CHLOROPHYLL IN COSMETICS* By EVERETTE M. BURDICK, PH.D. Fice-President and Research Director, •imerican Chlorophyll Division, Strong, Cobb and Company, Inc., Cleveland, Ohio Tins PAPER WILL briefly describe the more important properties of chlorophyll derivatives especially their deodorant action that govern their use in cosmetics. The recommended chlorophyll derivatives for various cosmetics will be discussed together with the methods of incorporation. In many cases special product formulation must be used to gain complete effectiveness, and technical "know-how" plays an important role in this phase of chlorophyll refining. Not only should the right chlorophyll deriv- atives be used and in the proper purity, but also in the correct amount. A number of cosmetics now on the market containing chlorophyll are tried and proved, others remain as question-marks for their value of chloro- phyll. The latter do not contain either the proper amounts or the most adequate derivatives for maximum effectiveness. Where qualitative and quantitative analyses are important, as in therapeutic products, the amount and type of chlorophyll should be clearly stated on the label. However, this is not the case with cosmetics. There has been some misuse and mis- representation of chlorophyll through exploitation because of the consumer acceptance of the chemical substance and confidence in its value, but most of these are rapidly disappearing from the market. NOMENCLATURE OF CHLOROPHYLL AND CHLOROPHYLLINS Commercially, chlorophyll derivatives are divided into two classes--the "oil-soluble chlorophylIs" and the "water-soluble chlorophylIs." These terms are quite self-explanatory. The water-soluble chlorophylIs are known in the trade as "chlorophyllins." Their isolation, chemical process- ing, and refinement require very different methods, and those connected with the production. of "oil-soluble chlorophylIs" will be described first. OIL-SOLUBLE CHLOROPHYLL A pure form of natural chlorophyll can be made commercially by the well- * Presented at the December 10, 1953, Meeting, New York City. 85

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