The Pharmaceutical Journal AND Transactions. VOL. II.-No. I.-JULY 1, 1871. THE APPLICATION OF THE MOLECULAR ROTATION TO THE DETERMINATION OF THE VALUE OF CINCHONA BARKS. BY DR. E. J. DE VRIJ. The strong deviation of the plane of polarization in different direction or different intensity by all the known cinchona alkaloids, induced me to try to apply this action to test the value of the cinchona barks; and, although I readily confess that my experiments in this direction are far from being complete, yet the results already obtained seem to me interesting enough to fix attention on this new method of investigation, so that their publication may, perhaps, afford some interest. Before proceeding to the description of my method, it may, perhaps, not be superfluous to state the principles upon which it is based. The molecular rotations of the cinchona alkaloids which are known with certainty are the following:Quinine: in alcoholic solution [a]j=184°35) De Vrij and [a]j=287°·16„, } Alluard. in acid solution. Quinidine: in alcoholic solution [a]j=144° 61 Bouchardat. Pasteur. in acid solution . . [a]j, not yet determined. Besides these four alkaloids, about whose existence all chemists agree, and whose properties are well known, there exists in the cinchona barks still a fifth alkaloid, which is amorphous, soluble in ether, and whose compounds with acids are equally amorphous. I have long been uncertain if this alkaloid has an action on the plane of polarization, and it is only very recently that I became persuaded that it deviates from that plane slightly to the right. I have, however, not yet succeeded in determining the exact amount of this deviation, because this alkaloid is always yellow-coloured, and very difficult to obtain perfectly pure. It is clear from the preceding that the different cinchona alkaloids possess a different rotation, and that some of them deviate the plan of polarization in an opposite direction. Therefore, in examining optically the combined alkaloids of any bark, three cases can occur: THIRD SERIES, No. 53. 88-93 I. The alkaloids may prove inactive, viz. to exercise no deviation at all. This case, although not yet observed by me, may present itself, if the relative quantities of the alkaloids are such that their opposite deviations neutralize each other. II. They are turned to the right (dextrogyre =) if the quantity of quinidine, cinchonine or amorphous alkaloid exceeds that of quinine or cinchonidine. III. They are turned to the left (lævogyre =) if the quantity of quinine or cinchonidine exceeds that of the other alkaloids. From the facts mentioned, it appears that the deviation produced by quinine is different, depending on its being observed in solution in alcohol or in a diluted acid. It is very probable that this difference exists in the same direction with the other alkaloids, and its determination will be very desir able. Taking now in consideration that, of the five mentioned alkaloids, two of them, viz. the quinine and the amorphous alkaloid, are very soluble in ether, whilst the three remaining alkaloids are sparingly soluble in this liquid; it follows that, if the alkaloids are treated with ether, the deviation exercised by the part insoluble in ether will prove to be very different from that observed before. This dif ferent deviation may be the following: (1.) No deviation, if the part insoluble in ether contains enough of cinchonidine to neutralize the opposite deviation of the cinchonine.* (2.) Deviation to the right (dextrogyre) if the part insoluble in ether consists of cinchonine or quinidine, that of the eventually present cinchonidine. The or both of them, or if their quantity is superior to intensity of the deviation may throw some light upon this alternative. soluble in ether consists either totally or chiefly of (3.) Deviation to the left (lævogyre), if the part incinchonidine. In this case the intensity of the deviation will equally throw light upon the alternative. sists in the difficulty to obtain solutions of the alkaThe great difficulty with these observations conloids which are not too much coloured. The first As quinidine deviates to the right like cinchonine, it can equally neutralize the deviation to the left of the cinchonidine. It is, however, very rare that cinchonidine and qui nidine occur in the same bark. Till now I have only found one example of this combined occurrence, viz. in the bark of C. Hasskarliana, Miq.), in which bark I found the four the hybrid from C. Calisaya and C. Pahudiana (the so-called alkaloids, together with the amorphous alkaloid soluble in ether. requisite to measure accurately the deviations is that the solution is colourless, and till now I have not yet succeeded in obtaining this desideratum, but have been obliged to be satisfied by obtaining solutions which had a slightly yellow colour. I obtained these solutions as follows:-After ascertaining the total amount of alkaloids in a bark, the alkaloids were dissolved in weak acetic acid, and to this solution added a few drops of basic acetate of lead. After separating the lead by a current of sulphuretted hydrogen the liquid, much discoloured by the precipitated sulphide of lead, was filtered, and the alkaloids precipitated by caustic soda. The precipitate being washed and dried, one may proceed to prepare the solution for the optical observation. The alkaloids are accurately weighed, and the determined weight called p. This quantity is dissolved in diluted sulphuric acid, and the volume of the solution accurately measured.* This volume is called V, and filtered immediately into the tube, in which it will be observed. This tube has a length of 100 millimetres. After the tube has been completely filled and closed, and it has been ascertained that its contents are perfectly clear and transparent, it can be observed in the instrument. If the different alkaloids are present in such quantities that their opposite deviations neutralize each other, the molecular rotation is = 0°, and this result needs only to be noted. If, however, a deviation is observed, this deviation is noted as a to the amount of degrees of deviation observed, either to the right or the left; for instance, a°=3°2, or a° 3°, etc. One has now the necessary data to calculate the molecular rotation = [a]j of the mixed alkaloids by using the formula: Weight and measure are of the metric system. The instrument used by me is the polarist robometer, of Wild. It is, however, clear that any other good instrument may be used. Although the sulphide of lead has a very favourable action in taking away a great part of the colour of the solution, its action is not the same with all kinds of bark. I am therefore unable to state with certainty the quantity of alkaloids which ought to be dissolved in a certain volume. It is desirable to make a solution which contains 0-1 of the alkaloids. This is, however, in general not possible, because of the too intense colour, wherefore the quantity of the alkaloids in the solution varies between 0-1 and 0-05. § These observations have been made by Dr. B. Simpson, Surgeon, of the Bengal Army, in my laboratory at the Hague, in February 1870. Total amount of alkaloids 1-5 per cent. [a]j = 26°35 K. 4. C. succirubra, from Darjeeling. Stem-bark of plants 34 years old. Total amount of alkaloids 5'6 per cent. [a]j = 13°59 K. The alkaloids consisted of quinine, cinchonidine (both lævogyre), cinchonine and amorphous alkaloid (both dextrogyre). 5. C. succirubra from Ootacamund. Renewed bark (fourth harvest). Total amount of alkaloids, 9 per cent. [a]j=55°55. The part insoluble in ether proved [a]j=199.8.. The same alkaloids as in 4, but more cinchonidine and less cinchonine. 6. C. officinalis from Darjeeling. Total amount of alkaloids 768 per cent. [a]j= Stem-bark (one year covered by moss). 56°.35. = The part insoluble in ether proved [a]j 130.20. The same alkaloids as in 4 and 5, but much more quinine, of which the quantity amounted to 3:4 per cent. 7. C. officinalis from Ootacamund. Renewed bark (second harvest). Total amount of alkaloids, 8 per cent. [a]j = 139° 49. The same alkaloids as in 6, but containing much more quinine; they were almost entirely soluble in ether. B.-OBSERVATIONS BY MYSELF. 1. C. Calisaya from Darjeeling. Bark of trees three years old. Total amount of alkaloids, 3 per cent. [a]j = 1200.7. The part insoluble in ether proved [a]j=1740·34 Z. The alkaloids consisted of cinchonine, quinine, amorphous alkaloid and cinchonidine. 2. C. hybrida from Darjeeling, probably from C. Calisaya and C. officinalis. Bark of trees three years old. = Total amount of alkaloids, 324 per cent. [a]j = 1789. The alkaloids consisted of quinine, cinchonidine, amorphous alkaloid and very little cinchonine. The part insoluble in ether was too small for observation. 3. C. succirubra from Darjeeling. Total amount of alkaloids 6 per cent. [a]j = 24°17. Stem-bark, sold in London in October, 1870. The alkaloids consisted of cinchonidine, cinchonine, amorphous alkaloid and quinine. 4. C. officinalis from Ceylon. Bark sold in London in November, 1870. Total amount of alkaloids 57 per cent. [a]j= 1450.84. The part insoluble in ether proved [a]j = 91°·964. The alkaloids consisted of quinine, cinchonidine, amorphous alkaloid and cinchonine. The quantity of pure quinine amounted to 3.7 per cent. 5. C. Calisaya from Java. and wiped, macerated with water (acidulated with Bark sold in April, 1870, at Amsterdam, un- hydrochloric acid) for twelve hours, this water der the name of "Java koningskina, No. 1." Total amount of alkaloids, 3-21 per cent. 96°.37. poured off and more added, washing and rubbing the membrane well. All these washings and the [a]j=first infusion of twelve hours, making 24 ounces, were filtered, precipitated with acetate of lead, and The alkaloids consisted of amorphous alkaloid, qui- treated with sulphuretted hydrogen, being the pronidine, cinchonine and a trace of quinine. cess mentioned in the U. S. Dispensatory, but the 6. C. Calisaya hybrida from Java (C. Hasskar-liquid pepsin was evaporated to zviij only, not to liana, Miq.). Bark sold in April, 1870, at Amsterdam, un- "Java koningskina, Nos. 2 and 3." Total amount of alkaloids 3·125 per cent. [a]j = 50°-2. The alkaloids consisted of quinine, quinidine, cinchonine, cinchonidine and amorphous alkaloid. 7. C. Calisaya from Java. dryness. To compare these preparations they were tried with coagulated albumen. No. 1. Six-tenths (5) of a grain of the dry mucus No. 2. One fluid drachm of the glycerine prepara- No. 3. Bark sold in April, 1870, at Amsterdam, un- utmost solving power, excepting of No. 1. Nos. 2 der the name of "Java koningskina, No. 4." Total amount of alkaloids 2:47 per cent. [a]j and 3 suffered losses of pepsin. No. 2 lost pepsin on account of being digested and warmed while still 20°. in contact with the mucous membrane, and I am sure considerable pepsin was lost, as the mass be 8. C. Pahudiana. Bark sold in April, 1870, at Amsterdam un- came quite soft and pulpy. The process should be der the name of "Bruine Javakina." * Total amount of alkaloids 1 per cent. [a]j=138°. The alkaloids consisted of quinine, cinchonidine and amorphous alkaloid, whilst the presence of cinchonine was dubious. 9. C. Calisaya from Bolivia. Eastern Bolivian bark. carried on cold. No. 3 lost some of the precipitate during washing. This process is not practicable in warm weather, as the liquors decompose rapidly. Summing up my experience, I should take No. 2 as the process furnishing the most permanent preparation, being agreeable both to the eye and the palate of the patient. It has a bright, clear straw-colour, an agreeable bland taste and could be made double the above strength. It is not subject to the changes and other objections of the powders, is ready when it passes out of the hands of the apothecary, without further mixing, and not objectionable in taste to the Total amount of alkaloids 4 per cent. [a]j=138°. tion of the Cinchona barks. The Hague, 20th April, 1871. PEPSIN. BY G. A. ZWICK. So much has been said and written about this remedy, that the subject would seem nearly exhausted. I desire, therefore, only to communicate the result of a few experiments just completed; these, with the investigations of others, may perhaps lead to the adoption of a formula for a preparation of this article in the next edition of the U. S. Pharmacopoeia. 1st. A fresh stomach of a pig was emptied and the slimy mucous substance scraped off, spread upon a glass plate and dried. 2nd. The mucous membrane (scraped off as above) was dissected from the body of the stomach, cut up into moderately fine pieces. This weighed 8 oz.; it was digested with 3viij pure glycerine (acidulated with zij muriatic acid) for twelve hours, expressed, and more glycerine added till zviij were again obtained. This fluid was set aside and separated after a few days; the clear was poured off and filtered, warming it a little to facilitate filtration. 3rd. Another pig's stomach was cleanly washed • The barks mentioned under 5, 6, 7 and 8 are the first products from the Cinchona plantations in Java brought into the market for sale. SYRUPUS CALCIS LACTO-PHOSPHATIS. BY WILLIAM NEERGAARD. In the Archives Générales de Médecine for December, 1869, and for January and February, 1870, Dr. L. Dusart recommends the use of a new preparation, which he terms the lacto-phosphate of lime, in which the lime salt is dissolved in free lactic acid. Dr. B. W. M'Cready, of Philadelphia, requested me to prepare a syrup containing that compound, and I adopted the following formula : Concentrated Lactic Acid, flzj Magma of freshly Precipitated Phosphate Mix the lactic acid with 2 fluid ounces of water and saturate it with the magma. Put the liquid upon a filter and add the rest of the water until 8 fluid ounces of filtrate are obtained. Pour this upon the sugar, contained in a bottle; shake occasionally until solution is effected and strain. No heat ought to be applied, else the syrup assumes a milky appearance. The syrup thus prepared contains between 2 and the lactic acid.—Amer. Journ. of Pharmacy. 3 grains of dry phosphate of lime in each fl3, besides CHINESE BLISTERING-FLIES. BY F. PORTER SMITH, M.B. LOND., M.R.A.S. [July 1, 1871.: One Chinese variety is called the "ash-coloured moth." The chú-kt is met with in Sechuen, Shansi, Honan and Hupeh, and frequents the Ailanthus, Broussonetia (Morus) The entomology of China is not peculiarly rich, when papyrifera and several other trees. They are met with we bear in mind its semi-tropical character as a climate. in great quantities in autumn, when they make a grindThe extreme, or considerable, cold of the country proves ing noise, and are collected by the country people, who fatal to the crowds of insects' which infest the house and sell them, fresh, to the druggists at a few pence per the field, but of which a mere salvage is saved to renew pound. They are capable of raising a blister, but are the sorts. In no country, however, is so much wealth much less powerful than the Mylabris cichorii, with gathered from the labours of insects as in China. The which they are combined in the treatment of hydroCoccus lacca, which produces the gum-lac; the Coccus phobia. The legs and wings are removed, and the bodies pehlah, which secretes the spermaceti-like wax of Chinese only used for medicinal purposes. They are recompharmacy; the Coccus manniparus, which prepares honey-mended in the Pun-ts'au, as a remedy in barrenness, sugar; the silkworm; the diplolepis gall produced upon impotency, menstrual disorders, deficient lochia, lumthe oak-tree; and the nut-galls (Wu-pei-tsze) produced bago, diseases of the eye, etc. The drug is curiously upon the Rhus semialata and Rhus succedanea, are in-directed to be used as a vaginal suppository in female stances, amongst others, of that ingenious turning to disorders. It is combined with olibanum, arsenic, sal account of things which is a strong habit of the utilita- ammoniac and rice-paste, as an application to struma of the neck. Their use in hydrophobia, along with the Mylabris, to produce strangury, is in accordance with Chinese theory that the bite of mad dog impregnates the person, who is not safe until the delivery of a foetal dog Centipedes, scorpions, pediculi, and many other larval by way of the urinary passages. Hydrophobia is with or imaginal forms of insects, are swallowed in wine as them the climax of the period of gestation, and they antidotal, derivative, and revulsive remedies. An ano- promote parturition by giving the Huechys and the Mymalous creature, called the Hia-ts'au-tung-ch'ung ("in labris internally; or, rather, they endeavour to induce summer a plant, in winter an insect"), is a capital abortion, as the drug is administered in wine at once in sample of a Chinese pet medicine. It is the Hepialus such quantities as to cause violent strangury. Along moth, with the Cordyceps Sinensis (fungus) growing para-patient they profess to find a little dog. The Chinese with the blood and other substances passed by the sitically upon it. rian Chinese. Insects, a large class, called in Chinese classifications, Chung, and including frogs, mollusks, etc., are consumed by the Chinese as internal remedies. Blistering-flies are largely used in China. They are employed as diuretics, and to produce criminal abortion, so that their sale to ordinary persons is scarcely legal, and their use for such a purpose heavily punished by the Manchu Code of China. The Mylabris cichorii (Pan-mau) the Telini fly of India, is largely used in the country, as in the composition of an eye-powder (Ye-ming-sha), commonly believed to be the dung of the bat. This insect is an excellent substitute for the Cantharis of European pharmacy. The Cantharis erythrocephala, a European species, is met with in North China, but the Cantharis vesicatoria has not been met with. common Species of so-called Epicauta are met with in China, and are apparently called Tsáu-mau, or Zizyphus bug, from their resemblance to the fruit of that genus of socalled "dates.' running more to legs and horns, is now generally put The genus Epicauta, known by their with Lytta and Cantharis. From this it may be gathered that the people die after DUST AND SMOKE.* the polarization of light, Professor Tyndall adverted to After a few preliminary experiments illustrative of Another kind of blistering-fly, new to European by the coarser particles of smoke. In the former the pharmacy, is the Chú-ki, or Ailanthus bug. It is called, direction of maximum polarization, as in the case of the the polarization of light by fine dust, by the sky, and literally, the "fowl of the Ailanthus fatida," from the sky, is at right angles to the illuminating beam. In noise which it makes in common with other cicadaceous the latter, according to the observations of Govi, the insects of the class Homoptera. It is also called Hung- maximum quantity of polarized light was discharged liang-tsze, or "red lady-bug," a curious coincidence with the name of a common English insect, the ladybird. Se- obliquely to the beam. Govi's observation of a neutral veral species or varieties of this insect are described or tion was positive and on the other side negative, was alluded to in the Pun-ts'au-kang-muh, or Chinese Phar- also referred to. The additional fact was then adduced point in such beam, on one side of which the polarizamacopoeia. The genus called Hucchys, from the Chinese name for blood, is met with in Java, as well as in North that the position of the neutral point varied with the and South China and other places. The head, thorax density of the smoke. Beginning, for example, with an and legs are black; the prothorax is red; the eyes are very prominent; a large red bright spot on each side of its direction was first observed to be inclined to the atmosphere thickened by the dense fumes of incense, the thorax above; the front pair of wings are dark- beam towards the source of illumination. Opening the resin, or gunpowder, and observing the neutral point, brown, appearing nearly black when closed on the back windows so as to allow the smoke to escapo gradually, of the insect; the hind pair of wings are pale with brown the neutral point moved down the beam, passed the end veins; and the belly of the creature is of a bright ver- of a normal drawn to the beam from the eye, and gradumilion-red colour. Mr. Frederick Smith, of the British Museum, informs me that Burmeister places this insect, which I have called the red cicada on page 237 of my work on Chinese materia medica, in the order Cicadina, family Stridulantia. This same gentleman also informs me that Olivier (Encycl. Méthod. v. 756) calls it the Cicada sanguinolenta, whilst Amyot and Serville describe it as the Huechys sanguinea. This latter name is redundant, as both the genus and species mean bloody. It would be better to call the Chinese species Huechys vesicatoria. ally moved forward several feet down the beam. The curiosities? And if you so ask, my object is in some |