushed seeds or roots of several Mimoseæ, as for instance, Albizzia lophantha Benth. (Acacia Willd.) is perhaps due to some allied compound.
The artificial preparation of mustard oil was discovered in 1855 by Zinin, and at the same time also by Berthelot and De Luca. It may be obtained in decomposing bromide of allyl by means of sulphocyanate of ammonium:—
C₃H₅Br · SCN(NH₄) = NH₄Br · C₃H₅SCN.
The liquid C₃H₅SCN, boiling at 161°, is sulphocyanate of allyl; if it is gently warmed with a little alcoholic potash, and then acidulated, the red coloration of ferric sulphocyanate is produced on addition of perchloride of iron, but by submitting the sulphocyanate of allyl to distillation it is at once transformed in the isosulphocyanate, i.e. in mustard oil; the latter is not coloured by ferric salts, but it would appear that in the cold emulsion of mustard, even at 0°, a little sulphocyanate makes also its appearance.
Mustard submitted to pressure affords about 23 per cent.[290] of a mild-tasting, inodorous, non-drying oil, solidifying when cooled to -17·5° C., and consisting of the glycerin compounds of stearic, oleic and Erucic or Brassic Acid. The last named acid, C₂₂H₄₂O₂, occurs also in the fixed oil of white mustard and of rape, and is homologous with oleic acid. Darby (1849) has pointed out the existence of another body, Sinapoleic Acid, C₂₀H₃⁸O₂, which occurs in the fixed oil of both black and white mustard. Goldschmiedt, in 1874, ascertained the presence also of Behenic Acid, C₂₂H₄₄O₂ in black mustard. Sinigrin being not altered by the extraction of the fatty oil, either by pressure or by means of bisulphide of carbon, the powdered seed, deprived of fatty oil, still yields the whole amount of the irritating “essential” oil. This important fact has been ingeniously used by Rigollot[291] for the preparation of his mustard paper.
[289] See also Radix Armoraciæ, p. 68.
[290] I have obtained as much as 33·8 per cent. by means of boiling ether.—F. A. F.
[291] Journ. de Pharm. vi. (1867) 269.
Mustard seed when ripe is devoid of starch; the mucilage which its epidermis affords amounts to 19 per cent. of the seed (Hoffmann). The ash constituents amounting to 4 per cent. consist chiefly of the phosphates of calcium, magnesium, and potassium.
=Uses=—Black mustard is employed in the form of poultice as a powerful external stimulant; but it is rarely used in its pure state, as the Flour of Mustard prepared for the table, which contains in addition white mustard, answers perfectly well and is at hand in every house.[292]
The essential oil of mustard dissolved in spirit of wine is occasionally prescribed as a liniment.
=Substitute=—Brassica juncea Hook. f. et Th. (Sinapis juncea L.) is extensively cultivated throughout India (where B. nigra is rarely grown), Central Africa, and generally in warm countries where it replaces B. nigra and is applied to the same uses. Its seeds constitute a portion of the mustard of Europe, as we may infer from the fact that British India exported in the year 1871-72, of “Mustard seed” 1418 tons, of which 790 tons were shipped to the United Kingdom, and 516 tons to France.[293] B. juncea is largely grown in the south of Russia and in the steppes north-east of the Caspian where it appears to flourish particularly well in the saline soil. At Sarepta in the Government of Saratov, an establishment has existed since the beginning of the present century where this sort of mustard is prepared for use to the extent of 800 tons of seed annually. The seeds make a fine yellow powder employed both for culinary and medicinal purposes. By pressure they yield more than 20 per cent. of fixed oil which is used in Russia like the best olive oil. The seeds closely resemble those of B. nigra and afford when distilled the same essential oil; it is largely made at Kiew.
SEMEN SINAPIS ALBÆ.
White Mustard; F. Moutarde blanche ou Anglaise; G. Weisser Senf.
=Botanical Origin=—Brassica alba Hook. f. et Th. (Sinapis alba L.) This plant appears to belong to the more southern countries of Europe and Western Asia. According to Chinese authors[294] it was introduced into China from the latter region. Its cultivation in England is of recent introduction, but is rapidly extending.[295] The plant is not uncommon as a weed on cultivated land.
[292] The best Flour of Mustard such as is made by the large manufacturers, contains nothing but brown and white mustard seeds. But the lower and cheaper qualities made by the same firms contain flour, turmeric, and capsicum. Unmixed flour of Black Mustard is however kept for those who care to purchase it.
[293] Annual Statement of the Trade and Navigation of British India, Calcutta, 1872. 62.
[294] Bretschneider, Study of Chinese Botan. Works, 1870. 17.
[295] Morton’s Cycloped. of Agriculture, ii. (1855) 440.
=History=—White mustard was used in former times indiscriminately with the brown. In the materia medica of the London Pharmacopœia of 1720 the two sorts are separately prescribed. The important chemical distinction between them was first made known in 1831 by Boutron-Charlard and Robiquet.[296]
=Production=—White mustard is grown as an agricultural crop in Essex and Cambridgeshire.
=Description=—Brassica alba differs from B. nigra in having the pods bristly and spreading. They are about an inch long, half the length being occupied by a flat veiny beak. Each pod contains 4 to 6 yellowish seeds about ¹/₁₂ of an inch in diameter and ⅒ of a grain in weight. The brittle, nearly transparent and colourless testa encloses an embryo of a bright pure yellow and of the same structure as that of black mustard. The surface of the testa is likewise pitted in a reticulate manner, but so finely that it appears smooth except under a high magnifying power.
When triturated with water the seeds form a yellowish emulsion of very pungent taste, but it is inodorous and does not under any circumstances yield a volatile oil. The powdered seeds made into a paste with cold water act as a highly stimulating cataplasm. The entire seeds yield to cold water an abundance of mucilage.
=Microscopic Structure=—The epidermal cells of white mustard afford a good illustration of a mucilage-yielding layer such as is met with, under many variations, in the seeds of numerous plants. The cuticle consists of large vaulted cells, exhibiting very regular hexagonal outlines when cut across.[297] The inner layer of the epidermis is made up of thin-walled cells, which when moistened swell and give off the mucilage. In the dry state or seen under oil, the outlines of the single cells of this layer are not distinguishable. The tissue of the cotyledons is loaded with drops of fatty oil and with granular albuminoid matter; starch which is present in the seed while young, is altogether absent when the latter reaches maturity.
=Chemical Composition=—White mustard deprived of fatty oil yields to boiling alcohol colourless crystals of Sinalbin, an indifferent substance, readily soluble in cold water, but sparingly in cold alcohol. From the able investigations of Will (1870) it follows, that it is to be regarded as composed of three bodies, namely:
Sulphocyanate of Acrinyl C⁸ H₇ N S O Sulphate of Sinapine C₁₆ H₂₅ N S O₉ Sugar C₆ H₁₂ O₆ ----------------- so that the formula C₃₀ H₄₄ N₂ S₂ O₁₆
[296] Journ. de Pharm. xvii. (1831) 279.
[297] An interesting object for the polarizing microscope.
represents according to Will the composition of sinalbin. It is actually resolved into these three substances when placed at ordinary temperatures, in contact with water and Myrosin, the latter of which is a constituent of white mustard as well as of brown (p. 66). The liquid becomes turbid, the first of the above-named substances separates (together with coagulated albumin) as an oily liquid, not soluble in water, but dissolving in alcohol or ether. This Sulphocyanate of Acrinyl is the rubefacient and vesicating principle of white mustard. It does not pre-exist, as shown by Will, in the seed, and cannot be obtained by distillation. By treating it with a salt of silver, Will obtained crystals of cyanide of acrinyl, C₈H₇NO: by warming it (or sinalbin itself, or an alcoholic extract of the seed) with caustic potash, sulphocyanide of potassium is produced. The presence of the latter may be indicated by adding a drop of perchloride of iron, when a blood-red coloration will be produced.[298]
Sulphate of Sinapine imparts to the emulsion of white mustard, in which it is formed, an acid reaction. Sinapine is itself an alkaloid, which has not yet been isolated, as it is very liable to change. Thus its solution on addition of a trace of alkali immediately assumes a bright yellow colour indicating decomposition, and a similar colour is produced in an aqueous extract of the seed.
The above statements show, that the chemical properties of sinalbin and its derivatives correspond closely with those of sinigrin (p. 66) and the substances which make their appearance in an emulsion of black mustard.
The other constituents of white mustard seed are nearly the same as those of black. The fat oil appears to yield in addition to the acids mentioned at p. 67, Benic or Behenic Acid, C₂₂H₄₄O₂. White mustard is said to be richer than black in myrosin, so that, as explained in the previous article, the pungency of the latter may be often increased by an addition of white mustard. By burning white mustard dried at 100° C., with soda-lime, we obtained from 4·20 to 4·30 per cent. of nitrogen, answering to about 28 per cent. of protein substances.[299] The fixed oil of the seed amounts to 22 per cent. The mucilage as yielded by the epidermis is precipitable by alcohol, neutral lead acetate, or ferric chloride, and is soluble in water after drying.
Erucin and Sinapic Acid, mentioned by Simon (1838)[300] as peculiar constituents of white mustard, are altogether doubtful, yet may deserve further investigation. The sinapic acid of Von Babo and Hirschbrunn[301] (1852) is a product of the decomposition of sinapine.
=Uses=—White Mustard seed reduced to powder and made into a paste with cold water act as a powerful stimulant when applied to the skin, notwithstanding that such paste is entirely wanting in essential oil. But for sinapisms they are actually used only in the form of the Flour of Mustard which is prepared for the table and which contains also Brown Mustard seed.
[298] The red compound thus formed with sulphocyanide is readily soluble in ether, yet in the case of white mustard we find it not to be so.
[299] Experiments performed by Mr. Weppen in my laboratory, 1869.—F. A. F.
[300] Gmelin, Chemistry, xiv. (1860) 521 and 529.
[301] Ibid. 521.
RADIX ARMORACIÆ
Horse-radish; F. Raifort (i.e. racine forte), Cran de Bretagne; G. Meerrettig.
=Botanical Origin=—Cochlearia Armoracia L., a common perennial with a stout tapering root, large coarse oblong leaves with long stalks, and erect flowering racemes 2 to 3 feet high. It is indigenous to the eastern parts of Europe, from the Caspian through Russia and Poland to Finland. In Britain and in other parts of Europe from Sicily to the polar circle, it occurs cultivated or semi-wild; in the opinion of Schübeler[302] it is not truly indigenous to Norway.
=History=—The vernacular name Armon is stated by Pliny[303] to be used in the Pontic regions to designate the Armoracia of the Romans, the Wild Radish (ῤαϕανὶς ἀγρία) of the Greeks, a plant which cannot be positively identified with that under notice.
Horse-radish is called in the Russian language Chren, in Lithuanian Krenai, in Illyrian Kren, a name which has passed into several German dialects, and as Cran or Cranson into French.
From these and similar facts, De Candolle[304] has drawn the conclusion that the propagation of the plant has travelled from Eastern to Western Europe.
Both the root and leaves of horse-radish were used as a medicine and also eaten with food in Germany and Denmark during the middle ages.[305] But the use of the former was not common in England until a much later period. The plant is mentioned in the Meddygon Myddfai and was known in England as Red-cole in the time of Turner, 1568, but is not quoted by him[306] as used in food, nor is it noticed by Boorde,[307] 1542, in his chapter on edible roots. Gerarde[308] at the end of the 16th century remarks that horse-radish—“is commonly used among the Germans for sauce to eat fish with, and such like meats, as we do mustard.” Half a century later the taste for horse-radish had begun to prevail in England. Coles[309] (1657) states that the root sliced thin and mixed with vinegar is eaten as a sauce with meat as among the Germans. That the use of horse-radish in France had the same origin is proved by its old French name Moutarde des Allemands.
The root to which certain medicinal properties had always been assigned, was included in the materia medica of the London Pharmacopœias of the last century under the name of Raphanus rusticanus.
=Description=—The root which in good ground often attains a length of 3 feet and nearly an inch in diameter, is enlarged in its upper part into a crown, usually dividing into a few short branches each surmounted by a tuft of leaves, and annulated by the scars of fallen foliage; below the crown it tapers slightly, and then for some distance is often almost cylindrical, throwing off here and there filiform and long slender cylindrical roots, and finally dividing into two or three branches. The root is of a light yellowish-brown; internally it is fleshy and perfectly white, and has a short non-fibrous fracture. Before it is broken it is inodorous, but when comminuted it immediately exhales its characteristic pungent smell. Its well-known pungent taste is not lost in the root carefully dried and not kept too long.
[302] Pflanzenwelt Norwegens (1873) 296.
[303] Lib. xix. c. 26 (Littré’s translation).
[304] Géographie Botanique, ii. (1855) 655.
[305] Meyer, Geschichte der Botanik, iii. (1856) 531; also Schübeler l. c.; Pfeiffer, Buch der Natur von Konrad von Megenberg, Stuttgart, 1861. 418.
[306] Herball, part 2. (1568) 111.
[307] Dyetary of Helth, Early English Text Society, 1870. 278.
[308] Herball, edited by Johnson, 1636, 240.
[309] Adam in Eden, or Nature’s Paradise, Lond. 1657. chap. 256.
A transverse section of the fresh root displays a large central column with a radiate and concentric arrangement of its tissues, which are separated by a small greyish circle from the bark, whose breadth is from ½ to 2 lines. In the root branches there is neither a well-defined liber nor a true pith. The short leaf-bearing branches include a large pith surrounded by a circle of woody bundles. The bark adheres strongly to the central portion, in which zones of annual growth are easily perceptible, at least in older specimens.
=Microscopic Structure=—The corky layer is made up of small tabular cells as usual in suberous coats. In the succeeding zone of the middle bark, thick-walled yellow cells are scattered through the parenchyme, chiefly at the boundary line of the corky layer. In the root the cellular envelope is not strikingly separated from the liber, whilst in its leafy branches this separation is well marked by wedge-shaped liber bundles, which are accompanied by a group of the yellow longitudinally-elongated stone-cells. The woody bundles contain a few short yellow vessels, accompanied by bundles of prosenchymatous, not properly woody cells. The centre, in the root, shows these woody bundles to be separated by the medullary parenchyma; in the branches the central column consists of an uniform pith without woody bundles, the latter forming a circle close to the cambium. The parenchyma of the whole root collected in spring is loaded with small starch granules.
=Chemical Composition=—Among the constituents of horse-radish root (the chemical history of which is however far from perfect) the volatile oil is the most interesting. The fresh root submitted to distillation with water in a glass retort, yields about ½ per mille of oil which is identical with that of Black Mustard as proved in 1843 by Hubatka. He combined it with ammonia and obtained crystals of thiosinammine, the composition of which agreed with the thiosinammine from mustard oil.
An alcoholic extract of the root is devoid of the odour of the oil, but this is quickly evolved on addition of an emulsion of White Mustard. The essential oil does not therefore pre-exist, but only sinigrin (myronate of potassium) and an albuminoid matter (myrosin) by whose mutual reaction in the presence of water it is formed (p. 66). This process does not go on in the growing root, perhaps because the two principles in question are not contained in the same cells, or else exist together in some condition that does not allow of their acting on each other,—a state of things analogous to that occurring in the leaves of Lauro-cerasus.
By exhausting the root with water either cold or hot, the sinigrin is decomposed and a considerable proportion of bisulphate is found in the concentrated decoction. Alcohol removes from the root some fatty matter and sugar (Winckler 1849). Salts of iron do not alter thin slices of it, tannic matters being absent. The presence of myrosin, which at present has been inferred rather than proved, ought to be further investigated. The root dried at 100° C afforded 11·15 per cent. of ash to Mutschler (1878).
=Uses=—An infusion or a distilled spirit of horse-radish is reputed stimulant, diaphoretic, and diuretic, but is not often employed.
=Substitute=—In India the root of Moringa pterygosperma Gärtn. is considered a substitute for horse-radish. It yields by distillation an essential oil of disgusting odour which Broughton, who obtained it in minute quantity, has assured us is not identical with that of mustard or of garlic.
CANELLACEÆ
CORTEX CANELLÆ ALBÆ.
Canella Bark, Canella Alba Bark; F. Canelle blanche; G. Canella-Rinde.
=Botanical Origin=—Canella alba Murray,[310] a tree, 20 to 30 or even 50 feet in height, found in the south of Florida, the Bahama Islands (whence alone its bark is exported), Cuba, Jamaica, Ste. Broix, Guadaloupe, Martinique, Barbadoes and Trinidad.
=History=—The drug was first mentioned in 1605 by Clusius,[311] who remarks that it had been then newly brought to Europe and had received the name of Canella alba (White Cinnamon). It was afterwards known as Costus Corticosus, Costus dulcis, Cassia alba, Cassia lignea Jamaicensis or Jamaica Winter’s Bark. Dale[312] writing in 1693 notices it as not unfrequently sold for Winter’s Bark. Pomet[313] (1694) describes it as synonymous with Winter’s Bark, and observes that it is common, yet but little employed.
The drug is mentioned by most subsequent writers, some of whom like Pomet probably confounded it with the bark of Cinnamodendron (p. 19). It is usually described as produced in Jamaica or Guadaloupe, from which islands no Canella alba is now exported. On the other hand, New Providence, one of the Bahamas whence the Canella alba of the present day is shipped, is not named. Nor do we find any allusion to the drug in the records of the Company (1630-50) which was formed for the colonization of New Providence and the other islands of the group, though their staple productions are frequently enumerated.[314]
Canella alba Murr. was described and figured by Sloane (1707) and still better by Patrick Brown in 1789, and Olaf Swartz in 1791.[315]
[310] Fig. in Bentley and Trimen, Medic. Plants, part 6 (1876).
[311] Exotica, 78.
[312] Pharmacologia, 432.
[313] Hist. des Drog. part i. 130.
[314] Calendar of State Papers, Colonial Series, 1584-1660, Lond. 1860.
[315] O. Swartz, Trans. of the Linnean Soc., i. 96. See also Bonnet, Monographie des Canellées, 1876.
=Collection=—In the Bahamas, where the drug is known as White-Wood Bark or Cinnamon Bark, it is collected thus:—preparatory to being stripped from the wood, the bark is gently beaten with a stick, which removes the suberous layer. By a further beating, the remaining bark is separated, and having been peeled off and dried, is exported without further preparation.[316]
=Description=—Canella bark occurs in the form of quills, more or less crooked and irregular, or in channelled pieces from 2 or 3 up to 6, 8, or more inches in length, ½ an inch to 1 or 2 inches in width, and a line or two in thickness. The suberous layer which here and there has escaped removal is silvery grey, and dotted with minute lichens. Commonly, the external surface consists of inner cellular layers (mesophlœum) of a bright buff, or light orange-brown tint, often a little wrinkled transversely, and dotted (but not always) with round scars. The inner surface is whitish or cinnamon-coloured, either smooth or with slight longitudinal striæ. Some parcels of canella show the bark much bruised and longitudinally fissured by the above-mentioned process of beating. The bark breaks transversely with a short granular fracture, which distinctly shows the three, or in uncoated specimens the two, cortical layers, that of the liber being the largest, and projecting by undulated rays or bundles into the middle layer, which presents numerous large and unevenly scattered oil-cells of a yellow colour.
Canella has an agreeable cinnamon-like odour, and a bitter, pungent acrid taste.[317] Even the corky coat is somewhat aromatic.
=Microscopical Structure=—The spongy suberous coat consists of very numerous layers of large cells with thin walls, showing an undulated rather than rectangular outline. The next small zone is constituted of sclerenchymatous cells in a single, double, or triple row, or forming dense but not very extensive groups. This tissue is sometimes (in unpeeled specimens) a continuous envelope, marking the boundary between the corky layer and the middle portion of the cellular layer; but an interruption in this thick-walled tissue often takes place when portions of it are enveloped and separated by the suberous layer.
The proper cellular envelope shows a narrow tissue with numerous very large cells filled with yellow essential oil. The liber forming the chief portion of the whole bark, exhibits thin prosenchymatous cells, which on traverse section form small bands of a peculiar horny or cartilaginous appearance, on which account they have been distinguished as horny liber (Hornbast of German writers).[318] The liber-fibres show reticulated marks due to the peculiar character of the secondary deposits on their cell-walls. The oil-cells in the liber are less numerous and smaller; the medullary rays are not very obvious unless on account of the crystalline tufts of oxalate of calcium deposited in the latter. This crystalline oxalate retains air obstinately, and has a striking dark appearance.
[316] Information communicated to me by the Hon. J. C. Lees, Chief-Justice of the Bahamas. The second beating would seem to be not always required.—D. H.
[317] A specimen in Sloane’s collection in the British Museum labelled “Cortex Winteranus of the Isles,” but under the microscope seen to be absolutely identical with canella alba, still retains its proper fragrance after nearly two centuries.—F. A. F.
[318] First figured and described by Oudemaus, —Aanteekeningen op het ... Gedeelte der Pharm. Neerlandica, 1854-56. 467.
=Chemical Composition=—The most interesting body in canella is the volatile oil, examined in 1843 under Wöhler’s direction by Meyer and von Reiche, who obtained it in the proportion of 0·94 from 100 parts of bark. They found it to consist of four different oils, the first being identical with the Eugenol or Eugenic Acid of oil of cloves; the second is closely allied to the chief constituent of cajuput oil. The other oils require further examination.[319]
The bark, of which we distilled 20 lb., afforded 0·74 per cent. of oil. This when distilled with caustic potash in excess was found to be composed of 2 parts of the acid portion and 1 part of the neutral hydrocarbon; the latter has an odour suggesting a mixture of peppermint and cajuput.
Meyer and von Reiche evaporated the aqueous decoction of canella, and removed from the bitter extract by alcohol 8 per cent. of mannite, which they ascertained to be the so-called Canellin described in 1822 by Petroz and Robinet.
The bark yielded the German chemists 6 per cent. of ash, chiefly carbonate of calcium. The bitter principle has not yet been isolated. An aqueous infusion is not blackened by a persalt of iron.
=Commerce=—Canella alba is collected in the Bahama Islands and shipped to Europe from Nassau in New Providence, the chief seat of trade in the group. In 1876 the export of the bark amounted to 125 cwt.
=Uses=—The bark is an aromatic stimulant, now but seldom employed. It is used by the West Indian negroes as a condiment.
BIXINEÆ.
SEMEN GYNOCARDIÆ
Chaulmugra Seed.
=Botanical Origin=—Gynocardia odorata R. Br. (Chaulmoogra Roxb., Hydnocarpus Lindl.), a large tree[320] with a globular fruit of the size of a shaddock, containing numerous seeds immersed in pulp. It grows in the forests of the Malayan peninsula and Eastern India as far north as Assam, extending thence along the base of the Himalaya westward to Sikkim.
=History=—The inhabitants of the south-eastern countries of Asia have long been acquainted with the seeds of certain trees of the tribe Pangieæ (ord. Bixineæ) as a remedy for maladies of the skin. In China a seed called Ta-fung-tsze is imported from Siam[321] where it is known as Lukrabo and used in a variety of cutaneous complaints. The tree affording it, which is figured in the Pun-tasao (circa A.D. 1596) has not been recognised by botanists, but from the structure of the seed it is obviously closely related to Gynocardia.[322]
[319] Gmelin, Chemistry, xiv. (1860) 210.
[320] Fig. in Bentley and Trimen, Medic. Plants, part. 26 (1877). Also in Christy, New Commercial Plants, No. 2 (1878).
[321] The Commercial Report from H. M. Consul-General in Siam for the year 1871, presented to Parliament, Aug. 1872, states that 48 peculs (6400 lb.) of Lukrabow seeds were exported from Bangkok to China in 1871. Sir Joseph Hooker (Report on the Royal Gardens at Kew, 1877, p. 33) has been informed by Mr. Pierre, the director of the Botanic Garden at Saigon, Cochin China, that the seeds have proved to derive from a Hydnocarpus (Gynocardia).—See also our article Semen Ignatii and Science Papers, p. 235.
[322] Hanbury, Notes on Chinese Mat. Med. (1862) 23.—Science Papers, 244. Dr. Porter Smith assumes the Chinese drug to be derived from G. odorata, but as I have pointed out, the seeds have a much stronger testa than those of that tree.—D. H.
The properties of G. odorata were known to Roxburgh who, Latinizing the Indian name of the tree, called it (1814) Chaulmoogra odorata. Of late years the seeds have attracted the notice of Europeans in India, and having been found useful in certain skin diseases, they have been admitted a place in the Pharmacopœia of India.
=Description=—The seeds, 1 to 1¼ inches long and about half as much in diameter, are of irregular ovoid form, and more or less angular or flattened by mutual pressure; they weigh on an average about 35 grains each. The testa is thin (about ¹/₅₀ of an inch), brittle, smooth, dull grey; within there is a brown oily kernel, marked with a darker colour at its basal end. The weight of the kernel is, on an average, twice that of the testa. The former encloses in its copious, soft albumen a pair of large, plain, leafy, heart-shaped cotyledons with a stout radicle. The taste of the kernel is simply oily.
=Microscopic Structure=—The testa is chiefly formed of cylindrical thick-walled cells. The albumen exhibits large angular cells containing fatty oil, masses of albuminous matter and tufted crystals of calcium oxalate. Starch is not present.
=Chemical Composition=—The kernels afforded us by means of ether 51·5 per cent. of fatty oil, which is almost colourless or somewhat brownish if the seeds are not fresh. Either extracted or expressed it is of no peculiar taste. The pressed oil concretes at 17° C.; that extracted by ether or bisulphide of carbon requires for solidification a lower temperature. The expressed oil is slightly fluorescent, less so that extracted by means of bisulphide of carbon. If the oil, either pressed or extracted, is diluted with the bisulphide, and then concentrated sulphuric or nitric acid is added, no peculiar coloration is produced.
From the powdered kernels deprived of oil, water removes the usual constituents, glucose, mucilage and albumin.
=Uses=—The seeds are said to have been advantageously used as an alternative tonic in scrofula, skin diseases and rheumatism. They should be freed from the testa, powdered, and given in the dose of 6 grains gradually increased. Reduced to a paste and mixed with Simple Ointment, they constitute the Unguentum Gynocardiæ of the Indian Pharmacopœia, which, as well as an expressed oil of the seeds may be employed externally in herpes, tinea, &c.[323]
[323] For particulars see Christy’s pamphlet alluded to above, p. 75.
=Substitute=—It has been suggested that the seeds of Hydnocarpus Wightiana Bl., a tree of Western India, and of H. venenata Gärtn., native of Ceylon, might be tried where those of Gynocardia are not procurable. The seeds of both species of Hydnocarpus (formerly confounded together as H. inebrians Vahl) afford a fatty oil which the natives use in cutaneous diseases.[324]
POLYGALEÆ
RADIX SENEGÆ.
Radix Senekæ; Senega or Seneka Root; F. Racine de Polygala de Virginie; G. Senegawurzel.
=Botanical Origin=—Polygala Senega L., a perennial plant with slender ascending stems 6 to 12 inches high, and spikes of dull white flowers resembling in form those of the Common Milkwort of Britain. It is found in British America as far north as the river Saskatchewan, and in the United States from New England to Wisconsin, Kentucky, Tennessee, Virginia and the upper parts of North Carolina, as well as in Georgia and Texas, not in the Rocky Mountains.
The plant, which frequents rocky open woods and plains, has become somewhat scarce in the Atlantic states, and as a drug is now chiefly collected in the west, the plant growing profusely in Iowa and Minnesota, west of New York.
=History=—The employment of this root among the Seneca Indians as a remedy for the bite of the rattlesnake attracted the notice of Tennent, a Scotch physician in Virginia; and from the good effects he witnessed he concluded that it might be administered with advantage in pleurisy and peripneumonia. The result of numerous trials made in the years 1734 and 1735 proved the utility of the drug in these complaints, and Tennent communicated his observations to the celebrated Dr. Mead of London in the form of an epistle, afterwards published together with an engraving of the plant, then called the Seneca Rattlesnake Root.[325] Tennent’s practice was to administer the root in powder or as a strong decoction, or more often infused in wine. The new drug was favourably received in Europe, and its virtues discussed in numerous theses and dissertations, one written in 1749 being by Linnæus.[326]
=Description=—Senega root is developed at its upper end into a knotty crown, in old roots as much as an inch in diameter, from which spring the numerous wiry aerial stems, beset at the base with scaly rudimentary leaves often of a purplish hue. Below the crown is a simple tap-root ²/₁₀ to ³/₁₀ of an inch thick, of contorted or somewhat spiral form, which usually soon divides into 2 or 3 spreading branches and smaller filiform rootlets.
[324] Waring, Pharm. of India, 1868. 27.
[325] Tennent (John), Epistle to Dr. Richard Mead concerning the epidemical diseases of Virginia, &c., Edinb. 1738.
[326] Amœnitates Academicæ, ii. 126.
The bark is light yellowish-grey, translucent, horny, shrivelled, knotted and partially annulated. Very frequently a keel-shaped ridge occurs, running like a shrunken sinew through the principal root; it has no connexion with the wood, but originates in a one-sided development of the liber-tissue. The bark encloses a pure, white woody column about as thick as itself. After the root has been macerated in water the bark is easily peeled off, and the peculiar structure of the wood can then be studied. The latter immediately below the crown is a cylindrical cord, cleft however by numerous, fine, longitudinal fissures. Lower down these fissures increase in an irregular manner, causing a very abnormal development of the wood. Transverse sections of a root therefore differ greatly, the circular wood portion being either penetrated by clefts or wide notches, or one-half or even more is altogether wanting, the space where wood should exist being in each case filled up by uniform parenchymatous tissue.
Senega root has a short brittle fracture, a peculiar rancid odour, and a very acrid and sourish taste. When handled it disperses in irritating dust.
=Microscopic Structure=—The woody part is built up of dotted vessels surrounded by short porous ligneous cells; the medullary rays consist of one or two rows of the usual small cells. There is no pith in the centre of the root. The clefts and notches are filled up with an uniform tissue passing into the primary cortical tissue without a distinct liber; the large cells of this tissue are spirally striated. In the keel-shaped rider the proper liber rays may be distinguished from the medullary rays. The former are made up of a soft tissue, hence the cortical part of the root breaks short together with the wood.
Neither starch granules nor crystals of oxalate of calcium are present in this root; the chief contents of its tissue are albuminoid granules and drops of fatty oil.
=Chemical Composition=—The substance to which the drug owes its irritating taste was distinguished by the name of Senegin by Gehlen as early as 1804, and is probably the same as the Polygalic Acid of Quevenne (1836) and of Procter (1859). Christophsohn (1874) extracted it by means of boiling water, evaporated the solution and exhausted the residue with boiling alcohol (0·853 sp. gr.). The liquid after a day or two, deposits the crude senegin, which is to be washed with alcohol (0·813 sp. gr.), and again dissolved in water, from which it is precipitated by a large excess of hydrate of baryum. The barytic compound, dissolved in water, is decomposed by carbonic acid, by which carbonate of baryum is separated, senegin remaining in solution. It is lastly to be precipitated by alcohol. It is amorphous, insoluble in ether and in cold water; it forms with boiling water a frothing solution. Like saponin, to which it is very closely allied, it excites violent sneezing.
Dilute inorganic acids added to a warm solution of senegin throw down a flocculent jelly of Sapogenin, the liquid retaining in solution uncrystallizable sugar. Alkalis give rise to the same decomposition; but it is difficult to split up the senegin completely, and hence the formulas given for this process are doubtful. Even the formula of senegin itself is not definitely settled. According to Christophsohn, the root yields about 2 per cent. of this substance; according to earlier authorities, who doubtless had it less pure, a much larger proportion. From Schneider’s investigations (1875) it would appear that the rootlets are richest in senegin.
Senega root contains a little volatile oil, traces of resin, also gum, salts of malic acid, yellow colouring matter, and sugar (7 per cent. according to Rebling, 1855). The Virginic Acid said by Quevenne to be contained in it, and the bitter substance Isolusin mentioned by Peschier, are doubtful bodies.
=Uses=—Senega is prescribed as a stimulating expectorant and diuretic, useful in pneumonia, asthma and rheumatism. It is much esteemed in America.
=Adulteration=—The drug is not liable to be wilfully falsified, but through careless collecting there is occasionally a slight admixture of other roots. One of these is American Ginseng (Panax quinquefolium L.) a spindle-shaped root which may be found here and there both in senega and serpentaria. The rhizome of Cypripedium pubescens Willd. has also been noticed; it cannot be confounded with that of Polygala Senega. The same may be said with regard to the rhizome of Cynanchum Vincetoxicum R. Brown (Asclepias L., Vincetoxicum officinale Mönch).
RADIX KRAMERIÆ.
Radix Ratanhiæ, Rhatanhiæ v. Rathaniæ; _Rhatany or Rhatania Root, Peruvian or Payta Rhatany_; F. Racine de Ratanhia; G. Ratanhiawurzel.[327]
=Botanical Origin=—Krameriæ triandra Ruiz et Pav., a small woody shrub with an upright stem scarcely a foot high and thick decumbent branches 2 to 3 feet long.[328] It delights in the barren sandy declivities of the Bolivian and Peruvian Cordilleras at 3000 to 8000 feet above the sea-level, often occurring in great abundance and adorning the ground with its red star-like flowers and silver-grey foliage.
The root is gathered chiefly to the north, north-east, and east of Lima, as at Caxatambo, Huanuco, Tarma, Jauja, Huarochiri and Canta; occasionally on the high lands about lake Titicaca. It appears likewise to be collected in the northern part of Peru, since the drug is now frequently shipped from Payta.
=History=—Hipolito Ruiz,[329] the Spanish botanist, observed in 1784 that the women of Huanuco and Lima were in the habit of using for the preservation of their teeth a root which he recognized as that of Krameria triandra, a plant discovered by himself in 1779. On his return to Europe he obtained admission for this root into Spain in 1796, whence it was gradually introduced into other countries of Europe.
The first supplies which reached England formed part of the cargo of a Spanish prize, and were sold in the London drug sales at the commencement of the present century. Some fell into the hands of Dr. Reece who recommended it to the profession.[330]
About 20 years ago there appeared in the European market some other kinds of rhatany previously unknown: of these the more important are noticed at pp. 81, 82.
[327] Ruiz and Pavon state that the root is called at Huanuco ratanhia. The derivation of the word which is of the Quichua language is obscure.
[328] Fig. in Bentley and Trimen, Medicinal Plants, part 30 (1876).
[329] Mem. de la R. Acad. med. de Madrid, i. (1797) 349—366.
[330] Medicinal and Chirurgical Review, Lond., xiii. (1806) ccxlvi.; also Reece, Dict. of Domest. Med., 1808.
=Description=—The root which attains a considerable size in proportion to the aerial part of the shrub, consists of a short thick crown, sometimes much knotted and as large as a man’s fist. This ramifies beneath the soil even more than above, throwing out an abundance of branching, woody roots (frequently horizontal) some feet long and ¼ to ½ an inch thick. These long roots used formerly to be found in commerce; but of late years rhatany has consisted in large proportion of the more woody central part of the root with short stumpy branches, which from their broken and bruised appearance have evidently been extracted with difficulty from a hard soil.
The bark which is scaly and rugged, and ⅒ to ¹/₂₀ of an inch in thickness, is of a dark reddish-brown. It consists of a loose cracked cork-layer, mostly smooth in the smaller roots, covering a bright brown-red inner bark, which adheres though not very firmly to a brownish yellow wood. The bark is rather tough, breaking with a fibrous fracture. The wood is dense, without pith, but marked with thin vessels arranged in concentric rings, and with still thinner, dark medullary rays. The taste of the bark is purely astringent; the wood is almost tasteless; neither possesses any distinctive odour.
Kr. cistoidea Hook, a plant scarcely to be distinguished from Kr. triandra, affords in Chili a rhatany very much like that of Peru. Its root was contributed to the Paris Exhibition of 1867.
=Microscopic Structure=—The chief portion of the bark is formed of liber, which in transverse section exhibits numerous bundles of yellow fibres separated by parenchymatous tissue and traversed by narrow brown medullary rays. The small layer of the primary bark is made up of large cells, the surface of the root of large suberous cells imbued with red matter. The latter also occurs in the inner cortical tissue, and ought to be removed by means of ammonia in order to get a clear idea of the structure. Many of the parenchymatous cells are loaded with starch granules; oxalate of calcium occurs in the neighbourhood of the liber bundles. The woody portion exhibits no structure of particular interest.
=Chemical Composition=—Wittstein (1854) found in the bark of rhatany (the only part of the drug having active properties) about 20 per cent. of a form of tannin called Ratanhia-tannic Acid, closely related to catechu-tannic acid. It is an amorphous powder, the solution of which is not affected by emetic tartar, but yields with ferric chloride a dark greenish precipitate. By distillation Eissfeldt (1854) obtained pyrocatechin as a product of the decomposition of ratanhia-tannic acid. The latter is also decomposed by dilute acids which convert it into crystallizable sugar and Ratanhia-red, a substance nearly insoluble in water, also occurring in abundance ready formed in the bark.
Grabowski (1867) showed that by fusing ratanhia-red with caustic potash, protocatechuic acid and phloroglucin[331] are obtained. Ratanhia-red has the composition C₂₆H₂₂O₁₁, the same, according to Grabowski, as an analogous product of the decomposition of the peculiar tannic acid occurring (as shown by Rochleder in 1866) in the horse-chestnut. The same red substance may also be obtained, as stated by Rembold (1868), from the tannic acid of the root of tormentil (Potentilla Tormentilla L.).
[331] See art. Kino.
As to rhatany root, Wittstein also found it to contain wax, gum and uncrystallizable sugar (even in the wood! according to Cotton[332]). Cotton further pointed out the presence in very minute quantity of an odorous, volatile, solid body, obtainable by means of ether or bisulphide of carbon; it occurs in a somewhat more considerable amount in the other sorts of rhatany. The root contains no gallic acid.
A dry extract of rhatany resembling kino used formerly to be imported from South America, but how and where manufactured we know not. It is however of some interest as containing a crystalline body which Wittstein who discovered it (1854) regards as Tyrosin, C₉H₁₁O₃, previously supposed to be exclusively of animal origin.[333] Städeler and Ruge (1862) assigned to it a slightly different composition, C₁₀H₁₃NO₃, and gave it the name of Ratanhin. It dissolves in hot water which is acidulated by a little nitric acid; the solution on boiling turns red, blue, and lastly green, and becomes at the same time fluorescent. Kreitmair (1875) extracted 0·7 per cent, of ratanhin from an old specimen of commercial extract of rhatany; but he did not succeed in obtaining it from other specimens. He also showed that ratanhin is not a constituent of the roots of Krameria. The same substance has been abundantly found by Gintl (1868) in the natural exudation called Resina d’Angelim pedra[334] which is met with in the alburnum of Ferreirea spectabilis Allem., a large Brazilian tree of the order Leguminosæ (tribe Sophoreæ). Peckolt, who first extracted it, named it Angelin; it forms colourless, neutral crystals yielding compounds both with alkalis and acids, which have been investigated by Gintl in 1869 and 1870.
=Uses=—Rhatany is a valuable astringent, but is not much employed in Great Britain.
=Other sorts of Rhatany=—Of the 20 to 25 other species of Krameria, all of them belonging to America, several have astringent roots which have been collected and used in the place of the rhatany of Peru. The most important of these drugs is that known as—
=Para Rhatany=,—so called from having been shipped from Pará in Brazil. Berg who described it in 1865 termed it Brazilian Rhatany, Cotton in 1868, Ratanhia des Antilles. It is a drug nearly resembling the following, but of a darker and less purple hue; it is also in longer sticks which are remarkably flexible, and covered with a thick bark having numerous transverse cracks.[335] It is apparently derived from the Krameria argentea of Martius,[336] the root of which is collected in the dry districts of the provinces of Bahia and Minas Geraes, that plant growing throughout north-eastern Brazil. It is also called Rhatany from Ceará.
[332] Etudes sur le Genre Krameria (thèse), Paris, 1868. 83.
[333] Gmelin, Chemistry, xiii. (1859) 358.
[334] See Vogl’s Paper on it in Pringsheim, Jahrbücher für wissenschaftliche Botanik, ix. (1874) 277-285.
[335] For further particulars, see Flückiger, Pharm. Journ., July 30, 1870. 84.
[336] Syst. Mat. Med. Bras., 1843. 51; Langgaard, Diccionario de Medicina, Rio de Janeiro, iii. (1865) 384.—Krameria argentea is figured in Flora Brasiliensis, Fascicul. 63 (1874, pg. 71) tab. 28.
=Savanilla or New Granada Rhatany.= The plant yielding it is Krameria tomentosa St. Hil. (Kr. Ixina var. β granatensis Triana, Kr. grandifolia Berg), a shrub 4 to 6 feet high covering large arid tracts in the valley of Jiron between Pamplona and the Magdalena in New Granada, in which locality the collection of the root was observed by Weir in 1864.[337] According to Triana it also grows at Socorro, south of Jiron. The same plant is found near Santa Marta and Rio Hacha in north-eastern New Granada, in British Guiana, and in the Brazilian provinces of Pernambuco and Goyaz.
The stem or root-crown of Savanilla rhatany is never so knotty and irregular as that of the Peruvian drug, nor are the roots so long or so thick. Separate pieces of root of sinuous form, 4 to 6 inches long and ²/₁₀ to ³/₁₀ of an inch thick are most frequent. The drug is moreover well distinguished by its dull purplish brown colour, its thick smooth bark marked with longitudinal furrows, and here and there with deep transverse cracks, and by the bark not easily splitting off as it does in common rhatany.
The anatomical difference depends chiefly upon the more abundant development of the bark which in thickness is ⅓ to ¼ the diameter of the wood. In Peruvian rhatany the cortical layer attains only ⅙ to ⅛ of the diameter of the woody column. The greater firmness of the suberous coat in Savanilla rhatany is due to its cells being densely filled with colouring matter.
Savanilla rhatany differs from the Peruvian root in its tannic matter. This becomes evident by shaking the powdered root (or bark) with water and iron reduced by hydrogen. The liquid filtered from the Savanilla sort and diluted with distilled water exhibits an intense violet colour, that from Peruvian rhatany a dingy brown; the latter turns light red by alkalis. Thin sections of the Peruvian root assume a greyish hue when moistened with a ferrous salt; Savanilla root by a similar treatment displays the above violet colour. The Savanilla root is richer in soluble matter and from the greater development of its bark may deserve to be preferred for medicinal use.
In the English market, Savanilla root is of less frequent occurrence than that of Pará.
A kind of rhatany attributed to Krameria secundiflora DC., a herbaceous plant of Mexico, Texas and Arkansas, was furnished to Berg in 1854, but has not been in commerce. Its anatomical structure has been described by Berg.[338]
[337] Hanbury, Origin of Savanilla Rhatany, in Pharm. Journ. vi. (1865) 460.—Also Science Papers, 333.—In that paper I referred the drug to a variety of Kr. Ixina which M. Cotton has shown to differ in no respect from St. Hilaire’s Kr. tomentosa, a conclusion in which, after careful re-examination of specimens, I fully agree.—D. H.
Fig. of Kr. Ixina in Bentley and Trimen, Med. Pl. part 10.
[338] Bot. Zeitung, 14th Nov. 1856. 797
GUTTIFERÆ
=CAMBOGIA.=
Gummi Gambogia, Gummi Gutti; Gamboge; F. Gomme Gutte; G. Gutti, Gummigutt.
=Botanical Origin=—Garcinia Morella Desrousseaux, var. β. pedicellata, a diœcious tree,[339] with handsome laurel-like foliage and small yellow flowers, found in Camboja, Siam (province of Chantibun and the islands on the east coast of the gulf of Siam), and in the southern parts of Cochin China. It was introduced about thirty years ago into Singapore where several specimens are still thriving (1873) on the estate of Dr. Jamie. The finest is now a tree of 20 feet high, with a trunk a foot in diameter, and a thick, spreading head of foliage.
G. Morella Desr.—The typical form of this tree having sessile male flowers grows in moist forests of Southern India and Ceylon, and is capable of affording good gamboge.
G. pictoria Roxb., a large tree of Southern India, produces a sort of gamboge found by Christian (1846) essentially the same as that of Siam. It has been examined more recently by Broughton (1871) who states it to be quite equal to that of G. Morella. We have also been unable to find any difference between the product of G. pictoria as sent from Ceylon and common gamboge. Garcinia pictoria moreover is thought by Sir Jos. Hooker to agree with G. Morella.
=History=—The Chinese had intercourse with Camboja as early as the time of the Sung dynasty (A.D. 970-1127); and a Chinese traveller who visited the latter country in 1295-97, describes gamboge and the method of obtaining it by incisions in the stem of the tree.[340] The celebrated Chinese herbal Pun-tsao, written towards the close of the 16th century, mentions gamboge (Tang-hwang) and gives a rude figure of the tree. The drug is regarded by the Chinese as poisonous, and is scarcely employed except as a pigment.
The first notice of the occurrence of gamboge in Europe is in the writings of Clusius[341] who describes a specimen brought from China by the Dutch Admiral, Jacob van Neck, and given to him in 1603, under the name of Ghittaiemou.[342] It appears that shortly after this time it began to be employed in medicine in Europe, for in 1611, Michael Reuden, a physician of Bamberg, made use of it as he stated in 1613.[343] He termed the drug a “novum gummi purgans,” or also, Gummi de Peru, the latter strange name no doubt being a corruption of the above mentioned Ghittaiemou. The appellation “gummi de Peru” is met with in pharmaceutical tariffs during the 17th and 18th centuries.
[339] It has been named Garcinia Hanburyi by Sir Joseph Hooker (Journ. of the Linnean Soc. xiv., 1873, 435), but I presume my lamented friend Daniel Hanbury would not have considered the plant under notice as a distinct species. Consult also Bentley and Trimen, Med. Plants, part 30.—F. A. F.
[340] Description de Camboge in Abel-Remusat’s Nouv. Mélanges asiatiques, i. (1829) 134.—The Chinese traveller calls the exudation Kiang-hwang which is the name for turmeric, but his description is unmistakeable.
[341] Exotica (1605) 82.
[342] Dr. R. Rost is of opinion that this word is derived from the Malay gătáh, gum, and the Javanese jamú signifying medicinal, such mixing of the two languages being of common occurrence.
[343] De nova gummi purgante, Lipsiæ, 1614. We have only seen the second edition published at Leiden in 1625, its preface dating from 1613.
Gamboge is one of the articles of the tariff of the pharmaceutical shops of the City of Frankfort in 1612: “Gutta gemou, a strong purgative dried juice, coming from the Kingdom of Patana in the East Indies.” Patana or Patani is the most populous province of the east coast of the peninsula of Malacca. The Dutch established there a factory in 1602, and were followed in 1612 by the English. The settlement was abandoned in 1700; gamboge was probably brought there from the opposite shore of the gulf of Siam.[344]
In 1615, a considerable quantity of gamboge was offered for sale in London by the East Indian Company. The entry respecting it in the Court Minute Books of the company under date October 13, 1615, is to this effect:—Three chests, one rundlet, and a basket, containing 13, 14, or 15 hundredweights, more or less, of Cambogium “a drugge unknown here,”—the use of which, was much commended as a “a gentle purge,” were offered for sale at 5s. per lb., but met with no purchaser.
Jacob Bontius,[345] a Dutch physician, resident, towards 1629, in Batavia, stated that “gutta Cambodja,” as he termed the drug, came from the country of the same name; he supposed it to be derived from an Euphorbiaceous plant.
Parkinson,[346] who was an apothecary of London and wrote in 1640, speaks of this “Cambugio,” called by some Catharticum aureum, as a drug of recent importation which arrived in the form of “wreathes or roules” yellow within and without.
In the London Pharmacopœia of 1650, gamboge is called Gutta Gamba[347] or Ghitta jemou.
The mother plant of the drug was not fully examined and figured until 1864; yet in 1677 already, Hermann, a German physician residing in Ceylon, had pointed out that it was a Garcinia.[348]
=Secretion=—We have examined a portion of a branch two inches in diameter of the gamboge-tree,[349] and have found the yellow gum-resin to be contained chiefly in the middle layer of the bark in numerous ducts like those occurring in the roots of Inula Helenium and other roots of the same natural order. A little is also secreted in the dotted vessels of the outermost layer of the wood, and in the pith. The wood, which is white, acquires a bright yellow tint when exposed to the vapour of ammonia or to alkaline solutions.
=Production=—At the commencement of the rainy season the gamboge-collectors start for the forest in search of the trees which in some localities are plentiful. Having found one of the full size they make a spiral incision in the bark round half the circumference of the trunk, and place a joint of bamboo to receive the sap which slowly exudes for several months. When it first issues from the tree, it is a yellowish fluid, which after passing through a viscid state hardens into the gamboge of commerce.
[344] Flückiger, Documente zur Geschichte der Pharmacie, 1876. 41.
[345] De Medicina Indorum, lib. iv. Lugduni Batav. (1642) 119. 150.
[346] Theatrum Botanicum (1640) 1575.
[347] This name is the Hindustani Gótáganbá, signifying according to Moodeen Sheriff (Suppl. to Pharm. of India, 83) juice or extract of rhubarb. It is still applied to gamboge.
[348] Hanbury in Trans. of Linn. Soc. xxiv. (1864) 487. tab. 50; also Science Papers, 1876. 326.
[349] Obligingly sent to us by Dr. Jamie of Singapore.
The trees grow both in the valleys and on the mountains and will yield on an average in one season enough to fill three joints of bamboo 20 inches in length by 1½ inches in diameter. The tree appears to suffer no injury provided the tapping is not more frequent than every other year.[350]
According to Dr. Jamie of Singapore, the gamboge-tree grows most luxuriantly in the dense jungles. The best time for collecting is from February to March or April. The trees, the larger the better, are wounded by a parang or chopping-knife, in various parts of the trunk and large branches, when prepared bamboos are inserted between the root and the bark of the trees. The bamboo cylinders being tied or inserted, are examined daily till filled, which generally takes from 15 to 30 days. Then the bamboos are taken to a fire, over which they are gradually rotated till the water in the gum-resin is evaporated and it gets sufficiently hard to allow of the bamboo being torn off.[351]
=Description=—The drug arrives in the form of sticks or cylinders 1 to 2½ inches in diameter, and 4 to 8 inches in length, striated lengthwise with impressions from the inside of the bamboo. Often the sticks are agglutinated, or folded, or the drug is in compressed or in shapeless masses. It is when good of a rich brownish orange tint, dense and homogeneous, breaking easily with a conchoidal fracture, scarcely translucent even in thin splinters. Touched with water it instantly forms a yellow emulsion. Triturated in a mortar it affords a brilliant yellow powder, slightly odorous. Gamboge has a disagreeable acrid taste.
Much of the gamboge shipped to Europe is of inferior quality, being of a brownish hue or exhibiting when broken a rough, granular, bubbly surface. Sometimes it arrives imperfectly dried and still soft.
=Chemical Composition=—Gamboge consists of a mixture of resin with 15 to 20 per cent. of gum. The resin dissolves easily in alcohol, forming a clear liquid of fine yellowish-red hue, and not decidedly acid reaction. It forms darker-coloured solutions with ammonia or the fixed alkalis, and a copious precipitate with basic acetate of lead. Perchloride of iron colours a solution of the resin deep blackish brown.
By fusing purified gamboge resin with potash, Hlasiwetz and Barth (1866) obtained acetic acid and other acids of the same series, together with phloroglucin, C₆H₃(OH)₃, pyrotartaric acid, C₅H₈O₄, and isuvitinic acid, C₆H₃CH₃(COOH)₂.
The gum which we obtained to the extent of 15·8 per cent. by completely exhausting gamboge with alcohol and ether, was found readily soluble in water. The solution does not redden litmus, and is not precipitated by neutral acetate of lead, nor by perchloride of iron, nor by silicate or biborate of sodium. It is therefore not identical with gum arabic.
[350] Spenser St. John, Life in the Forests of the Far East, Lond. 1862. ii. 272.
[351] Pharm. Journ. iv. (1874) 803.
=Commerce=—The drug finds its way to Europe from Camboja by Singapore, Bangkok, or Saigon. In 1877 the first place exported 240 peculs, Bangkok in 1875 no less than 346 peculs, value 48,835 dollars; from Saigon there have of late been shipped from 30 to 40 peculs annually (one pecul = 133·3 lbs. = 60·479 kilogrammes).[352]
=Uses=—Gamboge is a drastic purgative, seldom administered except in combination with other substances.
=Adulteration=—The Cambojans adulterate gamboge with rice flour, sand, or the pulverized bark of the tree,[353] which substances may be easily detected in the residue left after exhausting the drug successively by spirit of wine and cold water.
=Other Sources of Gamboge=—Although the gamboge of European commerce appears to be exclusively derived from the form of the plant named at the head of this article, Garcinia travancorica Beddome, is capable of yielding a similar drug which may be collected to some small extent for local use, but not for exportation. It is a beautiful tree of the southern forests of Travancore and the Tinnevelly Ghats (3,000 to 4,500 feet). According to its discoverer Lieut. Beddome,[354] it yields an abundance of bright yellow gamboge.
OLEUM GARCINIÆ
Concrete Oil of Mangosteen, Kokum Butter.
=Botanical Origin.=—Garcinia indica Choisy (G. purpurea Roxb. Brindonia indica Dup. Th.), an elegant tree with drooping branches and dark green leaves.[355] It bears a smooth round fruit the size of a small apple, containing an acid purple pulp in which are lodged as many as 8 seeds. The tree is a native of the coast region of Western India known as the Concan, lying between Daman and Goa.
=History=—The fruit is mentioned by Garcia d’Orta(1563) as known to the Portuguese of Goa by the name of Brindones. He states that it has a pleasant taste though very sour, and that it is used in dyeing; and further that the peel serves to make a sort of vinegar. Several succeeding authors (as Bauchin and Ray) have contented themselves with repeating this account.
As to the fruit yielding a fatty oil, we find no reference to such fact till about the year 1830, when it was stated in an Indian newspaper[356] that an oil of the seeds is well known at Goa and often used to adulterate ghee (liquid butter). It was afterwards pointed out as the result of some experiments that the oil was of an agreeable bland taste and well adapted for use in pharmacy. A short article on Kokum Butter was published by Pereira[357] in 1851. With the view of bringing the substance into use for pharmaceutical preparations in India, it has been introduced into the Pharmacopœia of India of 1868.
[352] Report from H. M. Consul-General in Siam for 1875. 9.
[353] Spenser St. John, op. cit.
[354] Flora Sylvatica, Madras, part xv. (1872) tab. 173.
[355] Fig. Bentley and Trimen, Medic. Plants, part 31 (1878).
[356] Quoted by Graham, Catal. of Bombay Plants, 1839. 25.
[357] Pharm. Journ. xi. (1852) 65.
=Preparation=—The seeds are reniform, somewhat crescent-shaped or oblong, laterally compressed and wrinkled, ⁶/₁₀ to ⁸/₁₀ of an inch long by about ⁴/₁₀ broad. Each seed weighs on an average about eight grains. The thick cotyledons, which are inseparable,[358] have a mild oily taste. Examination under the microscope shows them to be built up of large reticulated cells containing a considerable proportion of crystalline fat readily soluble in benzol. In addition globular masses of albuminous matter occur which with iodine assume a brownish yellow hue. With perchloride of iron the walls strike a greenish-black.
The process followed by the natives of India (by whom alone the oil is prepared) has been thus described:—The seeds having been dried by exposure for some days to the sun are bruised, and boiled in water. The oil collects on the surface, and concretes when cool into a cake which requires to be purified by melting and straining.
=Description=—Kokum Butter is found in the Indian bazaars in the form of egg-shaped or oblong lumps about 4 inches long by 2 inches in diameter, and weighing about a quarter of a pound. It is a whitish substance, at ordinary temperatures, firm, dry, and friable, yet greasy to the touch. Scrapings (which are even pulverulent) when examined in glycerin under the microscope show it to be thoroughly crystalline. They have a mild oily taste, yet redden litmus if moistened with alcohol.
By filtration in a steam-bath, kokum butter is obtained perfectly transparent and of a light straw-colour, concentrating again at 27·5° C. into a white crystalline mass: some crystals appear even at 30°. Melted in a narrow tube, cooled and then warmed in a water bath, the fat begins to melt at 42·5 C., and fuses entirely at 45°. The residue left after filtration of the crude fat is inconsiderable, and consists chiefly of brown tannic matters soluble in spirit of wine.
When kokum butter is long kept it acquires an unpleasant rancid smell and brownish hue, and an efflorescence of shining tufted crystals appears on the surface of the mass.
=Chemical Composition=—Purified kokum butter boiled with caustic soda yields a fine hard soap which, when decomposed with sulphuric acid, affords a crystalline cake of fatty acids weighing as much as the original fat. The acids were again combined with soda and the soap having been decomposed, they were dissolved in alcohol of about 94 per cent. By slow cooling and evaporation crystals were first formed which, when perfectly dried, melted at 69·5° C.: they are consequently Stearic Acid. A less considerable amount of crystals which separated subsequently had a fusing point of 55°, and may be referred to Myristic Acid.
A portion of the crude fat was heated with oxide of lead and water, and the plumbic compound dried and exhausted with ether, which after evaporation left a very small amount of liquid oil, which we refer to Oleic Acid.
Finally the sulphuric acid used at the outset of the experiments was saturated and examined in the usual manner for volatile fatty acids (butyric, valerianic, &c.) but with negative results.
[358] The embryo, according to Bentley and Trimen (l. c.) consists chiefly of the thickened radicle, and is almost devoid of cotyledons.
The fat of the seeds of G. indica was extracted by ether and examined chemically in 1857 by J. Bouis and d’Oliveira Pimentel.[359] It was obtained to the extent of 30 per cent., was found to fuse at 40° C. and to consist chiefly of stearin (tristearin). The seeds yielded 1·72 per cent. of nitrogen. Their residue after exhaustion by ether afforded to alkaline solutions or alcohol a fine red colour.
=Uses=—The results of the experiments above-noted show that kokum butter is well suited for some pharmaceutical preparations. It might also be advantageously employed in candle-making, as it yields stearic acid more easily and in a purer state than tallow and most other fats. But that it is possible to obtain it in quantities sufficiently large for important industrial uses, appears to us very problematical.
DIPTEROCARPEÆ
=BALSAMUM DIPTEROCARPI.=
Balsamun Gurjunæ; Gurjun Balsam, Wood Oil.
=Botanical Origin=—This drug is yielded by several trees of the genus Dipterocarpus, namely—
D. turbinatus Gärtn. f. (D. lævis Ham., D. indicus Bedd), a native of Eastern Bengal, Chittagong and Pegu to Singapore, and French Cochin China.
D. incanus Roxb., a tree of Chittagong and Pegu.
D. alatus Roxb., growing in Chittagong, Burma, Tenasserim, the Andaman Islands, Siam, and French Cochin China.
D. zeylanicus Thw. and D. hispidus Thw., indigenous to Ceylon.
D. crispalatus ... abounding, together with D. turbinatus and D. alatus, in French Cochin China.
D. trinervis Bl., a native of Java and the Philippines, and D. gracilis Bl., D. littoralis Bl., D. retusus Bl. (D. Spanoghei Bl.), trees of Java supply a similar useful product which as yet appears to be of less commercial importance.[360]
The Gurjun trees are said by Hooker[361] to be among the most magnificent of the forests of Chittagong. They are conspicuous for their gigantic size, and for the straightness and graceful form of their tall unbranched trunk, and small symmetrical crown of broad glossy leaves. Many individuals are upwards of 200 feet high and 15 feet in girth.
=History=—Gurjun balsam was enumerated as one of the productions of Ava by Francklin[362] in 1811, and in 1813 it was briefly noticed by Ainslie.[363] Its botanical origin was first made known by Roxburgh, who also described the method by which it is extracted.
[359] Comptes Rendus, xliv. (1857) 1355.
[360] That of D. trinervis is especially used in Java. Filet, Plantkundig Woordenboek voor Nederlandsch Indië, Leiden, 1876, No. 6157.
[361] Himalayan Journal, ed. 2, ii. (1855) 332.
[362] Tracts on the Dominions of Ava, Lond. 1811. 26.
[363] In the Catalogue des Produits des Colonies françaises, Exposition Universelle de 1878, p. 175, it is stated that the balsam of D. alatus in French Cochin China is preferred, being a “huile b’anche.”
The medicinal properties of Gurjun balsam were pointed out by O’Shaughnessy[364] as entirely analogous to those of copaiba; and his observations were confirmed by many practitioners in India. This has obtained for the drug a place in the Pharmacopœia of India (1868).
=Extraction=—A recent account of the production of this drug is found in the Reports of the Jury of the Madras Exhibition of 1855. It is there stated that Wood Oil, as the balsam is commonly called, is obtained for the most part from the coast of Burma and the Straits, and is procured by tapping the trees about the end of the dry season. Several deep incisions are made with an axe into the trunk of the tree and a good-sized cavity scooped out. In this, fire is placed, and kept burning until the wood is somewhat scorched, when the balsam begins to exude, and is then led away into a vessel of bamboo. It is afterwards allowed to settle, when a clear liquid separates from a thick portion called the “guad.” The oil is extracted year after year, and sometimes there are two or three holes in the same tree. It is produced in extraordinary abundance; from 30 to 40 gallons according to Roxburgh may sometimes be obtained from a single tree in the course of a season, during which it is necessary to remove from time to time the old charred surface of the wood and burn afresh.
If a growing tree is felled and cut into piece, the oleo-resin exudes and concretes on the wood, very much, it is said, resembling camphor (?) and having an aromatic smell.
=Description=—As Gurjun balsam is the produce of different trees as well as of different countries, it is not surprising to find that it varies considerably in its properties.
The following observations refer to a balsam of which 400 lb. were recently imported from Moulmein for a London drug firm. It is a thick and viscid fluid, exhibiting a remarkable fluorescence, so that when seen by reflected light it appears opaque and of dingy greenish grey; yet when placed between the observer and strong daylight it is seen to be perfectly transparent and of a dark reddish-brown.[365] It has a weak aromatic copaiba-like odour and a bitterish aromatic taste without the persistent acridity of copaiba. Its sp. gr. at 16·9° C. is 0·964.
[364] Mat. Med. of Hindoostan, Madras, 1813. 186.
[365] Bengal Dispensatory, 1842. 22.
With the following liquids Gurjun affords perfectly clear solutions which are more or less fluorescent, namely pure benzol (from benzoate of calcium), cumol, chloroform, sulphide of carbon, essential oils. On the other hand, it is not entirely soluble in methylic, ethylic, or amylic alcohol; in ether, acetic ether, glacial acetic acid, acetone, phenol (carbolic acid), or in caustic potash dissolved in absolute alcohol. Many samples of commercial benzin also are not capable of dissolving the oleo-resin perfectly, but we have not ascertained on what constituent of such benzin this depends. We have further noticed that that portion of petroleum which is known as Petroleum Ether, containing the most volatile hydrocarbons, does not wholly dissolve the oleo-resin. One hundred parts of the balsam warmed and shaken with 1000 parts of absolute alcohol yielded on cooling a precipitate of resin amounting when dried to 18·5 parts. All concentrated solutions of the balsam are precipitated by amylic alcohol.
If the balsam is kept for a long time in a stoppered vessel at 100° C. it simply becomes a little turbid; but about 130° C. it is transformed into a jelly, and on cooling does not resume its former fluidity. Balsam of copaiba heated in a closed glass tube to 220° C. does not at all lose its fluidity, whereas Gurjun balsam becomes an almost solid mass.
=Chemical Composition=—Of the balsam 6·99 grammes dissolved in benzol and kept in a water bath until the residue ceased to lose weight, yielded 3·80 grammes of a dry, transparent, semi-fluid resin, corresponding to 54·44 per cent., and 45·56 of volatile matters expelled by evaporation. But another sample afforded us much less residue. By submitting larger quantities of the above balsam to the usual process of distillation with water in a large copper still, 37 per cent. of volatile oil were easily obtained. The water passing over at the same time did not redden litmus paper. A dark, viscid, liquid resin remained in the still.
The essential oil is of a pale straw-colour and less odorous than most other volatile oils. Treated with chloride of calcium and again distilled, it begins to boil at 210° C. and passes over at 255°-260° C., acquiring a somewhat empyreumatic smell and light yellowish tint. The purified oil has a sp. gr. of 0·915;[366] it is but sparingly soluble in absolute alcohol or glacial acetic acid, but mixes readily with amylic alcohol.
According to Werner (1862) this oil has the composition C₂₀H₃₂ like that of copaiba. He says it deviates the ray of polarized light to the left, but that prepared by one of us deviated strongly to the right, the residual resin dissolved in benzol being wholly inactive. The oil does not form a crystalline compound with dry hydrochloric acid, which colours it of a beautiful blue.[367] De Vry[368] states that the essential oil after this treatment deviates the ray to the right.
The resin contains, like that of copaiba, a small proportion of a crystallizable acid which may be removed by warming it with ammonia in weak alcohol. That part of the resin which is insoluble even in absolute alcohol,[369] we found to be uncrystallizable. The Gurgunic Acid, as the crystallized resinous acid is called by Werner,[370] but which it is more correct to write Gurjunic, may consequently be prepared by extracting the resin with alcohol (·838) and mixing the solution with ammonia. From the ammoniacal solution gurjunic acid is precipitated on addition of a mineral acid, and if it is again dissolved in ether and alcohol it may be procured in the form of small crystalline crusts. From the specimen under examination we were not successful in obtaining indubitable crystals.
[366] 0·944 according to Werner; 0·931 O’Shaughnessy; 0·928 De Vry (1857).
[367] This magnificent colouring matter is not dissolved by ether.
[368] Pharm. Journ. xvi. (1857) 374.
[369] The sample of gurjun balsam examined by Werner as well as the resin it contained were entirely soluble in boiling potash lye.
[370] Gmelin, Chemistry, xvii. 545.
Gurjunic acid, C₄₄H₆₈O₈ according to Werner, melts at 220° C., and concretes again at 180° C.; it begins to boil at 260° C., yet at the same time decomposition takes place. By assigning to this acid the formula C₄₄H₆₄O₅ + 3H₂O, which agrees well with Werner’s analytical results, we may regard it as a hydrate of abietinic acid, the chemical behaviour of which is perfectly analogous. Gurjunic acid is soluble in alcohol 0·838, but not in weak alcohol; it is dissolved also by ether, benzol, or sulphide of carbon (Werner).
In copaiba from Maracaibo, Strauss (1865) discovered Metacopaivic Acid which is probably identical with gurjunic; the former, however, fuses at 206° C.
The amorphous resin forming the chief bulk of the residue of the distillation of the balsam, has not yet been submitted to exact analysis. We find that after complete desiccation it is not soluble in absolute alcohol. A crystallized constituent of Gurjun, which we obtained from a balsam of unknown origin, has been shown[371] to answer to the formula C₂₈H₄₆O₂. Its crystals, belonging to the asymmetric system, melt at 126°-130°C.; they are entirely devoid of acid character. A comparative examination of the product of each of the above named species of Dipterocarpus would be highly desirable.
=Commerce=—Gurjun balsam is exported from Singapore, Moulmein, Akyab and the Malayan Peninsula, and is a common article of trade in Siam. It is likewise produced in Canara in Southern India. It is occasionally shipped to Europe. More than 2000 lb. were offered for sale in London under the name of East India Balsam Capivi, 4th October 1855; and in October 1858, a no less quantity than 45 casks appeared in the catalogue of a London drug-broker. It is now not unfrequent in the London drug sales.
=Uses=—In medicine it has hitherto been employed only as a substitute for copaiba, and chiefly in the hospitals of India.
In the East its great use is as a natural varnish, either alone or combined with pigments; and also as a substitute for tar as an application to the seams of boats, and for preserving timber from the attacks of the white ant. To the first application it is often made better appropriated[372] by boiling it, so that the essential oil is evaporated.
Wood Oil of China—The oleo-resin of Dipterocarpus must not be confounded with the so-called Wood Oil of China, which is of a totally different nature. The latter is a fatty oil expressed from the seeds of Aleurites cordata Müll. Arg. (Dryandra cordata Thunb. Elaeococca Vernicia Sprgl. Prodromus xv. part 2, p. 724), the well-known Tung tree of the Chinese. It is a large tree of the order Euphorbiaceæ, found in China and Japan. The oil is an article of enormous consumption among the Chinese, who use it in the caulking and painting of junks and boats, for preserving woodwork, varnishing furniture, and also in medicine. In the commercial reports of H.M. Consuls in China (No. 5, 1875, p. 3, 26) we find that this oil is largely exported from Hankow: 199·654 peculs in 1874, and forms an article of import at Ningpo: 15·123 peculs in 1874 (pecul = 133·33 lb. avoirdupois). It is, however, not shipped to foreign countries. The oil of the Tung tree is also extremely remarkable on account of its chemical properties as shown by Cloëz (1875-1877).
[371] Flückiger, Pharm. Journ. (1878) 725, with fig.
[372] Catalogue of the French Colonies, Paris Exhibition, 1878, 101, quoted above.
MALVACEÆ
RADIX ALTHÆÆ
Marshmallow Root; F. Racine de Guimauve; G. Eibischwurzel.
=Botanical Origin=—Althæa officinalis L., the marshmallow, grows in moist places throughout Europe, Asia Minor, and the temperate parts of Western and Northern Asia, but is by no means universally distributed. It prefers saline localities such as in Spain the salt marshes of Saragossa, the low-lying southern coasts of France near Montpellier, Southern Russia, and the neighbourhood of salt-springs in Central Europe. In southern Siberia Althæa has been met with by Semenoff (1857) ascending as high as 3,000 feet in the Alatau mountains, south of the Balkash Lake.
In Britain it occurs in the low grounds bordering the Thames below London, and here and there in many other spots in the south of England and of Ireland.
The cultivated marshmallow thrives as far north as Throndhjem in Norway, and has been naturalized in North America (salt marshes of New England and New York) and Australia. It is largely cultivated in Bavaria and Württemberg.
=History=—Marshmallow had many uses in ancient medicine, and is described by Dioscorides as Άλθαία, a name derived from the Greek verb ἀλθειν, to heal.
The diffusion of the plant in Europe during the middle ages was promoted by Charlemagne who enjoined[373] its culture (A.D. 812) under the name of “Mismalvas, id est alteas quod dicitur ibischa.”
=Description=—The plant has a perennial root attaining about a foot in length and an inch in diameter. For medicinal use the biennial roots of the cultivated plant are chiefly employed. When fresh they are externally yellowish and wrinkled, white within and of tender fleshy texture. Previous to drying, the thin outer and a portion of the middle bark are scraped off, and the small root filaments are removed. The drug thus prepared and dried consists of simple whitish sticks 6 to 8 inches long, of the thickness of the little finger to that of a quill, deeply furrowed longitudinally and marked with brownish scars. Its central portion, which is pure white, breaks with a short fracture, but the bark is tough and fibrous. The dried root is rather flexible and easily cut. Its transverse section shows the central woody column of undulating outline separated from the thick bark by a fine dark outline shaded off outwards.
The root has a peculiar though very faint odour, and is of rather mawkish and insipid taste, and very slimy when chewed.
[373] Pertz, Monumenta Germaniæ historica, Legum tom. i. (1835) 181.—Ibischa from the Greek ὶβίσκος.
=Microscopic Structure=—The greater part of the bark consists of liber, abounding in long soft fibres, to which the toughness of the cortical tissue is due. They are branched and form bundles, each containing from 3 to 30 fibres separated by parenchymatous tissue. Of the cortical parenchyme many cells are loaded with starch granules, others contain stellate groups of oxalate of calcium, and a considerable number of somewhat larger cells are filled with mucilage. The last named on addition of alcohol is seen to consist of different layers.
The woody part is made up of pitted or scalariform vessels, accompanied by a few ligneous cells and separated by a parenchymatous tissue, agreeing with that of the bark. On addition of an alkali, sections of the root assume a bright yellow hue.
=Chemical Composition=—The mucilage in the dry root amounts to about 25 per cent. and the starch to as much more. The former appears from the not very accordant analysis of Schmidt and of Mulder to agree with the formula C₁₂H₂₀O₁₀, thus differing from the mucilage of gum arabic by one molecule less of water. It likewise differs in being precipitable by neutral acetate of lead. At the same time it does not show the behaviour of cellulose, as it does not turn blue by iodine when moistened with sulphuric acid, and it is not soluble in ammoniacal solution of oxide of copper.
The root also contains pectin and sugar (cane-sugar according to Wittstock), and a trace of fatty oil. Tannin is found in very small quantity in the outer bark alone.
In 1826 Bacon, a pharmacien of Caen, obtained from althæa root crystals of a substance at first regarded as peculiar, but subsequently identified with Asparagin, C₄H₈N₂O₃, H₂O. It had been previously prepared (1805) by Vauquelin and Robiquet from Asparagus, and is now known to be a widely diffused constituent of plants.[374] Marshmallow root does not yield more than 0·8 to 2·0 per cent. Asparagin crystallizes in large prisms or octohedra of the rhombic system; it is nearly tasteless, and appears destitute of physiological action. Its relation to succinic acid may be thus represented:—
Succinic acid: C₂H₄ {COOH; Asparagin: C₂H₃(NH₂) {CONH₂ {COOH {COOH.
Asparagin is quite permanent whether in the solid state or dissolved, but it is easily decomposed if the solution contains the albuminoid constituents of the root, which act as a ferment. Leguminous seeds, yeast or decayed cheese induce the same change, the final product of which is succinate of ammonium, the asparagin taking the elements of water and hydrogen set free by the fermentation, thus—
C₄H₈N₂O₃ + H₂O + 2H = 2NH₄, C₄H₄O₄ Asparagin. Succinate of Ammonium.
Under the influence of acids or bases, or even by the prolonged boiling of its aqueous solution, asparagin is converted into Aspartate of Ammonium, C₄H₆(NH₄)NO₄, of which the hydrated asparagin contains the elements.
[374] It plays an interesting part in the germination of the seeds of papilionaceous and other plants. It is abundant in the young plants, but in most it speedily disappears. Its presence can be proved in the juice by means of the microscope and absolute alcohol, in which latter asparagin is insoluble. See Pfeffer in Pringsheim’s Jahrb. f. wiss. Bot. 1872. 533-564.—Borodin in Bot. Zeitung, 1878. 801 and seq.
These transformations, especially the former, are undergone by the asparagin in the root, if the latter has been imperfectly dried, or has been kept long, or not very dry. Under such conditions, the asparagin gradually disappears, and the root then yields a brownish decoction, sometimes having a disagreeable odour of butyric acid. There is no doubt that a protein-substance here acts as a ferment. The sections of the root when touched with ammonia or caustic lye should display a bright yellow, not a dingy brown, colour.
The peeled root dried at 100° C. and incinerated afforded us 4·88 of ash, rich in phosphates.
=Uses=—Althæa is taken as a demulcent; it is sometimes also applied as an emollient poultice. It is far more largely used on the continent than in England.
FRUCTUS HIBISCI ESCULENTI
Capsulæ Hibisci esculenti; Uëhka, Okro, Okra, Bendi-kai[375]; F. Gombo (in the French Colonies).
=Botanical Origin=—Hibiscus esculentus L. (Abelmoschus esculentus Guill. et Perr.) an herbaceous annual plant 2 to 3 or even 10 feet high, indigenous to the Old World.[376] It has been found growing abundantly wild on the White Nile by Schweinfurth, and also in 1861 by Col. Grant in Unyoro, 2° N. lat., near the lake Victoria Nyanza, where it is known to the natives as Bameea.
The plant is now largely cultivated in several varieties in all tropical countries.
=History=—The Spanish Moors appear to have been well acquainted with Hibiscus esculentus, which was known to them by the same name that it has in Persian at the present day—Bámiyah. Abul Abbas el-Nebáti, a native of Seville learned in plants, who visited Egypt in A.D. 1216, describes[377] in unmistakeable terms the form of the plant, its seeds and fruit, which last he remarks is eaten when young and tender with meat by the Egyptians. The plant was figured among Egyptian plants in 1592 by Prosper Alpinus,[378] who mentions its uses as an external emollient.
The powdered fruits as imported from Arabia Felix were known for some time (about the year 1848) in Europe as Nafé of the Arabs. They are noticed in the present work from the circumstance that they have a place in the Pharmacopœia of India.
=Description=—The fruit is a thin capsule, 4 to 6 or more inches long and about an inch in diameter, oblong, pointed, with 5 to 7 ridges corresponding to the valves and cells, each of which latter contains a single row of round seeds. It is covered with rough hairs and is green or purplish when fresh; it has a slightly sweet mucilaginous taste and a weak herbaceous odour. Like many other plants of the order, Hibiscus esculentus abounds in all its parts with insipid mucilage.
[375] Uëhka in Arabic, according to Schweinfurth. Okro or Okra are common names for the plant in the East and West Indies. Bendi-kai, a Canarese and Tamil word, is used by Europeans in the South of India. Gigambo in Curaçao.
[376] Fig. Bentley and Trimen, Med. Plants, part 35 (1878).
[377] Ibn Baytar, Sontheimer’s translation, i. 118; Wüstenfeld, Geschichte der Arab. Aerzte etc. 1840. 118.
[378] De plant. Ægypt., Venet. 1592. cap. 27.
=Microscopic Structure=—A characteristic part for microscopic examination are the hairs of the fruit. They exhibit at the base one large cell, but their elongated and often slightly curved end is built up at a considerable number of small cells, without any solid contents. The middle and outer zone of the pericarp shows enormous holes filled up with colourless mucilage. In polarized light it is easily seen to be composed of successive layers.
=Chemical Composition=—It is probable that the fruits contain the same mucilage as Althæa, but we have had no opportunity of investigating the fact. Landrin[379] says it turns violet with iodine and yields no mucic acid when treated with nitric acid. Popp, who examined the green fruits in Egypt, states[380] that they abound in pectin, starch and mucilage. He found that when dried they afforded 2 to 2·4 per cent. of nitrogen, and an ash rich in salts of lime, potash and magnesia. The ripe seeds gave 2·4-2·5 per cent. of nitrogen; their ash 24 per cent. of phosphoric acid.
=Uses=—The fresh or dried, unripe fruits are used in tropical countries as a demulcent like marshmallow, or as an emollient poultice, for which latter purpose the leaves may also be employed. They are more important from an economic point of view, being much employed for thickening soups or eaten boiled as a vegetable. The root has been recommended as a substitute for that of Althæa.[381] The stems of the plant yield a good fibre.
STERCULIACEÆ
=OLEUM CACAO.=
Butyrum Cacao, Oleum Theobromatis; Cacao Butter, Oil of Theobroma; F. Beurre de Cacao; G. Cacaobutter, Cacaotalg.
=Botanical Origin=—Cacao seeds (from which Cacao Butter is extracted) are furnished by Theobroma Cacao L., and apparently also by Th. leiocarpum Bernoulli, Th. pentagonum Bern., and Th. Salzmannianum Bern.[382] These trees are found in the northern parts of South America and in Central America as far as Mexico, both in a wild state and in cultivation.
=History=—Cacao seeds were first noticed by Capitan Gonzalo Fernandez de Oviedo y Valdés (1514-1523), who stated[383] that they had been met with by Columbus, being used among the inhabitants of Yucatan instead of money. They were likewise pointed out to Charles V., by Cortes in one of his letters to the Emperor, dated Temixtitan, Sept. 3rd 1526.[384] The tree as well as the seeds and their uses, were at length described by Benzoni,[385] who lived in the new world from 1541 to 1555. Clusius figured the seeds in his “Notæ in Garciæ Aromatum historiam,” Antwerpiæ, 1582.
[379] Journ. de Pharm. 22 (1875) 278.
[380] Archiv der Pharmacie, cxcv. (1871) 142.
[381] Della Sudda, Rép. de Pharm., Janvier, 1860. 229.
[382] Bernoulli, Uebersicht der bis jetzt bekannten Arten von Theobroma.—Reprinted from Denkschriften der Schweizerischen Gesellschaft für Naturwissenschaften, xxiv. (Zürich, 1869) 4°. 376.
[383] Historia general y naturel de las Indias islas y terra firme del mar oceano, iii. (Madrid, 1853) 253.
[384] Vedia, Cartas de relacion enviadas al emperador Carlos V. desde Nueva España. Madrid, 1852. T. 1.
[385] Chavveton (Urbain) Hist. nouv. du Nouveau Monde ... extraite del’ italien de M. Hierosme Benzoni Milanais. 1579. p. 504.
Cacao butter was prepared and described by Homberg[386] as early as 1695, at which time it appears to have had no particular application, but in 1719 it was recommended by D. de Quelus[387] both for ointments and as an aliment.
An essay published at Tübingen in 1735[388] called attention to it as “novum atque commendatissimum medicamentum.” A little later it is mentioned by Geoffroy[389] who says that it is obtained either by boiling or by expressing the seeds, that it is recommended as the basis of cosmetic pomades and as an application to chapped lips and nipples, and to hæmorrhoids.
=Production=—Cacao butter is procured for use in pharmacy from the manufacturers of chocolate, who obtain it by pressing the warmed seeds. These in the shelled state yield from 45 to 50 per cent. of oil. The natural seeds consist of about 12 per cent. of shell (testa) and 88 of kernels (cotyledons).
=Description=—At ordinary temperatures cacao butter is a light yellowish, opaque, dry substance, usually supplied in the form of oblong tablets having somewhat the aspect of white Windsor soap. Though unctuous to touch, it is brittle enough to break into fragments when struck, exhibiting a dull waxy fracture. It has a pleasant odour of chocolate, and melts in the mouth with a bland agreeable taste. Its sp. gr. is 0·961; its fusing point 20° to 30° C.
Examined under the microscope by polarized light, cacao butter is seen to consist of minute crystals. It is dissolved by 20 parts of boiling absolute alcohol, but on cooling separates to such an extent that the liquid retains not more than 1 per cent. in solution. The fat separated after refrigeration is found to have lost most of its chocolate flavour. Litmus is not altered by the hot alcoholic solution.
Cacao butter in small fragments is slowly dissolved by double its weight of benzol in the cold (10° C.), but by keeping partially separates in crystalline warts.
=Chemical Composition=—The fat under notice is composed, in common with others, of several bodies which by saponification furnish glycerin and fatty acids. Among the latter occurs also oleic acid,[390] contained in that part of the cacao butter which remains dissolved in cold alcohol as above stated. In fact by evaporating that solution a soft fat is obtained. But the chief constituents of cacao butter appear to be stearin, palmitin, and another compound of glycerin containing probably an acid of the same series richer in carbon,—perhaps arachic acid, C₂₀H₄₀O₂, or “theobromic acid” C₆₄H₁₂₈O₂, as suggested in 1877 by Kingzett.
[386] Hist. d. l’Acad. Roy. des Sciences, tome ii. depuis 1686 jusqu’à 1699, Paris, 1733. p. 248.
[387] Hist. nat. du Cacao et du Sucre, Paris, 1719. (According to Haller, Bibl. Bot. ii. 158.)
[388] B. D. Mauchart præside—dissertation Butyrum Cacao. Resp. Theoph. Hoffmann.
[389] Tract. de Mat. Med. ii. (1741) 409.
[390] See article Amygdalæ dulces.
=Uses=—Cacao butter, which is remarkable for having but little tendency to rancidity, has long been used in continental pharmacy; it was introduced into England a few years ago as a convenient basis for suppositories and pessaries.
=Adulteration=—The description given of the drug sufficiently indicates the means of ascertaining its purity.
LINEÆ
SEMEN LINI.
Linseed, Flax Seed; F. Semence de Lin; G. Leinsamen, Flachssamen.
=Botanical Origin=—Linum usitatissimum L., Common Flax, is an annual plant, native of the Old World, where it has been cultivated from the remotest times. It sows itself as a weed in tilled ground, and is now found in all temperate and tropical regions of the globe. Heer regards it as a variety evolved by cultivation from the perennial L. angustifolium Huds.
=History=—The history of flax, its textile fibre and seed, is intimately connected with that of human civilisation. The whole process of converting the plant into a fibre fit for weaving into cloth is frequently depicted on the wall-paintings of the Egyptian tombs.[391] The grave-clothes of the old Egyptians were made of flax, and the use of the fibre in Egypt may be traced back, according to Unger,[392] as far as the 23rd century B.C. The old literature of the Hebrews[393] and Greeks contains frequent reference to tissues of flax; and fabrics woven of flax have actually been discovered together with fruits and seeds of the plant in the remains of the ancient pile-dwellings bordering the lakes of Switzerland.[394]
The seed in ancient times played an important part in the alimentation of man. Among the Greeks, Alcman in the 7th century B.C., and the historian Thucydides, and among the Romans Pliny, mention linseed as employed for human food. The roasted seed is still eaten by the Abyssinians.[395]
Theophrastus expressly alludes to the mucilaginous and oily properties of the seed. Pliny and Dioscorides were acquainted with its medical application both external and internal. The latter, as well as Columella, exhaustively describes flax under its agricultural aspect. In an edict of the Emperor Diocletian De pretiis rerum venalium[396] dating A.D. 301, linseed is quoted 150 denarii, sesamé seed 200, hemp seed 80, and poppy seed 150, the modius castrensis, equal to about 880 cubic inches.[397] The propagation of flax in Northern Europe as of so many other useful plants was promoted by Charlemagne.[398] It seems to have reached Sweden and Norway before the 12th century.[399]
[391] Wilkinson, Ancient Egyptians, iii. (1837) 138, &c.
[392] Sitzungsberichte der Wiener Akademie, Juni 1866.
[393] Exod. ix. 31; Lev. xiii. 47, 48; Isaiah xix. 9.
[394] Heer in Trimen’s Journ. of Bot. i. (1872) 87.
[395] A. de Candolle, Géogr. Botanique, 835.—A. Braun, Flora, 1848. 94.
[396] See p. 65, note 1.
[397] The English imperial gallon = 277·27 cubic inches.
[398] For further historical information on flax in ancient times, we may refer to Hehn, Kulturpflanzen und Hausthiere ... Berlin, 1870. 97, 430.
[399] Schübeler, Die Pflanzenwelt Norwegens, Christiania, 1873-1875. p. 332.
=Description=—The capsule which is globose splits into 5 carpels, each containing two seeds separated by a partition. The seeds are of flattened, elongated ovoid form with an acute edge, and a slightly oblique point blunt at one end. They have a brown, glossy, polished surface which under a lens is seen to be marked with extremely fine pits. The hilum occupies a slight hollow in the edge just below the apex. The testa which is not very hard encloses a thin layer of albumen surrounding a pair of large cotyledons having at their pointed extremity a straight embryo. The seeds of different countries vary from ¼ to ⅙ of an inch in length, those produced in warm regions being larger than those grown in cold. We find that 6 seeds of Sicilian linseed, 13 of Black Sea and 17 of Archangel linseed weigh respectively one grain.
When immersed in water, the seeds become surrounded by a thin, slippery, colourless, mucous envelope, which quickly dissolves as a neutral jelly, while the seed slightly swells and loses its polish. The seed when masticated has a mucilaginous oily taste.
=Microscopic Structure=—On examining the testa under almond oil or oil of turpentine, the outlines of the epidermal cells are not distinctly visible. But under dilute glycerin or in water the epidermis quickly swells up to 3 or 4 times its original thickness; on warming, the entire epidermis is resolved into mucilage, except a thin skeleton of cell-walls, which withstands even the action of caustic lye. The formation of the mucilage may be conveniently studied by the use of a solution of ferrous sulphate, with which thin sections of the testa should be moistened. Other structural peculiarities may be seen if they are imbued with concentrated sulphuric acid, washed and then moistened with a solution of iodine. The application of polarized light is also useful. By the latter means crystalloid granules of albuminoid matter become visible if the sections are examined under oil. The tissue of the albumen and the cotyledons abounds in drops of fatty oil.
=Chemical Composition=—The constituent of chief importance is the fixed oil which the seed contains to about ⅓ of its weight. The proportion obtained by pressure on a large scale is 20 to 30 per cent. varying with the quality of the seed. The oil when pressed without heat and when fresh has but little colour, is without unpleasant taste, and does not solidify till cooled to -20° C. The commercial oil however is dark yellow, and has a sharp repulsive taste and odour. On exposure to the air, especially after having been heated with oxide of lead, it quickly dries up to a transparent varnish consisting chiefly of Linoxyn, C₃₂H₅₄O₁₁. The crude oil increases in weight 11 to 12 per cent., although at the same time its glycerin is destroyed by oxidation.
By saponification, linseed oil yields glycerin, and 95 per cent. of fatty acids, consisting chiefly of Linoleic Acid, C₁₆H₂₆O₂, accompanied by some oleic, palmitic, and myristic acid. The action of the air transforms linoleic acid into the resinoid Oxylinoleic Acid, C₁₆H₂₆O₅. Linoleic acid appears to be contained in all drying oils, notably in that of poppy seed. It is not homologous either with ordinary fatty acids or with the oleic acid of oil of almonds, C₁₈H₃₄O₂. The chemistry of the drying oils, especially those of linseed and poppy, has been particularly investigated by Mulder.[400]
The viscid mucilage of linseed cannot be filtered till it has been boiled. It contains in the dry state more than 10 per cent. of mineral substances, when freed from which and dried at 110° C. it corresponds, like althæa-mucilage, to the formula C₁₂H₂₀O₁₀. The seeds by exhaustion with cold or warm water afford of it about 15 per cent. By boiling nitric acid it yields crystals of mucic acid; by dilute mineral acids it is broken up into dextrogyre gum and sugar and cellulose.[401]
Linseed contains about 4 per cent. of nitrogen corresponding to about 25 per cent. of protein-substances. After expression of the oil these substances remain in the cake so completely that the latter contains 5 per cent. of nitrogen, and constitutes a very important article for feeding cattle.
In the ripe state linseed is altogether destitute of starch, though this substance is found in the immature seed in the very cells which subsequently yield the mucilage. The latter may be regarded as in analogous cases to be a product of the transformation of starch.
The amount of water retained by the air-dry seed is about 9 per cent.
The mineral constituents of linseed, chiefly phosphates of potassium, magnesium, and calcium, amount on an average to 3 per cent., and pass into the mucilage. By treating thin slices of the testa and its adhering inner membrane with ferrous sulphate, it is seen that this integument is the seat of a small amount of tannin.
=Production and Commerce=—Flax is cultivated on the largest scale in Russia, from which country there was imported into the United Kingdom in 1872 linseed to the value of 3 millions sterling. The shipments were made in about equal proportion from the northern and the southern ports of Russia.
The imports from India in the same year amounted in value to £1,144,942, and from Germany and Holland to £144,108. The total import in 1872 was 1,514,947 quarters, value £4,513,842.
The cultivation of flax in Great Britain appears to be declining. The area under this crop in 1870 was 23,957 acres; in 1871, 17,366 acres; in 1872, 15,357 acres; and in 1873, 14,683 acres. The last named area reckoning the yield at 2 to 2½ quarters of seed per acre would represent a production of about 30,000 to 38,000 quarters.
[400] His numerous investigations on this subject have been published in a separate pamphlet, of which we have before us a German translation: G. J. Mulder, Die Chemie der austrocknenden Oele ... Berlin, 1867, pp. 255.
[401] Kirchner and Tollens, Annalen der Chemie, 175 (1874) 215.
In English price-currents, eight sorts of linseed are enumerated, namely, English, Calcutta, Bombay, Egyptian, Black Sea and Azof, Petersburg, Riga, Archangel. The first three appear to fetch the highest prices.
=Uses=—In medicine, linseed is chiefly used in the form of poultice which may be made either of the seed simply ground or of the pulverized cake. In either case the powder should not be long stored, as the oil in the comminuted seed is rapidly oxidized and fatty acids produced. An infusion of the seeds called Linseed Tea is a common popular demulcent remedy.
=Adulteration=—Linseed is very liable to adulteration with other seeds, especially when the commodity is scarce. The admixture in question is due in part to careless harvesting and in part to intentional additions. In 1864 the impure condition of the linseed shipped to the English market had become so detrimental to the trade that the importers and crushers founded an association called The Linseed Association of London, by which they bound themselves to refuse all linseed containing more than 4 per cent. of foreign seeds, and this step very rapidly improved the quality of the article.[402]
[402] Greenish in Yearbook of Pharmacy, 1871. 590; Pharm. Journ. Sept. 9, 1871. 211.
As the druggist has to purchase linseed meal, he must of necessity rely to some extent on the character of the oil-presser from whom he derives his supplies. The presence of the seeds of Cruciferæ (as rape and mustard) which is common, may be recognized by the pungent odour of the essential oil which they develope in contact with water. The introduction of cereals would also be easily discovered by iodine, which strikes no blue colour in a decoction of linseed. The microscope will also afford important aid in the examination of linseed cake or meal.
ZYGOPHYLLEÆ
LIGNUM GUAIACI.
Lignum sanctum; Guaiacum Wood, Lignum Vitæ; F. Bois de Gaïac; G. Guaiakholz, Pockholz.
=Botanical Origin=—This wood is furnished by two West Indian species of Guaiacum, namely:—
1. G. officinale L., a middle-sized or low evergreen tree, with light blue flowers, parapinnate leaves having ovate, very obtuse leaflets in 2, less often in 3 pairs, and 2-celled fruits. It grows in Cuba, Jamaica (abundantly on the arid plains of the south side of the island), Les Gonaives in the N.W. of Hayti (plentiful), St. Domingo, Martinique, St. Lucia, St. Vincent, Trinidad, and the northern coast of the South American continent. This tree affords the Lignum Vitæ of Jamaica (of which very little is imported), a portion of that shipped from the ports of Hayti, and probably the small quantity exported by the United States of Colombia.
2. G. sanctum L., a tree much resembling the preceding, but distinguishable by its leaves having 3 to 4 pairs of leaflets which are very obliquely obovate or oblong, passing into rhomboid-ovate, and mucronulate; and a 5-celled fruit. It is found in Southern Florida, the Bahama Islands, Key West, Cuba, St. Domingo (including the part called Hayti) and Puerto Rico, and is certainly the source of the small but excellent Lignum Vitæ exported from the Bahamas as well as of some of that shipped from Hayti.
=History=—There can be no doubt but that the earliest importations of Lignum Vitæ were obtained from St. Domingo, of which island, Oviedo[403] who landed in America in 1514 mentions the tree, under the name of Guayacan, as a native. He points out its fruits as yellow and resembling two joined lupines, which could only be said with reference to G. officinale, and would not apply to the ovoid five-cornered fruits of G. sanctum. Oviedo appears however to have been aware of two species, one of which he found in Española (St. Domingo) as well as in Nagrando (Nicaragua) and the other in the island of St. John (Puerto Rico), whence it was called Lignum sanctum.
The first edition of Oviedo was printed in 1526; but some years before this the wood must have been known in Germany, as is evident by the treatises written in 1517, 1518, and 1519 by Nicolaus Poll,[404] Leonard Schmaus[405] and Ulrich von Hutten.[406] The last which gives a tolerable description of the tree, its wood, bark, and medicinal properties, was translated into English in 1533 by Thomas Paynel, canon of Merton Abbey, and published in London in 1536 under the title—“Of the wood called Guaiacum that healeth the Frenche Pockes and also helpeth the gout in the feete, the stoone, the palsey, lepree, dropsy, fallynge euyll, and other dyseases.” It was several times reprinted.
In the old pharmacy the products of destructive distillation of guaiacum wood were known as Oleum ligni sancti. It must have consisted of the substances which we mention further on in the following article.
=Description=—The wood (always known in commerce as Lignum Vitæ) as imported consists of pieces of the stem and thick branches, usually stripped of bark, and often weighing a hundredweight each. It is remarkably heavy and compact. Its sp. gr. which exceeds that of most woods is about 1·3.
Lignum Vitæ is mostly imported for turnery,[407] and the chips, raspings and shavings are the only form in which it is commonly seen in pharmacy. A stem 7 to 8 inches in diameter cut transversely exhibits a light-yellowish zone of sapwood about an inch wide, enclosing a sharply defined heartwood of a dark greenish brown. Both display alternate lighter and darker layers, which especially in the sapwood are further distinguished by groups of vessels. In this manner are formed a large number of circles resembling annual rings, the general form of which is evident, though the individual rings are by no means well defined. More than 20 such rings may be counted in the sapwood of a log such as we have mentioned, and more than 30 in the heartwood. The pithless centre is usually out of the axis. The medullary rays are not visible to the naked eye, but may be seen by a lens to be very numerous and equidistant. The pores of the heartwood may be distinguished as containing a brownish resin, while those of the outermost layer of sapwood are empty.
[403] Natural Hystoria de las Indias, Toledo, 1526. fol. xxxvii.
[404] Decura Morbi Gallici per Lignum Guayacanum libellus, printed in 1535 but dated 19 Dec. 1517, 8 pages 8°.
[405] De Morbo Gallico tractatus, Salisburgi, November 1518,—reprinted in the Aphrodisiacus of Luisinus, Lugd. Bat. 1728. 383.—We have only seen the latter.
[406] Ulrichi de Hutten equitis de Guaiaci medicina et morbo gallico liber unus, 4°. (26 chapters) Moguntiæ, 1519.
[407] It is much used for the wheels (technically “sheaves”) of ships’ blocks (pulleys), the circumference of which ought to consist of the white sapwood. It is also required for caulking mallets, skittle balls and for the large balls used in American bowling alleys, for which purposes it should be as sound and homogeneous as possible.
In the thickest pieces sapwood is wanting, and even in stems of about a foot in diameter it is reduced to ⅕ of an inch. It is of looser texture than the heartwood and floats on water, whereas the latter sinks. Both sapwood and heartwood owe their tenacity to an extremely peculiar zigzag arrangement[408] of the woody bundles. The sapwood is tasteless. The heartwood has a faintly aromatic and slightly irritating taste, and when heated or rubbed emits a weak agreeable odour.
The bark which was formerly officinal but is now almost obsolete, is very rich in oxalate of calcium and affords upon incineration not less than 23 per cent. of ash. It contains a resin distinct from that of the wood, and also a bitter acrid principle.[409]
The Lignum Vitæ of Jamaica (G. officinale) and that of the Bahamas (G. sanctum), of which authentic specimens have been kindly placed at our disposal by Mr. G. Shadbolt, display the same appearance as well as microscopic structure.[410]
=Microscopic Structure=—The wood consists for the most part of pointed, not very long, ligneous cells (libriform), traversed by one-celled rows of medullary rays. There are also thin layers of parenchymatous tissue, to which the zones apparent in a transverse section of the drug are due. The pitted vessels are comparatively large but not very numerous. The structure of the sapwood is the same as that of the heartwood, but in the latter the ligneous cells are filled with resin. The parenchymatous cells contain crystals of oxalate of calcium.
=Chemical Composition=—The only constituent of any interest is the resin which the heartwood contains to the extent of about a fourth of its weight. The sapwood afforded us 0·91 and the heartwood 0·60 per cent. of ash.
=Commerce=—Lignum Vitæ varies much in estimation, according to size, soundness, and the cylindrical form of the logs. The best is exported from the city of Santo Domingo, whither it is brought from the interior of the island. The quantity shipped from this port during 1871 was 1494 tons;[411] 220 tons were exported in 1877 from Puerto Plata on the northern coast of the island. The wood obtained from the Haytian ports (of the western part of the same island) is much less esteemed in the London market.
[408] It has been remarkably well pointed out already by Valerius Cordus (obiit 1544). See Gesner’s edition of his Hist. Stirpium Argentorat., 1561. 191.
[409] See also Oberlin et Schlagdenhauffen, Journ. de Pharm. 28 (1878) 246 and plate vi.
[410] That of Guaiacum arboreum DC. is apparently very different. This tree, occurring in New Granada, has already been noticed (1571-1577) by Francisco Hernandez (Nova plantarum, animal, et mineral. mexicanor. hist., Romæ 1651, fol. 63) under the name of Guayacan. He mentions its large umbels with yellow flowers, those of Guaiacum officinale, the “Hoaxacan” or Lignum sanctum, being blue. In the Prodromus Floræ Neo-Granatentis (Ann. Scienc. nat. xv., 1872. p. 361) J. E. Planchon also describes Guaiacum arboreum, known there as Guayacan polvillo; its wood is of an almost pulverulent fracture.
[411] Consular Reports presented to Parliament, Aug. 1872.
Some small wood of good quality comes from the Bahamas, and an ordinary quality, also small, from Jamaica. From the latter island, the quantity exported in 1871 was only 14 tons;[412] from the Bahamas in the same year 199 tons.[413] Lignum Vitæ was shipped from Santa Marta in 1872 to the extent of 115 tons.[414]
Hamburg is also an important place for the wood under notice; in 1877 there were imported 22,404 centners from S. Domingo and 3551 centners from Venezuela.
=Uses=—Guaiacum wood is only retained in the pharmacopœia as an ingredient of the Compound Decoction of Sarsaparilla. It is probably inert, at least in the manner in which it is now administered.[415]
=Adulteration=—In purchasing guaiacum chips it is necessary to observe that the non-resinous sapwood is absent, and still more that there is no admixture of any other wood. A spurious form of the drug seems to be by no means rare in the United States.[416]
RESINA GUAIACI
Guaiacum Resin; F. Résine de Gaïac; G. Guaiakharz.
=Botanical Origin=—Guaiacum officinale L., see preceding article.
=History=—Hutten[417] in 1510 stated that guaiacum wood when set on fire exudes a blackish resin which quickly hardens, but of which he knew no use. The resin was in fact introduced into medicine much later than the wood. The first edition of the London Pharmacopœia in which we find the former named is that of 1677.
=Production=[418]—In the island of St. Domingo, whence the supplies of guaiacum resin are chiefly derived, the latter is collected from the stems of the trees, in part as a natural exudation, and in part as the result of incisions made in the bark. In some districts as in the island of Gonave near Port-au-Prince, another method of obtaining it is adopted. A log of the wood is supported in a horizontal position above the ground by two upright bars. Each end of the log is then set on fire, and a large incision having been previously made in the middle, the melted resin runs out therefrom in considerable abundance. 36,350 lbs. of it have been exported in 1875 from Port-au-Prince.
The resin is collected chiefly from G. officinale, which affords it in greater plenty than G. sanctum.
[412] Blue Book—Island of Jamaica for 1871.
[413] Blue Book for Colony of Bahamas for 1871.
[414] Consular Reports, Aug. 1873. 746.
[415] The ancient treatment of syphilis by guaiacum which gained for the drug such immense reputation, consisted in the administration of vast quantities of the decoction, the patient being shut up in a warm room and kept in bed.—See Hutten’s pamphlet quoted before, and its numerous reprints and translations.
[416] Schulz, in the (Chicago) Pharmacist, Sept. 1873.
[417] Op. cit. at p. 101.
[418] We have to thank Mr. Eugène Nau of Port-au-Prince for the information given under this head, as well as for some interesting specimens.
=Description=—The resin occurs in globular tears ½ an inch to 1 inch in diameter, but much more commonly in the form of large compact masses, containing fragments of wood and bark. The resin is brittle, breaking with a clean, glassy fracture; in thin pieces it is transparent and appears of a greenish brown hue. The powder when fresh is grey, but becomes green by exposure to light and air. It has a slight balsamic odour and but little taste, yet leaves an irritating sensation in the throat.
The resin has a sp. gr. of about 1·2. It fuses at 85° C., emitting a peculiar odour somewhat like that of benzoin. It is easily soluble in acetone, ether, alcohol, amylic alcohol, chloroform, creosote, caustic alkaline solutions, and oil of cloves; but is not dissolved or only partially by other volatile oils, benzol or bisulphide of carbon. By oxidizing agents it acquires a fine blue colour, well shown when a fresh alcoholic solution is allowed to dry up in a very thin layer and this is then sprinkled with a dilute alcoholic solution of ferric chloride. Reducing agents of all kinds, and heat produce decoloration. An alcoholic solution may be thus blued and decolorized several times in succession, but it loses at length its susceptibility. This remarkable property of guaiacum was utilized by Schönbein in his well-known researches on ozone.
=Chemical Composition=—The composition of guaiacum resin was ascertained by Hadelich (1862) to be as follows:—
Guaiaconic Acid, 70·3 per cent. Guaiaretic Acid, 10·5 ” Guaiac Beta-resin, 9·8 ” Gum, 3·7 ” Ash constituents, 0·8 ” Guaiacic Acid, colouring matter (Guaiac-yellow), and impurities, 4·9 ”
If the mother-liquor obtained in the preparation of the potassium salt of guaiaretic acid (vide infra) is decomposed by hydrochloric acid, and the precipitate washed with water, ether will extract from the mass Guaiaconic Acid, a compound discovered by Hadelich, having the formula C₃₈H₄₀O₁₀. It is a light brown, amorphous substance, fusing at 100° C. It is without acid reaction but decomposes alkaline carbonates, forming uncrystallizable salts easily soluble in water or alcohol. It is insoluble in water, benzol, or bisulphide of carbon, but dissolves in ether, chloroform, acetic acid or alcohol. With oxidizing agents it acquires a transient blue tint.
Guaiaretic Acid, C₂₀H₂₆O₄, discovered by Hlasiwetz in 1859, may be extracted from the crude resin by alcoholic potash or by quicklime. With the former it produces a crystalline salt; with the latter an amorphous compound: from either the liquid, which contains chiefly a salt of guaiaconic acid, may be easily decanted. Guaiaretic acid is obtained by decomposing one of the salts referred to with hydrochloric acid, and crystallizing from alcohol. The crystals, which are soluble also in ether, benzol, chloroform, carbon bisulphide or acetic acid, but neither in ammonia nor in water, melt below 80° C., and may be volatilized without decomposition. The acid is not coloured blue by oxidizing agents.
By exhausting guaiacum resin with boiling bisulphide of carbon a slightly yellowish solution is obtained (containing chiefly guaiaretic acid?), which, on addition of concentrated sulphuric acid, turns beautifully red.
After the extraction of the guaiaconic acid there remains a substance insoluble in ether to which the name Guaiac Beta-resin has been applied. It dissolves in alcohol, acetic acid or alkalis, and is precipitated by ether, benzol, chloroform or carbon bisulphide in brown flocks, the composition of which appears not greatly to differ from that of guaiaconic acid.
Guaiacic Acid, C₁₂H₁₆O₆, obtained in 1841 by Thierry from guaiacum wood or from the resin, crystallizes in colourless needles. Hadelich was not able to obtain more than one part from 20,000 of guaiacum resin.
Hadelich’s Guaiac-yellow, the colouring matter of guaiacum resin, first observed by Pelletier, crystallizes in pale yellow quadratic octohedra, having a bitter taste. Like the other constituents of the resin, it is not a glucoside.
The decomposition-products of guaiacum are of peculiar interest. On subjecting the resin to dry distillation in an iron retort and rectifying the distillate, Guaiacene (Guajol of Völckel), C₅H₈O, passes over at 118° C. as a colourless neutral liquid having a burning aromatic taste.
At 205°-210° C., there pass over other products, Guaiacol, C₆H₄·OCH₃·OH, (methylic ether of pyrocatechin), and Kreosol C₆H₃·OH(CH₃)₂. Both are thickish, aromatic, colourless liquids, which become green by caustic alkalis, blue by alkaline earths, and are similar in their chemical relations to eugenic acid. Guaiacol has been prepared synthetically by Gorup-Besanez (1868) by combining iodide of methyl, CH₃I, with pyrocatechin, C₆H₄(OH)₂.
After the removal by distillation of the liquids just described, there sublime upon the further application of heat pearly crystals of Pyroguaiacin, C₃₈H₄₄O₆, an inodorous substance melting at 180° C. The same compound is obtained together with guaiacol by the dry distillation of guaiaretic acid. Pyroguaiacin is coloured green by ferric chloride, and blue by warm sulphuric acid. The similar reactions of the crude resin are probably due to this substance (Hlasiwetz).
Beautiful coloured reactions are likewise exhibited by two new acids which Hlasiwetz and Barth obtained (1864) in small quantity together with traces of fatty volatile acids, by melting purified resin of guaiacum with potassium hydrate. One of them is isomeric with pyrocatechuic acid.
=Uses=—Guaiacum resin is reputed diaphoretic and alterative. It is frequently prescribed in cases of gout and rheumatism.
=Adulteration=—The drug is sometimes imported in a very foul condition and largely contaminated with impurities arising from a careless method of collection.
RUTACEÆ
CORTEX ANGOSTURÆ.
Cortex Cuspariæ; Angostura Bark, Cusparia Bark, Carony Bark; F. Ecorce d’Angusture de Colombie; G. Angostura-Rinde.
=Botanical Origin=—Galipea Cusparia St. Hilaire (G. officinalis Hancock, Bonplandia trifoliata Willd., Cusparia trifoliata Engler 1874, Flora Brasil. 113), a small tree, 12 to 15 feet high, with a trunk 3 to 5 inches in diameter, growing in abundance on the mountains of San Joaquin de Caroni in Venezuela, between 7° and 8° N. lat., also according to Bonpland[419] near Cumana. According to Hancock,[420] who was well acquainted with the tree, it is also found in the Missions of Tumeremo, Uri, Alta Gracia, and Cupapui, districts lying eastward of the Caroni and near its junction with the Orinoko. The bark is brought into commerce by way of Trinidad.
=History=—Angostura Bark is said to have been used in Madrid by Mutis as early as 1759[421] (the year before he left Spain for South America,) but it was certainly unknown to the rest of Europe until much later. Its real introducer was Brande, apothecary to Queen Charlotte, and father of the distinguished chemist of the same name, who drew attention to some parcels of the bark imported into England in 1788.[422] In the same year a quantity was sent to a London drug firm by Dr. Ewer of Trinidad, who describes it[423] as brought to that island from Angostura by the Spaniards. The drug continued to arrive in Europe either by way of Spain or England, and its use was gradually diffused. In South America it is known as Quina de Caroni and Cascarilla del Angostura.
=Description=—The bark occurs in flattish or channelled pieces, or in quills rarely as much as 6 inches in length and mostly shorter. The flatter pieces are an inch or more in width and ⅛ of an inch in thickness. The outer side of the bark is coated with a yellowish-grey corky layer, often soft enough to be removeable with the nail, and then displaying a dark brown, resinous under surface. The inner side is light brown with a rough, slightly exfoliating surface indicating close adhesion to the wood, strips of which are occasionally found attached to it; the obliquely cut edge also shows that it is not very easily detached. The bark has a short, resinous fracture, and displays on its transverse edge sharply defined white points, due to deposite of oxalate of calcium. It has a bitter taste and a nauseous musty odour.
[419] Humboldt, Reise in die Aequinoctialgegenden des neuen Continents, iv. (Stuttgart, 1860), 252.—Humboldt and Bonpland in 1804 obtaining, from the Caroni river, flowering branches of the “Cuspa” (l. c. 1. 300) or “Cuspare,” as it is called by the Indians, believed it to constitute a new genus. In 1824 St. Hilaire ascertained it to belong to the genus Galipea.
The tree is figured in Bentley and Trimen, Med. Plants, part 26 (1877).
[420] Observations on the Orayuri or Angustura Bark Tree,—Trans. of Medico-Botanical Society, 1827-29.—Hancock endeavoured to prove his tree distinct from G. Cusparia St. Hil., but Farre and Don who subsequently examined his specimens decided that the two were the same. With the assistance of Prof. Oliver, I also have examined (1871) Hancock’s plant, comparing it with his figure and other specimens, and have arrived at the conclusion that it is untenable as a distinct species.—D. H.
[421] Martiny, Encyklopädie, i. (1843) 242.
[422] Brande, Experiments and Observations on the Angustura Bark. 1791. 2nd ed. 1793.
[423] London Med. Journ. x. (1789) 154.
=Microscopic Structure=—The most striking peculiarity is the great number of oil-cells scattered through the tissue of the bark. They are not much larger than the neighbouring parenchymatous cells, and are loaded with yellowish essential oil or small granules of resin. Numerous other cells contain bundles of needle-shaped crystals of oxalate of calcium or small starch granules. The liber exhibits bundles of yellow fibres, to which the foliaceous fracture of the inner bark is due. The structure of the bark under notice has been very minutely described and figured by Oberlin and Schlagdenhauffen.[424]
=Chemical Composition=—Angostura bark owes its peculiar odour to an essential oil which it was found by Herzog[425] to yield to the extent of ¾ per cent. It is probably a mixture of a hydrocarbon (C₁₀H₁₆) with an oxygenated oil. Its boiling point is 266° C. Oberlin and Schlagdenhauffen obtained 0·19 per cent. of the oil, and found it to be slightly dextrogyre; it assumes a fine red colour when shaken with aqueous ferric chloride, and turns yellow with concentrated sulphuric acid.
[424] Journ. de Pharm. et de Chimie, 28 (1877), 226; plates I, II, III. The bark is also figured by Berg, Anatomischer Atlas, Tab. 37.
[425] Archiv d. Pharm. xcii. (1858) 146.
The bitter taste of the bark is attributed to a substance pointed out in 1833 by Saladin and named Cusparin. It is said to be crystalline, neutral, melting at 45° C., soluble in alcohol, sparingly in water, precipitable by tannic acid. The bark is stated to yield it to the extent of 1·3 per cent. Herzog endeavoured to prepare it but without success, nor have Oberlin and Schlagdenhauffen met with it. The latter chemists, on the other hand, isolated an alkaloid Angosturine C₁₀H₄₀NO₁₄. It is in thin prisms, melting at 85° and yielding a crystallized chlorhydrate or sulphate. Angosturine turns red when touched with concentrated sulphuric acid, or green if nitric acid or iodic acid, or other oxydizing substances, have been previously mixed with the sulphuric acid. The alcoholic solution of the alkaloid is of decidedly alkaline reaction. A cold aqueous infusion of angostura bark yields an abundant red-brown precipitate with ferric chloride. Thin slices of the bark are not coloured by solution of ferrous sulphate, so that tannin appears to be absent.
=Uses=—Angostura bark is a valuable tonic in dyspepsia, dysentery and chronic diarrhœa, but is falling into disuse.
=Adulteration=—About the year 1804, a quantity of a bark which proved to be that of Strychnos Nux Vomica reached Europe from India, and was mistaken for Cusparia. The error occasioned great alarm and some accidents, and the use of angostura was in some countries even prohibited. The means of distinguishing the two barks (which are not likely to be again confounded) are amply contained in the above-given descriptions and tests, and at length pointed out by Oberlin and Schlagdenhauffen. They also described the bark of Esenbeckia febrifuga Martius (Evodia febrifuga Saint Hilaire), a Brazilian tree belonging to the same natural order. Maisch[426] was the first to draw attention to this “new false Angostura bark.” It is at once distinguished by being devoid of aromatic properties; its taste is purely bitter.