1 September 2010 Influence of the absorption behavior of sunscreens in the short-wavelength UV range (UVB) and the long-wavelength UV range (UVA) on the relation of the UVB absorption to sun protection factor
Author Affiliations +
Abstract
The absorption of filter substances in sunscreens, reducing the incident ultraviolet (UV) radiation, is the basis for the protecting ability of such formulations. The erythema-correlated sun protection factor (SPF), depending mainly on the intensity of the UVB radiation, is the common value to quantify the efficacy of the formulations avoiding sunburn. An ex vivo method combining tape stripping and optical spectroscopy is applied to measure the absorption of sunscreens in the entire UV spectral range. The obtained relations between the short-wavelength UV (UVB) absorption and the SPF confirm a clear influence of the long-wavelength UV (UVA) absorption on the SPF values. The data reflect the historical development of the relation of the concentration of UVB and UVA filters in sunscreens and points to the influence of additional ingredients, e.g., antioxidants and cell-protecting agents on the efficacy of the products.

1.

Introduction

Ultraviolet active filters are the decisive components in sunscreens, reducing the intensity of the sun radiation reaching the living cells of the human body.1 Therefore, it seems worthwhile to use a recently proposed ex vivo spectroscopic method2 to investigate the relation between the UV filter absorption to the classical sun protection factor (SPF). This SPF value has been used for a number of years to quantify the sunscreen protection. It is strongly correlated to the well-investigated sun-induced injury to the human body—the formation of an erythema, well-known as sunburn.3

The erythema action spectrum4 shows a strong efficacy of the short-wavelength UV (UVB) part of the sun radiation. Influences of an additional radiation in the long-wavelength UV (UVA) range are outlined by the terms photoaugmentation and/or photoaddition.5

Photoaugmentation describing the potentiation of UVB induced effects by long-wave radiation is confirmed, e.g., for the erythemal component of the sunburn reaction but not for the sunburn cell production.6 Photoaddition was found to be the main process determining the erythemally effective irradiance, taking into account the additional influence of UVA radiation on the UVB efficacy.7

In this paper the influence of the absorption behavior of sunscreens in the UVB and UVA ranges on the UVB absorption/SPF relation is determined. To obtain a broad overview, sunscreens that have been developed during recent years are taken into account.

2.

Methods

2.1.

Volunteers

The sunscreen was applied on the flexor forearms of six healthy volunteers (in total one-third males and two-thirds females), aged between 23 and 45years (skin phototypes I to III).8 The volunteers stayed in an inner room without sun exposure (room temperature about 21°C ) from half an hour before the examination started until the end of the examination. The ethical approval for these experiments was obtained from the Ethics Committee of the Charité Universitaetsmedizin Berlin, Department of Dermatology, Berlin, Germany. All volunteers gave their written informed consent.

2.2.

Sunscreen Application

The investigated sunscreens were bought directly before the measurements were carried out (commercial samples) or were freshly prepared [COLIPA (European Cosmetics Toiletry and Perfumery Association) emulsions and model formulations], thus guaranteeing that all products were used within their date labeling. Samples with the following SPF values were investigated: 4, 6, 8, 12, 13, 16, 20, 25, 26, 30, 50, 55, and 60.

A precleaning of the skin was realized by rinsing the flexor forearm with cold water and drying it with a paper towel afterward. We applied 2mgcm2 of the commercial sunscreens or model formulations to an area of 8×10cm2 corresponding to the COLIPA standard.3

2.3.

Tape-Stripping

The tape-stripping procedure; as described previously,9, 10 started 1h after sunscreen application, transferring the stratum corneum layer by layer to the tape strips together with the UV filters. After pressing the adhesive tapes (tesa film, 5529, Beiersdorf, Hamburg, Germany, width: 19mm ) onto the human skin with a stamp (pressure: 15kPcm2 ) the strips were quickly removed. Ten tapes were taken from the treated and untreated skin areas.

2.4.

Spectroscopic Measurements

The absorption spectra were recorded immediately after removal — within 15s — to avoid disturbances by diffusion processes inside the adhesive layer, which result in a homogeneous distribution of the UV filters.11, 12

The spectra of the tape strips together with an empty tape as a reference were recorded in the range 240to500nm using the UV/VIS spectrometer Lambda 5 (PerkinElmer, Frankfurt/Main, Germany) with an integrating sphere and a rectangular beam diameter of 8×10mm2 .

The software UV Winlab Version 2.70.01 (PerkinElmer, Frankfurt/Main, Germany) was used to correct the corneocyte-correlated influences and to calculate the sum of the transmission spectra.

2.5.

Sum Transmission Spectra and Average Sum Transmission Values

The sum transmission spectra in the complete UV range (see Fig. 1 in the following section) were calculated by adding the spectra of all tape strips with a detectable amount of UV filters on the basis of the absorbance values. The obtained sum spectrum was subsequently changed to the transmission values.

Fig. 1

Determination of the sum transmission spectrum and the corresponding areas beneath the sum spectrum used to determine the average UVA und UVB sum transmissions (sunscreen sample 7 with SPF 16).

055008_1_042005jbo1.jpg

The areas beneath the last curve (sum transmission spectrum) are the basis on which we calculated the average sum transmission values, representing the remaining intensity after sunscreen application in the corresponding spectral ranges:

  • 1. average UV sum transmission, dividing the area measured in the range of 280to400nm by the spectral interval 120

  • 2. average UVB transmission, dividing the area measured in the range of 280to320nm by the spectral interval 40

  • 3. average UVA transmission, dividing the area measured in the range of 320to400nm by the spectral interval 80.

All spectroscopic data discussed hereafter are mean values balancing out the interindividual differences found for different volunteers as a result of a varying skin profile determined by furrows and wrinkles.11

3.

Results and Discussion

The applied protocol resulted in the sum transmission spectra describing the absorption behavior of the filter substances applied with sunscreens under ex vivo conditions which were taken as the basis to calculate average sum transmission values.

3.1.

Average Sum Transmission Spectrum

The protocol determining the sum transmission spectra was described previously2 and in the previous section. Figure 1 illustrates the development of a sum transmission curve taking into account the individual spectra of the tape strips removed one by one.

The area beneath the sum transmission curve and the calculated average UV sum transmission values reflect the influence of the applied UV filters on the incident UV radiation. In the given example, the average UV sum transmission resulted in 12% transmission, the average UVB sum transmission resulted in 2% transmission, and the average UVA sum transmission resulted in 18% transmission.

The corresponding data determined for all investigated sunscreens are taken to discuss the relationship between the characteristic values of the UVB filter — described by the average UVB sum transmission — and the SPF. To understand the influence of the variable UVB/UVA intensity ratio, the average UVA sum transmission was also taken into account.

3.2.

Relation of the Absorption Behavior in the UVB Range to SPF

In a first step, the originally determined average UVB sum transmission values obtained after tape stripping and spectroscopic measurements are compared with the corresponding SPF values declared by the sunscreen producers (Table 1 ).

Table 1

Summary of the average UVB sum transmission values in relation to the SPF values.

Filter SubstancesSampleSPFAverage UVB SumTransmission (%T)
A144.3
Model emulsion262.8
F, A, G384.1
G, D, F482.9
Model emulsion5110.7
G, A, I6123.1
B, C7130.4
A, D, E8162.3
H, D, J, A9161.9
H, D, J10202.1
D, H, J, G, I11202.6
G, A, I12201.2
F, D, N, G, I13253.9
H, D, J, I14261.5
D, M, A, G, I15302.1
I, E, H, J, D16500.6
Model emulsion17551.4
A, K, I, L18600.4

Model emulsions: the filter substances contained in the model emulsions are not available for publication.

Filter substances: A, ethylhexyl methoxycinnamate; B, octyl dimethyl PABA; C, benzophenone-3; D, butyl methoxy dibenzoylmethane; E, phenylbenzimidazole sulfonic acid; F, bis ethylhexyloxyphenol methoxyphenol methoxyphenyl triazine; G, octocrylene H, 4-methylbenzylidene camphor; I, titanium dioxide; J, octyl triazone; K, methylene bis-benzotriazolyl tetramethylbutylphenol; L, zinc oxide; M, diethylhexyl butamido triazone; N, butyl methylpropianate citronellolphenyl.

It is obvious that the UVB sum absorption obtained for sunscreens with identical SPF values varies to a high extent.

In a previous publication,13 the UVB sum transmission as a measure of the active UVB radiation intensity was correlated to the SPF demonstrating the principal relation of the spectroscopic data and the SPF. The connection of the data was described by an exponential trend line.

Enlarging the number of sunscreens by taking into account formulations with a broader variation of the UVB/UVA ratio, including the “historical” formulations with an extremely low UVA protection, give new insights.

In the graph presented in Fig. 2 , the reciprocal UVB transmissions are used to obtain linear trend lines of these data to the SPF values. In the graph, three trend lines can be recognized with a higher variation of the individual points around the middle rank. The existence of the different trend lines becomes understandable when we take into account the interaction of the UVB and the UVA radiation producing the erythema.

Fig. 2

Relation of the reciprocal values of the average UVB sum transmissions to SPF.

055008_1_042005jbo2.jpg

The available spectroscopic data enabled the calculation of the sample specific UVB/UVA relation factors FUVBUVA dividing the average UVB sum transmission by the average UVA sum transmission.

Two samples belonging to the upper and the lower trend lines are both shown in Fig. 3 to illustrate the differences in the UVB/UVA relation.

Fig. 3

Sum transmission spectra of sunscreens belonging to the upper and the lower trend lines in Fig. 2: line A, sample 7, SPF=13 ; line B, sample 11, SPF=20 .

055008_1_042005jbo3.jpg

The calculated factors given in Table 2 quantify the absorption behavior of the investigated sunscreens in the UVB and the UVA range, thus describing the possible influence of photoaugmentation and/or photoaddition. The given mean values of the UVB/UVA relation (row 2 of the table) clearly describe the affiliation of the UVB transmissions to one of the three trend lines with a stronger variation for the samples collected in the middle trend line. This underlines a clear influence of the accompanying radiation intensity in the UVA range on the UVB/SPF correlation. Without an absorption in the UVA range, the UVB filter concentration must be much higher to obtain the same SPF value.

Table 2

Correlation of the position of the reciprocal values of the average UVB sum transmission and the SPF values (Fig. 2) to the UVB/UVA factors.

Mean ValueRange of Measured Values
Upper trend line0.030.01–0.06
Middle trend line0.120.05–0.22
Lower trend line0.280.22–0.35

As well as these clear dependencies, two exceptions exist in the group of the investigated sunscreens. First, a small amount of overlap between the ranges found for the FUVBUVA factors collected in the upper and the middle trend lines (lines 2 and 3 in the third row of Table 2). Second, the two samples marked by arrows in Fig. 2, both with an SPF of 20, vary considerably in the UVB/UVA factor (upper point FUVBUVA=0.13 , lower point FUVBUVA=0.36 ). These exceptions hint to the influences of parameters affecting the formation of the erythema in addition to the changes in the UVB/UVA relation, e.g., ingredients with antioxidizing or cell-protecting qualities, etc.14, 15, 16, 17, 18.

Generally, the different trend lines reflect, illustratively, the historical development of the filter types used in sunscreens. Originally, sunscreens were restricted to contain only a UVB filter, resulting in the four points on the upper curve measured for historical formulations not now on the market, These historical sunscreens contained high amounts of UVB filter to obtain reasonable SPF values, because of the missing UVA absorption.

Later in sunscreen development, UVA filters were added, resulting in a higher UVB/UVA relation. This situation is reflected by the sunscreens found in the middle trend line. In this group of formulations, a relatively broad variation around the trend line occurs.

The lowest trend lines summarize three highly effective modern sunscreens with a high absorption in the UVA range, lowering the absorption necessary in the UVB range to realize the measured SPF. This underlines the fact that spectroscopic data are suited to estimate, in an orientated manner, the size of the SPF values taking into account the absorption behavior in the UVB and the UVA ranges. The application of this method is of special interest for the investigation of filter substances not yet approved, not using human but porcine skin.19, 20

The discussion concerning the SPF is limited to one biological response to the formation of erythema with an individual dependence on the intensity of the incident radiation. It is to be expected that corresponding investigations considering other described sun-induced injuries will provide additional and possibly quite different insights. Therefore, it is important to characterize the efficacy of sunscreens not by different effects of biological responses in the human organism, but by noninvasive spectroscopic measurements, as described in this paper.

4.

Conclusion

The results presented in this paper demonstrate that the described noninvasive method of sum transmission measurements, based on tape stripping, is well suited to characterize the UV absorption of sunscreens under ex vivo conditions. It can be used to distinguish between the absorption properties of sunscreens in the UVB and UVA spectral ranges. Therefore, the results are well suited to develop a universal spectral sun protection factor (USPF), which describes the protection efficiency of sunscreens in relation to the absorption in the whole spectral range of sun radiation.

Acknowledgments

We would like to thank the Foundation “Skin Physiology” of the Donor Association for German Science and Humanities for financial support.

References

1. 

Diffey B., “Sunscreens: expectation and realization,” Photodermatol. Photoimmunol. Photomed., 25 233 –236 (2009). https://doi.org/10.1111/j.1600-0781.2009.00459.x 0905-4383 Google Scholar

2. 

Weigmann H. J., Schanzer S., Teichmann A., Durat F., Antoniou C., Schaefer H., Sterry W., Lademann J., “Ex vivo spectroscopic quantification of sunscreen efficacy: proposal of a universal sun protection factor,” J. Biomed. Opt., 12 044013 –044021 (2007). https://doi.org/10.1117/1.2753365 1083-3668 Google Scholar

3. 

Colipa SPF Test Method, Bruxelles, 94/289-Oct. (1994). Google Scholar

4. 

Anders A., Altheide H. J., Knalmann M., Tronnier H., “Action spectrum for erythema in humans investigated with dye lasers,” Photochem. Photobiol., 61 200 –205 (1995). https://doi.org/10.1111/j.1751-1097.1995.tb03961.x 0031-8655 Google Scholar

5. 

Paul B. S., Parrish J. A., “The interaction of UVA and UVB in the production of threshold erythema,” J. Invest. Dermatol., 78 371 –374 (1982). https://doi.org/10.1111/1523-1747.ep12507481 0022-202X Google Scholar

6. 

Kaidbey K. H., Grove K. H., Kligman A. M., “The influence of longwave ultraviolet radiation on sunburn cell production by UVB,” J. Invest. Dermatol., 73 743 –745 (1979). https://doi.org/10.1111/1523-1747.ep12514324 0022-202X Google Scholar

7. 

Diffey B. L., Whillock M. J., McKinlay A. F., “A preliminary study on photoaddition and erythema due to UVB radiation,” Phys. Med. Biol., 29 419 –425 (1984). https://doi.org/10.1088/0031-9155/29/4/011 0031-9155 Google Scholar

8. 

Fitzpatrick J., Eisen A., Wolff K., Freedberg I., Austen K. F., Friedberg I. M., Austen K. F., Dermatology in General Medicine, 1 1694 McGraw-Hill, New York (1993). Google Scholar

9. 

Weigmann H. J., Lademann J., Meffert H., Schaefer H., Sterry W., “Determination of the horny layer profile by tape stripping in combination with optical spectroscopy in the visible range as a prerequisite to quantify percutaneous absorption,” Skin Pharmacol. Appl. Skin Physiol., 12 34 –45 (1999). 1422-2868 Google Scholar

10. 

Lademann J., Jacobi U., Surber C., Weigmann H. J., Fluhr J. W., “The tape stripping procedure—evaluation of some critical parameters,” Eur. J. Pharm. Biopharm., 72 317 –323 (2009). https://doi.org/10.1016/j.ejpb.2008.08.008 0939-6411 Google Scholar

11. 

Weigmann H. J., Schanzer S., Antoniou C., Herrling J., André V., Wünsch T., Schaefer H., Sterry W., Lademann J., “Development of a universal sunscreen protection factor (USPF) based on ex vivo spectroscopic measurements,” SOFW J., 7 2 –7 (2007). Google Scholar

12. 

Mavon A., Miquel C., Lejeune O., Payre B., Moretto P., “In vitro percutaneous absorption and in vivo stratum corneum distribution of an organic and a mineral sunscreen,” Skin Pharm. Physiol., 20 10 –20 (2007). https://doi.org/10.1159/000096167 Google Scholar

13. 

Weigmann H. J., Schanzer S., Herrling J., Wünsch T., André V., Schaefer H., Sterry W., Lademann J., “Spectroscopic characterization of the sunscreen efficacy—basis of a universal sunscreen protection factor,” SOFW J., 9 2 –10 (2006). Google Scholar

14. 

Darr D., Dunston S., Faust H., Pinnell S., “Effectiveness of antioxidants (vitamin C and E) with and without sunscreens as topical photo-protectants,” Acta Derm Venereol, 76 264 –268 (1996). 0001-5555 Google Scholar

15. 

Matsui M. S., Hsia A., Miller J. D., Hanneman K., Scull H., Cooper K. D., Baron E., “Non-sunscreen photoprotection: antioxidants add value to a sunscreen,” J. Investig. Dermatol. Symp. Proc., 14 56 –59 (2009). https://doi.org/10.1038/jidsymp.2009.14 1087-0024 Google Scholar

16. 

Lin J. Y., Tournas J. A., Burch J. A., Monteiro-Riviere N. A., Zielinski J., “Topical isoflavones provide effective photoprotection to skin,” Photodermatol. Photoimmunol. Photomed., 24 61 –66 (2008). https://doi.org/10.1111/j.1600-0781.2008.00329.x 0905-4383 Google Scholar

17. 

Kemeny L., Koreck A., Kis K., Kenderessy-Szabo A., Bodai L., Cimpean A., Paunescu V., Raica M., Ghyczy M., “Endogenous phospholipid metabolite containing topical product inhibits ultraviolet light-induced inflammation and DNA damage in human skin,” Skin Pharm. Physiol., 20 155 –161 (2007). https://doi.org/10.1159/000098702 Google Scholar

18. 

Reuter J., Jocher A., Stump J., Grossjohann B., Franke G., Schempp C. M., “Investigation of the anti-inflammatory potential of aloe vera gel (97.5%) in the ultraviolet erythema test,” Skin Pharm. Physiol., 21 106 –110 (2008). https://doi.org/10.1159/000114871 Google Scholar

19. 

Zastrow L., Ferrero L., Klein F., Groth N., “A major innovation in sun protection measurement—the integrated sun protection factor ISPF,” SOFW J., 9 12 –19 (2006). Google Scholar

20. 

Weigmann H. J., Schanzer S., Patzelt A., Bahaban V., Durat F., Sterry W., Lademann J., “Comparison of human and porcine skin for characterization of sunscreens,” J. Biomed. Opt., 14 024027 –1-6 (2009). https://doi.org/10.1117/1.3103340 1083-3668 Google Scholar
© (2010) Society of Photo-Optical Instrumentation Engineers (SPIE)
Hans-Jürgen Weigmann, Sabine Schanzer, Christina Antoniou, Wolfram Sterry, and Jürgen M. Lademann "Influence of the absorption behavior of sunscreens in the short-wavelength UV range (UVB) and the long-wavelength UV range (UVA) on the relation of the UVB absorption to sun protection factor," Journal of Biomedical Optics 15(5), 055008 (1 September 2010). https://doi.org/10.1117/1.3497047
Published: 1 September 2010
JOURNAL ARTICLE
4 PAGES


SHARE
Advertisement
Advertisement
Back to Top