Part 4

In the early stages of this work some experiments were made to see if potassium permanganate could be used to purify the lead precipitate by oxidizing the tar brought down in precipitation. It was found that the permanganate attacked the lead precipitate as well as the other organic matter in the vessel. This fact and the well-known value of permanganate in treating skin diseases, its use as an antidote for some kinds of alkaloid poisoning,[47] as an antidote given to cattle poisoned by plants,[48] and as an antidote for snake bites,[49] suggested its use as a remedy for Rhus poisoning. Maisch[50] mentioned that he had used it with success, but it never came into general use, probably on account of its staining the skin and clothing. In carrying out this work abundant opportunities for testing its value as a remedy for the dermatitis caused by poison ivy were afforded by many cases of accidental and intentional poisoning. The best example of the latter was obtained with the ether solution from the extraction of the lead precipitate in the Soxhlet apparatus (page 28). After removing the ether, a small drop of the residue was applied to the wrist as described. An itching red spot about the size of a dime was noticed in thirty-six hours, and it steadily increased in size. Nearly two days after the application of the poison, a dilute solution of potassium permanganate containing a little caustic potash was rubbed into the spot until the pimples were destroyed. A little black spot was left wherever there had been a pimple, showing that the permanganate had been reduced to oxide in the skin. The place was washed and nothing more was thought of it until the morning following, when it was noticed that the wrist had commenced to swell during the night, and the characteristic watery secretion was running from the poisoned spot. More permanganate solution was applied without potash and the wrist was bandaged, thinking that this would prevent the spreading of the eruption, but it really facilitated spreading by becoming saturated with the poisonous fluid and keeping it in contact with a larger surface of skin. In the meantime the swelling and inflammation had extended nearly to the elbow. The arm now had the appearance of having been bitten by a snake. To reduce the swelling it was immersed in hot water. This seemed to bring out the eruption very quickly and the blisters were treated with permanganate as fast as they appeared. The swelling was reduced, but returned during the night. On the evening following, the forearm was immersed in a bowl of hot permanganate solution containing a little caustic potash. The solution was kept as hot as could be borne for about half an hour. After this bath, the poison was completely oxidized, for the swelling was reduced and did not return, nor was there any fresh eruption. What appeared to be a severe case of poisoning was thus cured very quickly. The use of hot water not only reduces the swelling, but also helps to destroy the poison. The action of permanganate is also more rapid at high temperatures.

The oxidizing power of permanganate, as is well known, is greater in acid solution than in alkaline, five atoms of oxygen being available in the former and three in the latter, according to these equations:

2 KMnO_{4} + 3 H_{2}SO_{4} = K_{2}SO_{4} + 2 MnSO_{4} + 3 H_{2}O + 5 O. 2 KMnO_{4} + H_{2}O = 2 MnO_{2} + 2 KOH + 3 O.

Permanganate was used as a remedy in some cases mixed with dilute sulphuric acid, and in others, with zinc sulphate; also with lime water. It was found to be satisfactory whether used alone or with any of the substances mentioned, provided it was well rubbed into the skin. The concentration of the solution used was varied according to the location and condition of the eruption. Where the skin was thin or already broken, dilute solutions (one per cent.) were used. In one case, the eruption appeared in the palm of the hand where the skin was so thick that it was necessary to open it before the remedies could reach the poison. The difficulty of getting the remedy in contact with the poison in the skin is the reason why the eruption is hard to cure.

The remedy most commonly used for this eruption is an alcoholic solution of lead acetate. This remedy is unsatisfactory for the reason that its action consists in depositing an unstable lead compound of the poison in the skin where the conditions of moisture and temperature are favorable for its decomposition, liberating the poison with all its irritant properties. Moreover, alcoholic preparations should not be used because the alcohol dissolves the poison and, on evaporation, leaves it spread over a larger surface like a varnish. Potassium permanganate, however, oxidizes the poison completely. The only objection to the use of permanganate of which the writer is aware is that it stains the skin. The stain can be removed by vigorous scrubbing with soap, or it will wear off gradually in a few days. It can be removed at once by certain acids, but these should not be used by persons not familiar with their action.

With the knowledge of the facts mentioned, many solutions were tested for poison by applying them to the skin, and when an eruption appeared, it was cured quickly and permanently by rubbing in a permanganate solution, usually mixed with dilute sulphuric acid.

FOOTNOTES:

[16] Nitrogen was found very readily by the soda lime test in the tar left after extracting the original material with 50 per cent. alcohol, but was not found by the Lassaign test.

[17] Stevens. Amer. Jour. Pharm. 77, 255, June, 1905.

[18] Whenever it is stated in this paper that a solution was poisonous or not poisonous, the test was made by the writer upon himself.

[19] Liebig's Annalen, CXI, p. 215.

[20] Ueber Mategerbstoff, p. 20.

[21] Bull. Soc. Chim. (II), Vol. 2, 95 (1864).

[22] Berichte 19, 1735 (1886).

[23] Jour. Chem. Soc. 71, 1194 (1897).

[24] Berichte 19, 1740.

[25] Ibid. 1747; Annalen, 112, 97.

[26] Biochem. Pflan. II, 521.

[27] Ann. de Chim. et de Phys., 6th Series, XXII, 76 (1891).

[28] Treatise on Chem., Vol. III, Pt. III, 492.

[29] Les Sucres; Chem. der Zuck.; Biochem. der Pflan.

[30] Chem. Zeit. 23, Rep. 177.

[31] Loc. cit. 1, 209.

[32] On standing several weeks, a small quantity of tar separated out on the walls of the vessel, also a brown precipitate which was filtered off, suspended in water, and hydrogen sulphide was being passed in when an accident occurred and it was lost.

[33] "By warming with alkalies or barium hydroxide, rhamnose is colored yellow." Chem. der Zuck. I, 177.

[34] Ibid. 188.

[35] Ibid.

[36] Rayman, Sur L'Isodulcite, _Bull. Soc. Chim._ 47, 668 (1887).

[37] Acides Gummiques.

[38] Berichte XX, pp. 1089, 1091, 1188, 2566.

[39] Ann. de Chim. et de Phys. (6) XXII, 93 (1891).

[40] Biochem. der Pflan. I, 210.

[41] Comptes rendus CXV, 892.

[42] Amer. Chem. Jour. 28, 370.

[43] Amer. Jour. Pharm. 77, 255 (June, 1905); 78, 53 (Feb., 1906).

[44] A wax obtained from _Rhus succedanea_ was shown by Stahmer to contain palmitic acid and glycerol in the form of glycerol palmitate. _Annalen_ 43, 343, (1842).

[45] See Amer. Jour. Pharm. 77, 256.

[46] This section is added in the hope that it may be of use to others who are subject to this form of poisoning.

[47] Moor, N. Y. Med. Rec. 45 (1894), 200.

[48] Bull. No. 26, U. S. Dept. Agr., Div. of Bot. 47.

[49] Lacerda, Comptes rendus 93 (1881) 466-469.

[50] Amer. Jour. Med. Sci. 52 (1866), 285.

SUMMARY.

Leaves and flowers of the poison ivy plant were extracted with ether and the ether was removed by evaporation. In the residue, the following substances were found and studied: gallic acid, fisetin, the sugar rhamnose, and a poisonous tar, gum, or wax.

The lead compound of the poison was soluble in ether; this fact gave a means of separating the poisonous substance from the non-poisonous matter in one operation.

The poison was not volatile with vapor of acetic acid, or with vapor of alcohol.

The poisonous tar or wax was decomposed by acids and yielded gallic acid, fisetin, and rhamnose, showing the probable source of these compounds in the plant, and indicating that the poison is a complex substance of a glucoside nature.

It was found that a portion of the poisonous substance could be precipitated by lead acetate from a solution of the purified tar in 50 per cent. alcohol.

All cases of poisoning developed on the writer were easily cured with potassium permanganate.

The following method is suggested for obtaining the poisonous substance from the plant: Extract the plant with alcohol, filter, and precipitate at once with lead acetate. Wash the precipitate, dry, and extract with ether in Soxhlet extractors (loosely filled). Combine the ether extracts, mix with water, and pass in hydrogen sulphide. Separate the water and the ether solution, and filter the latter. Wash the ether solution thoroughly by shaking with water, and then evaporate at a low temperature.

BIOGRAPHY.

William Anderson Syme, the author of this dissertation, was born in Raleigh, N. C., on July 11, 1879. He was prepared for college at the Raleigh Male Academy, entered the North Carolina College of Agriculture and Mechanic Arts in 1896, and was graduated in 1899 with the degree B. S. He was an Instructor in Chemistry at the same College from January 1st, 1900, until June, 1903, when he received the degree M. S. for graduate work. In October following, he entered Johns Hopkins University as a graduate student in Chemistry, and was awarded one of the North Carolina Scholarships. His minor subjects are Physical Chemistry and Biology.