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, the Caucasian region, Western India, as well as in Southern Siberia. 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 Νάπυ,-Dioscorides as Νάπυ or Σίνηπι. Pliny notices three kinds which have been referred by Fée1 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. 3012 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. 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. 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 1s. 3d. to 6s. 8d. per quarter, but in 1347 and 1376 it was as high as 15s. and 16s1 In the accounts of the abbey of St. Germaindes-Prés in Paris, commencing A.D. 800, mustard is specifically mentioned as a regular part of the revenue of the convent lands.5 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 diameter and 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." 1 Botanique et Matière Méd. de Pline, ii. (1833) 446. * Mommsen in Berichte. d. Gesell. d. Wissenschaften zu Leipzig, 1851. 1-80. 3 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. of an inch in 4 Rogers, Hist. of Agriculture and Prices in England, i. (1866) 223. 5 Guérard, Polyptique de l'Abbé Irminon, Paris, i. (1844) 715. 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. 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. 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. 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. CN) The oil, which has the composition C4HNS or C3H5} S (allyl sulphocyanide), boils at 148° C.; it has a sp. gr. of 1017, 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 Sulphocyanide of allyl or mustard oil C4 H5 NS H KS 04 06 so that the formula C10 H18 KNS2 010 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. This albuminous body discovered by Bussy in 1839, but the com position 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 C6H10S = CHS, 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 garlick. 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.1 The artificial preparation of mustard oil was discovered in 1855 by Zinin, and at the same time also by Berthelot and De Luca. Mustard submitted to pressure affords about 23 per cent.2 of a mildtasting, 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, C20H3802, which occurs in the fixed oil of both black and white mustard. 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 1 See also Radix Armoracia, p. 68. 2 I have obtained as much as 33.8 per cent. by means of boiling ether.-F. A. È. Mustard prepared for the table, which contains in addition white mustard, answers perfectly well and is at hand in every house.1 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.2 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. 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 authors3 it was introduced into China from the latter region. Its cultivation in England is of recent introduction, but is rapidly extending. The plant is not uncommon as a weed on cultivated land. History-White mustard was used in former times indiscriminately with the brown. In the materia medica of the London Pharmacopoeia of 1720 the two sorts are separately prescribed. The important chemical distinction between them was first made known in 1831 by BoutronCharlard and Robiquet.5 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 of an inch in diameter and 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. 1 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. 2 Annual Statement of the Trade and Navigation of British India, Calcutta, 1872. 62. 3 Bretschneider, Study of Chinese Botan. Works, 1870. 17. 4 Morton's Cyclop. of Agriculture, ii. (1855) 440. 5 Journ. de Pharm. xvii. (1831) 279. 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.1 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: so that the formula C30 H44 N2 S2 016 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. 63). 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, CH'NO: 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.2 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. 1 An interesting object for the polarizing microscope. 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. F |