W UNITED STATES OF AMERICA *> * . FOUNDED 1836 WASHINGTON, D. C. B19574 COLLECTION OF REPRINTS BY ROBERT PETER tu i ■ w P47gc TABLE OF CONTENTS 1. An account of the vegetable alkalies. 2. On the mode of collecting and preserving objects of natural history. 3. Thoughts on some of the applications of chemistry to medicine. It. Notice of the Crab Orchard mineral springs. 5>. Remarks on the functions of respiration in animals, and on ventilation. 6. On the application of galvanic electric- ity to medicine. 7. On the influence of caloric on the living animal body. i.3?^ THE TRANSYLVANIA JOURNAL OF MEDICINE, AND anfte fSUm&ate Sciences. FOR APRIL, MAY AND JUNE. ,, ORIGINAL COMMUNICATIONS. Article I.—An account of the Vegetable Alkalies, including their Therapeutic action when applied internally, or by the En- dermic Method. By Robert Peter, M. D. of Lexington Kentucky.* AMONG the improvements which the researches of phi- losophers have, during the last thirty years, introduced into the sciences of chemistry and medicine, few perhaps are of greater importance than the discovery, and the application to the cure of diseases of the new alkaline bodies, called now the Vegetable Alkalies. In the days of our fathers in chemistry very little was known of those principles, or constituents, of vegetable substances, on which their active properties depended. Some of the proximate elements of vegetables must have been known at a very early period; such, for example, as were very obvious, or which were easily separated, as sugar, starch, gum, resin, &c; but the means of analysis used in those days were but little calculated to throw much light on the subject of vegetable chemistry. Vegetables were introduced into a retort, heat was applied, and the products of the process were condensed in a receiv- * Submitted as an Inaugural Thesis, to the Trustees and Medical Profewori of Transylvania University, February 20th, 1834. Vol. 7—No. 2. 20 158 Peter on the Vegetable Alkalies. er. These, of course, were water, empyreumatic oil, and in some cases, ammonia; and in the retort there remained more or less carbon. The gaseous products were not collected, for in those days the idea of coercing or examining air had not entered the brain of the philosopher. Thousands of plants were subjected to this ordeal, by some of the industri- ous eperimenters, with so little difference in the results, that they could not, by this means, distinguish the rank and pois- onous Hemlock from the bland and innocuous Cabbage, Later years have brought with them the knowledge of the art of examining and separating, without destroying, the proximate elements of vegetable substances. To the French chemists we are indebted, more than to any others, for the light thrown on this interesting department of nature, al- though those of the other nations of Europe, and even of America, have contributed to the mass. The term alkali has been applied for a great length of time to those bodies which possess the property of uniting with acids, so as to destroy, or neutralize, their acid proper- ties, and of forming compounds with them, called salts: this is the most important distinctive character of an alkali. Another property which they all possess, is that of changing delicate vegetable blue colours, such as that of violets, to green. They all dissolve in water and in alcohol, and this character is sufficient to distinguish them from another set of bodies, called alkaline earths, such as lime, barytes, &c, which, though they neutralize acids, and form salts with them, and change vegetable colours as the alkalies proper do, yet are sparingly soluble in water, or in alcohol. Until the year 1816, when Sertuerner announced the dis- covery of morphine, the existence of but three alkalies prop- er was known, viz. soda, potash and ammonia. The for- mer was denominated mineral alkali, the latter volatile alka- li; and potash, because it was obtained only from the ashes of burnt vegetables, was called vegetable alkali. The newly discovered alkalies possess no other analogies with the old alkalies proper than those of their solubility in alcohol, their Peter on the Vegetable Alkalies. 159 reaction with acids and with vegetable blues, as will present- ly be seen. Chemists had been so long accustomed to believe that there was but one vegetable alkali, that when others were presented, even to their senses, the lapse of some years was required to familiarize them to the unexpected discovery. Thus, in 1803 M. Derosne, apothecary of Paris, in the course of some experiments on opium, separated a white crystalline substance, of which he remarks, " its solution changes the blue colour of syrup of violets to green" a known property of the alkalies; yet the observation of this reaction did not suggest to him the probability of its real nature, nor did it induce him to extend his researches. He was thus on the very thresh- old of a most brilliant discovery, the promulgation of which was reserved for another more fortunate enquirer, Sertuerner, who, though he asserts that he made the discovery about the same time,* did not venture to announce the existence of a new vegetable alkali until thirteen years afterwards. Vauquelin, in 1808, while analyzing several plants of the genus Daphne, (D. thymelea, D. alpina, and D. gnidium,) discovered a substance which he described as follows; "very volatile; acts on vegetable colours like the alkalies" About six- teen years afterwards, when publishingan account of the same substance, as a new vegetable alkali, by the name of Daph- nine, he adverted to this circumstance, adding, that as at the time of his previous publication, "the existence of an alkali of a vegetable nature was not known, I did not ven- ture to affirm that it really was a vegetable alkali." The attention of philosophers was first aroused to this sub- ject by the announcement of the discovery of a new alkali in opium by Sertuerner, in 1816. The discovery was soon confirmed by Robiquet, but so great an apathy existed in the minds of chemists relative to this subject, that but little notice was taken of the matter until two years afterwards, when Pelletier and Caventou, attracted towards it and them * Seguin also discovered and described it about the same time (1804,) but did not venture to call it an alkali. Ann. de chemie, 92. 160 Peter on the Vegetable Alkalies. selves the general attention of the scientific, by their many interesting discoveries in this department of research. If we scan over the chemical history of the period from the time of the researches of Derosne to that of the discove- ries of Pelletier and Caventou, wa can easily account, in part, for the little attention which was paid to this subject, espe- cially by the British philosophres. We shall see that Wol- laston was commanding an engrossing homage by his discove- ry of platinum and its associate metals; and that his illus- trious cotemporary, Davy, was changing the very face of the science of chemistry by the discovery of the metallic bases of the old alkalies and earths, and by his researches into the nature of chlorine, &c. Iodine also, was discovered in this period, with many other important facts and substances. Sertuerner, pharmaceutist of Eimbeck, Hanover, was the first to announce positively the existence of an organic vegetable alkali; which he obtained from opium, and which he said, was the efficacious part of that drug. His process for obtaining it was to make a solution of opium in distilled water, and to supersaturate the solution with ammonia, which threw down a greyish white precipitate: this collected and washed with water, was the impure alkali, which he purified further by washing in cold aq. ammonia, and subsequent so- lution in diluted sulphuric acid, precipitation by ammonia, and cold alcohol. To ascertain the medical properties of this new substance, he tried its effects upon himself and three other persons, young gentlemen of his acquaintance. They each took half a grain dissolved in alcohol and diluted with water. General redness, even in the eyes, covered the whole body, particu- larly the cheeks; and the animal powers seemed to be raised. Half an hour afterwards, another half grain was taken by each, by which the effects were considerably increased, and a transitory inclination to vomit, and a stunning sensation in the head were felt. A quarter of an hour afterwards anoth- er half grain was administered: the young men instantly felt acute pains at the stomach, with a sense of weakness, Peter on the Vegetable Alkalies. 161 general stiffness, and faintness. He himself felt similar sen- sations, and on lying down, fell into a dozing reverie attend- ed with a throbbing in the extremities. Being now some- what alarmed for the consequences, they each took six or eight ounces of strong vinegar, which caused vomiting and ended the experiment. The physiological properties of this substance were studi- ed more at length two years afterwards, by Magendie and Orfila, and they and others have since contributed to make them fully known. No one, according to the strict logic of science, can deny, that Sertuerner was the first who discovered the alkaline principle of opium; yet an examination of the account of the experiments of Derosne, published thirteen years before, will leave a conviction that he separated and examined the very same substance, although he was not so fortunate as to prove its alkaline nature, nor to discover that it was the ac- tive principle of the drug. In the paper published by M. M. Derosne and Proust, published in the Annals de Chemie,tom. xlv. 1803, we find the following observations, which plainly show that Derosne had discovered the substance called by Sertuerner morphium, although he (Derosne,) did not distinguish it from another substance discovered at the same time, and known for a long time as " salt of Derosne," now, narcotine. " Caustic and car- bonated alkalies produce a copious precipitate in the aque- ous solution of opium." M. Proust considered this precipi- tate a pure resin, but Derosne thought it a compound body. He obtained it as follows; he precipitated it from a solution of opium in six parts of water, by carbonate of potash. Boiling alcohol took up three-fourths of this precipitate, and acquired a dark red colour, and the filtered alcoholic solu- tion yielded, on cooling, a reddish irregular crystallization. This, as I have before intimated, he supposed to be the same as the salt which he had obtained (now known as narcotine) by spontaneous granulation, on evaporating the aqueous solution of opium to the consistence of syrup and diluting i ■ 162 Peter on the Vegetable Alkalies. again with water. He remarks, however, " that it showed some difference, arising from the manner of obtaining it. Its taste is a little bitter, (the other was tasteless,) and it does not crystallize so regularly; its solution changes the blue colour of syrup of violets to green. It is soluble in alcohol, and its solution is not rendered turbid by the addition of water, but after a short time small crystals appear in the liquid." It must be evident to every chemist, that in this substance, M. Derosne had actually discovered one of the active prin- ciples of opium, morphine. His conclusions from his own experiments were, however, unphilosophical. They were as follows; that opium was a very compound substance, that it contained a narcotic volatile principle, extractive matter, mucilage, resin, oily matter resembling wax, a crystalline substance which is neither saline nor acid, a substance similar to albumen or gluten, a small quantity of caoutchouc, &c. In February, 1817, M. M. Pelletier and Magendie, in a paper to the Royal Academy of Sciences, Paris, announced that another vegetable alkali had been discovered, by the former gentleman, in the various kinds of ipecacuanha of the shops, which he called emetine; and which, from the ex- periments of the latter, M. Magendie, an account of which was appended, they asserted to be the active principle of that root. The next discovery of a vegetable alkali was by Pelletier and Caventou, who separated it from the nux vomica, and from the products of the other plants of the genus strychnos. In their paper, read to the Acad. Nat. Sciences, Aug. 10, 1818, they called the alkali Vaqueline, in honour of that distinguished chemist, who had been their preceptor; but on reflecting that the name which they respected so highly ought not to be connected with a substance of so poisonous a nature as their new discovery was, they changed it to strvch- nina J nine. About the same time, M. Boullay announced the discovery of a new alkaline principle of a poisonous nature, in the Cocculus Indicus, (seeds of the menispermum cocculus,) Peter on the Vegetable Alkalies. 163 which he called picrotoxine, from the circumstance of those seeds having been used to poison fish. In the same year, M. M. Pelletier and Caventou again appeared before the public with two new alkalies, obtained from peruvian bark, called by them cinchonine and quinine. In their memoir they acknowledge that the former principle had already been de- tected by M. Gomez of Lisbon, but state that he had neither ascertained its alkaline nature nor studied its combinations with acids; and that in a more recent memoir than that of Gomez, by M. Laubert, it was regarded as a pure crystalline resin; so that little attention had been paid to it by chemists. They justly claimed all the credit of the discovery of quinine. Peruvian bark, since its introduction into medicine, has been the subject of much chemical research; and the histo- ry of the examinations which it has undergone with a view to discover its nature, is interesting on more accounts than one—affording, among other things, another evidence how near a person may approach to the discovery of an impor- tant fact without actually making it. Dr. Maton was the first to point out the fact that an infu- sion of galls caused a precipitate in the infusion of Bark* M. Seguin, having at a later period discovered that gelatine was precipitated by the tannin of the infusion, affirmed that gelatine was the aictive principle of the peruvian bark, and instituted a number of experiments to prove that gelatine possessed all the febrifuge properties of that substance. An- drew Duncan, Jr. in Nicholson's Journal, Dec. 1803, attempts to prove that the substance in the bark, which is precipita- ted by infusion of galls is not gelatine, because it dissolves in alcohol, which gelatine does not; and calls this peculiar principle cinchonine. He found that it was precipitated also by carbonate of potash; and proceeding on the vague idea that every substance which was precipitated by galls and carb. potash, was cinchonine, he stated that that substance exists also in ipecacuanha, columbo, augustura, black and cayenne pepper, and opium. He evidently knew but little of the substance which he named, and did not separate nor 164 Peter on the Vegetable Alkalies. obtain it pure. Vauquelin, a few years afterwards, discov- ered the same substance, but did not obtain it pure; for in his account of it, in the Med. and Surg. Review, xv., 12,— he describes it as being of a " brown colour, bitter taste, less soluble in water than in alcohol, precipitating tart, emetic, but not glue." Dr. Bernardinus Anthony Gomez, of Lisbon,* seems to have been more successful in his researches, and to have ac- tually obtained cinchonine in a pure state. The process by which he obtained it was as follows, and is very similar, in many respects, to some processes used even at the present day. He made a spirituous extract of bark of the common consistence, which he mixed with distilled water and strain- ed. The aqueous solution was evaporated to the consistence of an extract, and successive portions of a well saturated solution of potash were added until every thing soluble in that menstruum was removed: the residuum was washed in cold water and dried. It was a white powdery substance, easily separated from the filter, bitter, inflammable, very lit- tle soluble in water, but soluble " enough, when recently pre- pared, in sulphuric ether, alcohol, diluted sulphuric, nitric and muriatic acids: in acetic, oxalic, citric, malic? but not in tartaric acid?" From these solutions it was precipitated by infusion of galls. This substance was undoubtedly a mixture of cinchonine and quinine; but although Gomez discovered that it dissolved in diluted acids, he did not ascer- tain that it neutralized them. He did not obtain any salt but the sulphate, nor did he guess that it was an alkaline body.t He obtained cinchonine in crystals by dissolving it in alcohol and allowing that substance to evaporate spon- taneously. He found some difference in it according to the kind of bark employed; owing, no doubt, to the different proportions in which cinchonine and quinine exist in the several kinds. The inferences which he drew from his ex- * Edinburgh Med. and Surg. Jour Oct 1811 v.-i / stance, 2Tl f • "* "re obtaincd> in the rorm °f »'". «™% bmat.on „„h „ peculiar acid; thus morphine is combined wift »ec„nic ac.d „ opium, ,he alkalies of bark are united Zllh •Solanine, Guaranine, Esenbeckin.J Peter on the Vegetable Alkalies. 173 kinic acid, and strychnine and brucine seem each to exist in combination with acids of a peculiar nature. A knowledge of these different properties and habitudes of the vegetable alkalies, renders the processes for obtaining them easily understood, some idea of which may be gleaned from the following summary. 1. The most common method pursued, to obtain those which are not readily soluble in water when pure, is to make an infusion or decoction of the vegetable in water, either pure or rendered slightly sour by the addition of sulphuric, muriatic, or acetic acids'; this solution is then concentrated by evaporation, and the vegetable alkali is precipitated from it by the addition of potash or ammonia in excess, or by boil- ing it with a sufficient quantity of caustic lime, or calcined magnesia. When potash or ammonia are used, the alkaline principle is separated in the form of powder, mixed only with the impurities of the vegetable; but when magnesia or lime are made use of, the alkali is mixed with the supera- bundant portion of those earths. The liquid, in either case, is filtered through paper, and the precipitate, which remains on the filter, is washed with cold water and dried. The al- kali is separated from the magnesia or lime, and at the same time, from some of the impurities, by dissolving it out by boiling the precipitate in alcohol. But even then it is usu- ally' highly coloured and impure. Various modes are used, according to the nature of the case, to purify the alkali. In some cases, crystallization from the solution in alcohol several times, will make it sufficiently pure, in others, washing with cold or diluted alcohol, with ether, or boiling with animal carbon, will purify it sufficient- ly. The most effectual mode is, to dissolve it in a diluted acid, and to boil the solution with animal carbon, then to precipitate the alkali from the purified solution by ammonia or magnesia. Subsequent solution in alcohol, and evapora- tion, will render it sufficiently pure. This, in general terms, is the process by which morphine, cinchonine, quinine, emetine, delphine, picrotoxine, atro- Vol. 7—No. 2. 20 j>7.j Peter on the Vegetable Alkalies. phine, corydaline, eupatorine, esenbeckine, paralline,