86 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS known method of Schertz [Schertz, F. M., "Isolation of Chlorophyll, Caro- tene and XanthoPhYll by Improved Methods," Ind. Eng. Chem., $0, 1073- 1075 (1938) ]. This oil-soluble natural chlorophyll is a mixture of chlorophyll a and chlorophyll •. Chlorophyll a has a blue-green color in solution and chlorophyll • has a more yellow-green color. Both are oil-soluble, have a wax-like nature and fluoresce a blood-red color. The commercially avail- able materials are very deep green colored liquids that are relatively stable in direct sunlight. They find their greatest use in the fields of coloring foods, waxes, soaps, candles, inks, paints, leathers, pharmaceuticals, and cosmetics. "Coppering" natural chlorophylis changes their color to bluer green and increases their light stability. The water-soluble chlorophyllins are pro- duced by alkaline saponification of the natural or oil-soluble chlorophyll. CHLOROPHYLLINS Sodium potassium magnesium chlorophyllins are available commercially and in most cases represent the most economical form of the chlorophyllins. Water solutions of these crude chlorophyllins have a characteristic green color, are relatively stable to direct sunlight and fluoresce a blood-red. When dried, they are extremely hygroscopic and thus difficult to prepare in solid form. Foods and pharmaceuticals consume most of the sodium potas- sium magnesium chlorophyllins. Just as in the case of the coppered oil- soluble chlorophyll it has been found convenient to increase both their tinc- torial strength and light stability of the chlorophyllins by coppering them. It should be pointed out that coppering these derivatives of chlorophyll does not destroy any of the beneficial or desirable properties of chlorophyll. Clarified water solutions are available commercially as are the dry powder forms. The purity of these materials is generally in the excess of 90 per cent. They are readily soluble in cold water producing characteristic green color solution and have a blue-black sheen in the dry form. Hainer has shown the aqueous solutions to be colloidal in nature [Hainer, R. M., et al., "Stud- ies of Copper Chlorophyllin--Odorant Systems." Presented before the Chemistry Section of the American Association for the Advancement of Science, Boston, December (1953), and the American Chemical Society, Kansas City, March (1954)]. They are quite stable in direct sunlight and have an exceptional high tinctorial value. They become insoluble at a pH below 6.5. It is this group of water-soluble derivatives that have found such widespread use during the past few years. By far, the greater part is consumed in cosmetics, pharmaceuticals, and dog foods. The acid forms of the water-soluble chlorophyllins (mainly chlorins and rhodins) combine with many metals such as iron, cobalt, nickel, mercury, zinc, silver, gold, etc., just as with copper and are produced similarly. These latter have not gained widespread use. The necessity of producing chlorophyll derivatives

CHLOROPHYLL IN COSMETICS 87 of sufficient potency and purity for their intended application must again be emphasized. When properly processed and used, the various chlorophyll derivatives are effective agents for blood regeneration [Craig, P. E., "A New Approach to the Treating of Hypochromic Anemia," Medical Times, 81, 44 (1953)], a general tonic [Burgi, E., "Chlorophyll Als Pharmakon, Monograph," Leipzig (1932)], for wound healing [Gruskin, B., "Chloro- phyll-Its Therapeutic Place in Acute and Suppurative Disease," z/m. •. Surg., 49, 49 (1940) and Moss, W. H., et al., "Effectiveness of Chloresium in Wound Healing and Deodorant Effects," •. ,'lm. Med. ,'lssoc., 140, 1336 (1949) ], body deodorization [Montgomery, R. M., et al, "Oral Administra- tion of Chlorophyll Fractions for Body Deodorization," Postgrad. Med., 8, 401 (1950), Taber, F. S., "Chlorophyll as a Deodorizer of Lochial and Men- strual Odors," •. Med. Soc. New •ersey, 48, 321 (1951), and Tebrock, S., "A Derivative of Chlorophyll (Daratol) as an Internal Deodorant," Propri- etary Assn. Meeting December, 1951, and Westcott, F. H., "Oral Chloro- phyll Fractions for Body and Breath Deodorization," N.Y. State •. Med., 50, 698 (1950)], and for treating of dental diseases [Hein, J. W., et al, "Chlorophyll as a Potential Caries-Preventive Agent," Penn. Dental •., 16, 221 (1949) and Rapp, G. W., et al., "Chlorophyll: The Green Wonder Drug," Illinois DentalS., 18,405 (1949) ]. Certain of the chlorophyll deriv- atives show bacteriostatic action, photodynamic action, affect hormones, and enhance the action of antibiotics [Rapp, G. W., et al., Ibid.]. "Chlorophyll 1953" by Walter H. Eddy reviews previous work. Literature dealing with the medical uses of chlorophyll and chlorophyll derivatives [Hainer, et al., Ibid., p. 4] has recently explained the deodorant action of the various chloro- phyll derivatives as being due to surface adsorption which is similar to the action of carbon black, charcoal, and silica gel. However, they also find it necessary to resort to both chemical and physical activity to explain com- pletely the observable deodorant effects. Chlorophyll and chlorophyll deriv- atives can effectively deodorize many odorous materials in vitro as well as in vivo such as thioglycolic acid, benzyl mercaptan, amyl mercaptan, hydrogen sulfide, trimethylamine, putrefactive products, butyric, propionic and ca- proic acids, eugenol, cineole, etc. It should be stressed that each of the above-mentioned materials is best deodorized by certain conditions of con- centration, temperature, and time. In many cases the presence of oxygen is advantageous. The above effects have been reported by Langley, L. L., et al. [at the Federal Proceedings, 12, 83 (1953) ], Ahmed, et al., ["A Proposed Method for Determining the Effect of Deodorants on the Elimination of Alcohol Breath," Sci. Ed., •. ,'lm. Pharm. ,'lssoc., 42, 240-242 (1953)], "A Study in the Measurements of Odors and the Odorizing Effects of Certain Materials" [Ibid., 42, 242-247 (1953)], Rapp, G. W., et. al. [Ibid., p. 5], Byran, A. H., ["An Analysis of the Chlorophyll Problem," Drug and Cosm. Ind., 72,612 (1953)], Hainer, R. M., etal., [Ibid., p. 4].