J. Soc.Cosmet. Chem.,38, 209-221 (July/August1987) The effect of solvents on the ultraviolet absorbance of sunscreens LOUISE E. AGRAPIDIS-PALOYMPIS and ROBERT A. NASH, St.John'sUniversity, Jamaica,NY 11439, and NADIM A. SHAATH,* Research & Development Laboratory, FeltonWorldwideInc., Brooklyn, NY 11237. Received March 25, 1987. Synopsis Theefficacy ofsunscreens isofteninfluenced bythesolvents in whichtheyaredissolved. In thisregard, the ultraviolet(UV) absorption spectra of 13 UVA andUVB sunscreen chemicals weredetermined in 12 solvents ofvarying polarity andcosmetic interest. Changes in boththewavelength ofmaximum absorbance (K max)andmolarabsorptivity (½)wereobserved formanyof thesunscreen-solvent systems studied. Observed hypsochromic andbathochromic shifts in Kmaxfora number ofsunscreen chemicals wererelated to theirstructure andpolarity.Polarsolvents shiftedtheK maxof polarsunscreens to shorter wavelengths (hypsochromic) andshifted lesspolarsunscreens to longer wavelengths (bathochromic). Ortho-substituted sunscreen chemicals, suchassalicylates andanthranilates experienced a minimumor no UV absorbance shift. With theexception of PABA,mostsunscreens showed increased absorbance in bothpolarandnon-polar solvents and decreased absorbance in semi-polar solvents,suchas hexylene glycoland C•2-C•5 alcohols benzoate. Theresults of thisstudyshould aidthecosmetic chemist in selecting appropriate solvents andvehicles for sunscreen chemicals. INTRODUCTION In 1960,Riegelman andPenna(1) werethefirstto observe markedchanges in theUV absorbance of p-aminobenzoic acid(PABA)andseveral lessimportantUV absorbers in five differentsolvents(water,alcoholUSP, polyethylene glycol400, isopropylpalmirate, andmineraloil). The authorsconcluded that a sunscreen's effectiveness couldbe influenced by the solventin whichit is dissolved. Twelveyearslater,Groves,usinga thin-filmspectrophotometer, confirmed the previous findingsfor a smallnumberof sunscreen chemicals in polyethylene glycol400, isopropyl palmitate,andmineraloil (2). Shiftsin the spectral absorbance of PABAin waterandisopropyl alcoholwerealso reportedby Cumpelik(3). Morerecently,Klein andDoshihaveshownthat the UV absorbance of severalimportantsunscreen chemicals, aloneand in combination with * Address all correspondence to: Dr. NadimA. Shaath,Technical Director,FeltonWorldwide,Inc., 599 JohnsonAve., Brooklyn,New York, 11237-USA. 209 210 JOURNAL OF THE SOCIETYOF COSMETICCHEMISTS eachother, will changeconsiderably when they are dissolvedin selectedliquid emollients (4). The presentstudy(5) was undertakento determinethe influenceof 12 cosmeticand relatedsolventsof varyingpolarityon the UV absorptioncharacteristics of 13 sunscreen chemicalsin orderto aid the cosmeticchemistin achievinga betterunderstanding of the interactions that arepossiblebetweenUV absorbers andliquid components usedin sunscreen formulations. EXPERIMENTAL MATERIALS Thirteen sunscreenchemicalswhich are widely used in cosmeticformulationswere tested.The list includedfive UVA (320 to 360 nm) absorbers (i.e., menthylanthranilate, oxybenzone, dioxybenzone, sulisobenzone, and butylmethoxydibenzoylmethane) andeight UVB (290 to 320 nm) absorbers (i.e., PABA, ethyl dihydroxypropyl PABA, octylcyanodiphenylacrylate, octyl methoxycinnamate, octyl salicylate,homomenthyl salicylate,octyl dimethyl PABA, and triethanolamine salicylate).All of the sunscreens tested,with the exceptionof butylmethoxydibenzoylmethane, havebeenassigned Category 1: safeandeffectivestatusby the FDA over-the-counter reviewpanel(6). Twelve solventswerealsoselectedfor study, baseduponeither their usagein cosmetic formulationor theirpolarity,andarelistedin TableI in decreasing orderof polarityin accordance with Vaughan'ssolubilityparameterassignments (7). Chromatographicanalysiswas performedon all sunscreens and solventsused in the studyin orderto confirmtheir purity. Our assays showedthat the materialsusedwere well within the purity specifiedby the supplier(i.e., not lessthan 98%). METHODOLOGY Solutionsfor UV spectralanalysiswere accuratelypreparedusing sunscreen-solvent Table I Solventsand Their Corresponding SolubilityParameters Listedin Decreasing Orderof Polarity Solubilityparameter Solvent Ethanol 70%-water at 25øC 30% 16.0 10% 13.9 Propylene glycol Ethanol 90%-water 14.0 Ethanol 12.8 Hexyleneglycol Methyl carbitol 12.3 10.7 Ethoxyethanol Isopropylmyristate 10.6 8.0 Isopropylpalmitate 7.8 C•2-C•5alcohols benzoate 7.6 Hexane 7.3 Mineral oil 7.0 SOLVENTS AND SUNSCREEN ABSORBANCE 211 combinations wherethe solubilityof the sunscreen waspossiblein the solventat room temperature.A 50 mg _+ 1 mg sampleof eachsunscreen wasweighedaccuratelyinto a 100-ml volumetricflaskandthen dilutedto the mark with solvent.The resultingstock solutionwasthen diluted 1:100 to yield a final sunscreen concentration of 5 mg/L. UV absorbance curves of each final dilution were obtained with the aid of a Perkin- ElmerLambda4B UV/VIS spectrophotometer. A background correction wasperformed using 1-cm quartz cellsfilled with blank solvent.The UV absorbance curvewasthen recorded by scanning wavelengths between200 and400 nm, usinga sampleof the final dilution in the 1-cmquartzcell. The wavelengthof maximumabsorbance (• max) and the corresponding absorbance valuewere determinedand displayedby the microprocessorunit of the spectrophotometer. The spectrophotometer's wavelengthaccuracy is _+0.3 nm and its absorbance accuracy is -+0.005 A when measured at 1,000 absorbanceunit (A). A holmium chloride standardcell was usedto calibratethe spectrophotometer and its microprocessor unit. Our resultswere within the specifications establishedfor the standardcell and the spectrophotometer. The molar absorptivity(½)wascalculatedfor eachtest solutionat the wavelengthsof maximumabsorbance (• max)in the ultravioletregions(UVA, UVB, andUVC). However, only the valuesin the UVA and UVB regionsare reportedin this paper(8). RESULTS The ultravioletabsorptionspectralproperties(X max and ½ values)of 13 sunscreen chemicalsin variouspolar, semi-polar,and non-polarsolventswere obtained. These data are summarizedin TablesII-IV as three separategroupsof compounds.Sunscreenswhere the • max is shiftedtowardsshorterwavelengths (hypsochromic or blue Table II UV SpectralData of Sunscreen ChemicalsShowingHypsochromic Shiftsin the •. max PABA Solvent Dioxybenzone }, max max Sulisobenzone Oxybenzone ½ •. max ½ •. max ß 9,300 Ethanol 70%-water 30% 266 13,600 326 9,400 324 8,600 321 Propylene glycol 272 14,500 326 9,100 324 7,500 322 8,400 Ethanol90%-water 10% Ethanol 271 272 13,800 13,100 326 327 9,400 9,300 325 326 8,900 8,400 324 325 9,500 9,400 Hexyleneglycol Methyl carbitol Ethoxyethanol Isopropylmyristate Isopropylpalmirate C•2-C•5alcoholsbenzoate 268 291 293 ins. ins. ins. 13,400 18,300 18,900 ins. ins. ins. 329 324 325 352 351 352 7,600 8,900 9,600 10,600 10,200 9,900 331 333 334 ins. ins. ins. 7,000 5,600 8,500 ins. ins. ins. 327 323 327 328 327 328 8,200 8,400 9,000 9,000 9,000 8,300 Hexane ins. ins. 351 13,100 ins. ins. 328 8,800 Mineral oil ins. ins. 352 11,400 ins. ins. 329 7,800 Wavelengthshift from non-polarto polar solvent Ah max = -27nm Ah max = -26nm Ah max = -10nm Ah max = -8nm 212 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS Table III UV SpectralData of Sunscreen Chemicals ShowingLittle or No Shiftin the X max Triethanolamine salicylate Octyl salicylate Homomenthyl salicylate Menthyl anthranilate Solvent X max E }x max E • max e Ethanol 70%-water 30% 298 2,800 308 4,900 306 4,800 336 5,600 Propylene glycol 298 2,100 307 4,800 307 3,700 335 4,800 297 298 3,000 2,900 305 307 4,000 4,200 305 306 4,300 4,600 337 338 5,000 5,000 Hexyleneglycol Methylcarbitol Ethoxyethanol Isopropylmyristate Isopropylpalmitate C12-C•5alcohols benzoate 298 301 301 ins. ins. ins. 2,200 3,100 3,000 ins. ins. ins. 306 309 310 309 308 309 3,900 4,000 4,000 4,200 4,600 3,900 306 307 307 308 307 308 2,300 4,800 4,700 5,100 5,000 4,900 339 338 339 338 337 337 4,800 5,700 5,600 4,600 4,700 6,200 Hexane Mineral oil ins. ins. ins. ins. 310 310 4,100 4,200 308 308 5,100 4,500 334 334 5,400 6,000 Ethanol 90%-water Ethanol 10% • max e Wavelengthshiftfrom A•. max = A•. max ---- A•. max ---- A•. max = non-polarto polar -- 3 nm -- 2 nm -- 2 nm q-2 nm solvent shift) in goingfrom non-polarto polarsolventsare listed in Table II. Sunscreens that experienced little or no shift in their }t max in the varioussolventstestedare listed in Table III. Sunscreens, where the }t max was shifted towardslonger wavelengths (bathochromicor red shift), are listed in Table IV. Experimentalvaluescouldnot be obtainedin thoseinstances wherethe sunscreen wasnot solublein the particularsolvent selectedfor studyand are soindicatedin eachtable. The change in thewavelength of maximumabsorbance (A }t max)fromtheleastpolar solvent(i.e., mineral oil) to the mostpolarsolvent(i.e., ethanol70%-water 30%) for each sunscreenis listed at the bottom of eachtable (II-IV). Where a sunscreenwas insoluble in eithera particularpolaror non-polar solvent,the A }t maxwascalculated betweenthe leastpolar solventand the mostpolar solventin which the sunscreen was soluble. In addition,selectedUV absorptionspectraof severalof the moreimportantsunscreen chemicalsin eachcategory(hypsochromic, bathochromic, and minimum or no shift), illustratingthe magnitudeof the shift in the }t max in both polarand non-polarsolvents, are alsopresentedin Figures1-5. DISCUSSION CHANGES IN WAVELENGTH OF MAXIMUM ABSORBANCE In orderfor the cosmeticchemistto estimatethe effectformulationcomponents haveon the UV characteristics of a particularsunscreen chemical,the polarityof the sunscreen andthe polarityof the components in thepreparation shouldbe determined. The rela- SOLVENTS AND SUNSCREEN ABSORBANCE O-IC'-IC'-IC'-IC'-IC'-IC'-IC'-IC'-IC'-I _.[_ II 0000 + II 213 214 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS r•O 72? • t Absorbance units •, / '%,., // x,, / \ /' \ ,, /' 100% ETHYL ALCOHOL I" / , !, 588,8 Wavelepgth (rim} ! ! ! -6.?62 • / / / ETHOXY Absorbance ETHANOL units i i Wavelength(rim) Figure 1. UV absorption spectra of PABAshowing a hypsochromic shiftin the •. maxin theUVB region (290 to 320 nm) from a lesspolarsolvent(ethoxyethanol)to a morepolarsolvent(ethanol). tive lipophilicity,a measureof a compound's relativepolarity,hasbeendeterminedby calculatingthe log of the partitioncoefficientbetweenoctanol,a modellipid, andwater (log P) for 15 sunscreen chemicals.Thesedata are listed in decreasing orderof polarity (i.e., increasinglog P values)in Table V. The log P valueswerecalculatedfrom the structural formula of each sunscreen in accordance with Rekker's method of deter- SOLVENTS AND SUNSCREEN 100% ETttY• ABSORBANCE 215 ALCOItOI, Absorbance units -8.881 38g.8 • 488 g Wavelength 8.7•2 n units 28e.• 38e•.e 488 e• Wavelength(nm) Figure2. UV absorption spectra of dioxybenzone showing a hypsochromic shiftin thek maxin theUVA region(320 to 360 nm) from a non-polarsolvent(hexane)to a polarsolvent(ethanol). mining hydrophobic fragmentalconstants (9). All of the sunscreen chemicals included in this paperare listedin Table V with the exceptionof sulisobenzone. Nevertheless, becauseof solubility (Table II) and structuralconsiderations, sulisobenzone is consideredto behighlypolar.The datareportedin TableV indicatethat therearetwo groups of sunscreens: onethat is morepolar(i.e., log P valuesbetween-0.02 to 2.84) and the otherthat is considered to be lesspolar(i.e., log P valuesbetween4.53 and6.08). The main ingredientin the cosmetic preparationthat usuallywill causethe k max to shift is the solventor vehicle.If the solventis very volatile and evaporates when the 216 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS 100% ETHYL ALCOHOL Absorbance units -- W•velength (nm•) I I ! ! • i i ! • I ! I ! • I Absorbancr units 8.88 Wavelength (nm) Figure 3. UV absorption spectraof octylsalicylate showingno apparentshiftin the X maxin the UVB region(290 to 320 nm) from a non-polarsolvent(hexane)to a polar solvent(ethanol). sunscreen formulationis placeduponthe skin, then other lessvolatileingredientsin high concentration will affectthe UV characteristics of the sunscreen chemical. If the sunscreen is polar(i.e., PABA, dioxybenzone, sulisobenzone, and oxybenzone), then interactionswith polar solventswill causethe UV absorbance spectrato shift towardsshorterwavelengths (TableII andFigure1). Thus PABA becomes lesseffective asthe polarityof the solventincreases and k max shiftsfrom the UVB regionto the UVC region.In the caseof the threebenzophenones tested,a hypsochromic shiftoccurs within the UVA region. SOLVENTS AND SUNSCREEN 100% 0 425 ETHYL ABSORBANCE 217 ALCOIIOL A Absorbance units / /' / Wavelength (nm), I -8.415 AL•o•noe HEXANE - units .0.005 Wavelength (nm) Figure 4. UV absorptionspectraof octyl p-methoxycinnamateshowinga bathochromic shift in the max in the UVB region(290 to 320 nm) from a non-polarsolvent(hexane)to a polarsolvent(ethanol). On the other hand, if the sunscreen is lesspolar (i.e., octyl dimethyl PABA, octyl cyanodiphenylacrylate, octyl p-methoxycinnamate, butyl methoxydibenzoylmethane, and ethyl dihydroxypropyl PABA), then interactionswith polar solventswill shift the UV absorbance spectrato longerwavelengths (TableIV; Figures4 and5). In the caseof octyl dimethylPABA, it still remainswithin the UVB regionregardless of the polarity of the solvent in which it dissolves.However, as the solvent becomeseither more or less polar, k max is displacedfrom 308 nm, the wavelengthof optimumprotectionfor a UVB absorber.In the caseof octyl p-methoxycinnamate, formulatingwith non-polar solventsshouldbe avoidedsincesuchsolventswill shiftthe k max awayfrom 308 nm. 218 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS 100%ETHYL ALCOHOL ,/•'•\,\ Absorbance units ',--•.--'"-"-",-,. "• 800 0 .•",./' II I • I • I • I •,, W•vele•th (nm)l Absorbance units I I i I • I ' , /,.'I 1 HEINE , O Waveleith (nm) Figure 5. UV absorption spectra of octyldimethylPABAshowinga bathochromic shiftin the h maxin the UVB region(290 to 320 nm) froma non-polarsolvent(hexane) to a polarsolvent(ethanol). Triethanolaminesalicylate,octyl salicylate,homomenthylsalicylate,and menthyl anthranilateshowedonly minor variationsin h max in both polarand non-polarsolvents(Table III and Figure 3). The minimum shift of the h max is due to the orthosubstitutedconfiguration of salicylates andanthranilates. The lonepair of electrons are involvedin the six-membered cyclicarrangementand, asa result, are not availablefor interaction with polarsolvents (Figure6). Hence,ortho-substituted compounds tendto exhibit moderateto low • max shiftsin polar solvents.Althoughoxybenzone and dioxybenzone bothmayforma six-membered cyclicalarrangement, similarto the salicy- latesandanthranilates, theyexhibitaddedpolaritydueto the additionalhydroxyand methoxygroups. A more in-depthexplanationfor the shiftsand changesobserved in the • max that occurwhen sunscreen chemicals aredissolvedin bothpolarand non-polarsolventshas beenprovidedin separatereportsby Shaath(10, 11). SOLVENTS AND SUNSCREEN Table ABSORBANCE 219 V RelativeLipophilicity of Sunscreen ChemicalsBasedUpon Their CalculatedPartition Coefficients Between Octanol CTFA Other names Log P @25øc 1,2,3-Propanetriol, 1-(4-aminobenzoate) - 0.02 Sulisobenzone - 1.51 name Glyceryl PABA Benzophenone-4 PABA Benzophenone-8 Cinoxate Benzophenone-3 Ethyl dihydroxypropylPABA Amyl dimethyl PABA Butylmethoxydibenzoylmethane Menthyl anthranilate Octyl salicylate Homosalate Octyl methoxycinnamate Octocrylene Octyl dimethyl PABA CHANGES and Water IN MOLAR p-Amino benzoicacid Dioxybenzone Ethoxyethylmethoxy cinnamate Oxybenzone Ethyl-4-bis(2-hydroxypropyl-aminobenzoate) Amyl dimethylPABA Butylmethoxydibenzoylmethane Menthyl-O-aminobenzoate 2-Ethylhexylsalicylate Homomenthylsalicylate Ethylhexyl-p-methoxycinnamate Octyl cyanodiphenylacrylate 2-Ethylhexyl-p-dimethylaminobenzoate 0.74 2.15 2.55 2.63 2.84 4.53 4.86 5.05 5.30 5.61 5.65 5.69 6.08 ABSORPTIVITY In additionto shiftsin X max, both increases and decreases in the molar absorptivities (½)of sunscreenchemicalswere alsoobservedin the varioustest solvents. In general,andwith the exception of PABA, the restof theUVA andUVB sunscreens selectedfor studyshowedincreased ½ valuesat X max in both polar(ethanol-water systems) andnon-polar (hexane andmineraloil) solvents. In contrast, thereweresignificant decreasesin ½ values at • max when the sunscreenchemicals were dissolved in semi-polar solvents suchashexylene glycolandC•2-C•5alcohols benzoate. Thesedata (takenfrom Data TablesII-IV) havebeensummarizedin TablesVI andVII. Reduction in molarabsorptivity variedbetween12%and55% forhexylene glycoland between7% and28% forC•2-C•5 alcohols benzoate. In addition,employinga spectrophotometric technique suggested byVogelman etal. (12),overall reduction in thearea H 6 I 0 -- Menthyl (a) ø I 0 -- Octyl (b) Figure6. Stericconfiguration ofortho-substituted molecules, (a)menthyl anthranilate and(b)octylsalicylate. 220 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS Table VI Sunscreens andSolventSystems That Showed Changes in MolarAbsorptivity Approximate Sunscreen Solventexhibiting Solventexhibiting increased decreased molarabsorptivity reductionin molar molarabsorptivity absorptivity UVA Absorbers Dioxybenzone Hexane Sulisobenzone Menthyl anthranilate Ethanol 90%-water Ethanol 70%-water 10% 30% Butylmethoxydibenzoyl- Ethanol 90%-water 10% Ethanol 90%-water 10% methane Oxybenzone Hexyleneglycol Methyl carbitol Isopropylpalmitate Isopropylmyristate Hexyleneglycol C12-C15alcoholsbenzoate 40% 37% 25% 25% 24% 24% Mineral oil 18% underthe absorbance-vs-wavelength curveof 32% to 35% wasobserved for oxyben- zone,dioxybenzone, andoctylcyanodiphenylacrylate, andtherewasa 75% reduction for triethanolamine salicylate in goingfrompolarto non-polarsolvents. Klein hasrecentlyreported(4, 13) almostcompletesuppression of UV absorbance spectra of octyldimethylPABA,octylp-methoxycinnamate, andbenzophenones alone and in combinationwith eachother in two branched-chain liquid fatty esters(i.e., isostearyl neopentanoate and isopropyl linoleate).Klein'sfindingfor octyldimethyl PABA in isostearyl neopentanoate hasbeenconfirmedin our laboratory. The principalcharacteristics of a UV absorption bandareits position(k max)andits intensityor molarabsorptivity (½).In thecaseof thelatter,½values at k maxofmostof the sunscreen chemicalstestedwere greatestin polarand non-polarsolventsand reducedin hexylene glycolandC•2-C•5alcohols benzoate. Drasticreductions in ½value Table VII Sunscreens and SolventSystems That ShowedChangesin Molar Absorptivity Solventexhibiting increased Sunscreen Solventexhibiting decreased molarabsorptivity molar absorptivity Approximate reductionin molar absorptivity UVB Absorbers PABA Ethyl dihydroxypropyl Ethoxyethanol Ethanol 90%-water 30% Ethanol Hexyleneglycol 33% 23% Ethanol 70%-water Ethanol 70%-water Hexyleneglycol C12-C15alcoholsbenzoate 21% 25% Methyl carbitol Hexyleneglycol Ethanol 70%-water 30% Hexane Isopropylmyristate Hexane Hexyleneglycol Hexyleneglycol 29% 20% PABA Octyl dimethyl PABA Octyl p-methoxy 30% 30% cinnamate TEA salicylate Octyl salicylate Homomenthylsalicylate Octyl-2-cyanodiphenylacrylate Ethanol C12-C15 alcoholsbenzoate 55% 28% SOLVENTS AND SUNSCREEN ABSORBANCE 221 in suchsemi-polarsolventswould requireincreasingthe concentration of requiredsunscreenfor maximumprotectionor, in the caseof branched-chain liquid fatty esters, replacementwith a moreappropriatesolvent. In conclusion, the wavelengthof maximumabsorbance (h.max)in the UVA and UVB regionsof the spectrum andthe resultantmolarabsorptivity (E)of a sunscreen chemical oftenwill be affectedby the solventin which it is dissolved.The changesobservedin thesetwo importantparameters appearto be stronglyinfluencedby the polarityand chemicalstructureof both the sunscreen and the solvent.The resultsof the present study of the interactionbetweensunscreens and solventsprovidepracticalinformation that cosmeticchemistsmay find usefulin formulatingsunscreen preparations. REFERENCES (1) S. Riegelmanand R. P. Penna,Effectof vehiclecomponents on the absorptioncharacteristics of sunscreen compounds, J. Soc.Cosmet. Chem.11, 280-291 (1960). (2) G. A. Groves,Factorsinfluencingthe formulationof sunscreens, Amer.Cosm.Perf., 87, 54-58 (July 1972). (3) B. M. Cumpelik, Sunscreens at skin applicationlevels:Direct spectrophotometric evaluation,J. Soc. Cosmet.Chem., 31, 361-366 (1980). (4) K. Klein and I. Doshi, Sunscreen/solvent interactions:An in-vitro evaluation, 14th International IFSCC Congress, September16-19, 1986, Barcelona,Spain. (5) For a moredetailedexplanationof the experimental procedureandresults,referto: L. E. AgrapidisPaloympis,TheInfluence ofSolvent ontheUV Absorbance ofSunscreens, M.S. Thesis,St. John'sUniversity (1987). (6) Department of Health, Educationand Welfare, US FDA, Sunscreen drug productsfor over-thecounterhumanuse,Fed.Reg.,43(166), 36206-38269 (1978). (7) C. Vaughan, Using solubility parametersin cosmeticformulations,J. Soc.Cosmet.Chem.36, 319-333 (1985). (8) Spectrometry nomenclature, Anal. Chem.56, 125 (1984). (9) R. F. Rekker, The Hydrophobic Fragment Constant (ElsevierScientificPublishingCompany,New York), 1977. (10) N. A. Shaath,The chemistryof sunscreens, Cosmetics and Toiletries,101, 55 (March 1986). (11) N. A. Shaath,On theTheoryof UltravioletAbsorption of Sunscreen Chemicals, AnnualMeeting ofthe Society Cosmetic Chemists, New York, December1986,J. Soc.Cosmet.Chem., 82, 193-207 (May/ June 1987). (12) J. Vogelman,E. Nieves,J. Brind, R. Nash, and N. Orentreich,A spectrophotometric methodfor determiningrelativeSPFvaluesof sunscreen preparations, J. AppliedCosmetol., 1, 1-11 (1985). (13) K. Klein, Van Dyk Division,Mallinckrodt,Inc., Belleville,NJ 07109, privatecommunication.