Professional Documents
Culture Documents
Intern J of Cosmetic Sci - 2015 - Li - The Adsorption Behaviour and Photoprotection Effect of UV Filter Absorbed On The
Intern J of Cosmetic Sci - 2015 - Li - The Adsorption Behaviour and Photoprotection Effect of UV Filter Absorbed On The
12247
Keywords: adsorption isotherm, adsorption kinetics, chemical analysis, hair treatment, photodamage, UV filters
Synopsis lumiere ont ete identifies par diverses methodes, y compris la degra-
OBJECTIVE: Butyl methoxydibenzoylmethane (BMBM, an UVA dation des proteines, la degradation du tryptophane, la peroxyda-
absorber, the maximum absorptive wavelength is about 360 nm), tion lipidique, et les changements de surface dans les cheveux
octylmethoxycinnamate (OMC, an UVB filter, the maximum exposes a une irradiation.
absorptive wavelength is about 310 nm), benzophenone-3 (an
RESULTATS: Les resultats ont montre que l’adsorption de filtres
UVA and UVB filter, the maximum absorptive wavelength is about UV se produit assez rapidement et atteint l’equilibre apres environ
288 and 323 nm) and octyl salicylate (an UVB filter, the maxi- 1 h. Le taux et le montant de l’adsorption augmentaient avec la
mum absorptive wavelength is about 307 nm) are four types of UV concentration initiale. La quantite d’adsorption de chaque filtre UV
filters. This report presents the adsorption behaviours and effects of a ete tracee en fonction de sa concentration a l’equilibre. La capa-
these filters on hair cuticles. cite d’adsorption de 2% BMBM etait plus elevee que celle des autres
METHODS: Adsorption amounts of each UV filter on the hair sur- filtres UV. La peroxydation lipidique et la degradation des proteines
face were determined via the depletion method, and the photopro- de cheveux etaient significativement reduites dans les echantillons
tective effects of these filters were identified by various methods, traites avec de la benzophenone-3, le salicylate d’octyle, et MOC. La
including protein degradation, tryptophan degradation and lipid degradation du tryptophane n’etait pas significativement amelioree
peroxidation in hair exposed to irradiation. dans tous les traitements.
RESULTS: Results showed that adsorption of UV filters occurred CONCLUSION: La cinetique d’adsorption des filtres est comparable
fairly rapidly and reached equilibrium after approximately 1 h. The a un modele cinetique de pseudo-second ordre et leurs isothermes
rate and amount of adsorption increased with increasing initial d’adsorption correspondent au modele d’adsorption de Freundlich.
concentration. The adsorption amount of each UV filter was plotted L’adsorption suit un processus endothermique. Les filtres UV ont
against its equilibrium concentration. The adsorption capacity of un effet sur la protection des cheveux contre le photovieillisse-
2% BMBM was higher than that of the other UV filters. Lipid per- ment. Les effets des filtres UVB sont meilleurs que ceux des filtres
oxidation and protein degradation of hair were significantly UVA.
reduced in samples treated with benzophenone-3, octyl salicylate
and OMC. Tryptophan degradation was not significantly improved
in any of the treatments. Introduction
CONCLUSION: The adsorption kinetics of the filters is comparable It is easy to become obsessed with the skin when mentioned photo-
with a pseudo-second-order kinetic model and that their adsorption protection. However, hair is also susceptible to the sun as the skin.
isotherms match the Freundlich adsorption model. Adsorption fol- This observation has been reported using UV sources as a labora-
lowed an endothermic process. UV filters have effect on protecting tory simulation of sunlight [1]. Hair fibres exposed to sunlight may
hair from photodamage. The effect of UVB filters is better than lead to physical and chemical changes [2]. As physical changes,
UVA filters. dryness, reduced strength, rough surface texture, colour fading,
decreased lustre, stiffness and brittleness can be mentioned, as
Re sume chemical changes, shifts in hair proteins, lipids and pigments may
OBJECTIF: Les butyl methoxydibenzoylmethane (BMBM), oc- occur [2].
tylmethoxycinnamate (MOC), benzophenone-3 et octylsalicylate Hair photodamage can be caused by UVA, UVB and visible radi-
sont quatre types de filtres UV. Ce rapport presente les comporte- ations, and the effects of different wavelength range vary. UVB
ments d’adsorption et les effets de ces filtres sur les cuticules des radiation is mainly responsible for protein loss, whereas UVA radia-
cheveux adsorption. tion promotes hair colour change [3]. The UVB is largely absorbed
METHODES: Les quantites d’adsorption de chaque filtre UV sur la by the cuticle, whereas UVA reaches through the cuticle layers and
surface des cheveux ont ete determinees par la methode de l’epuise- produces free radical/reactive oxygen species (ROS) through inter-
ment, ainsi que les effets protecteurs de ces filtres vis-a-vis de la action with endogenous photosensitizers, which is related to the
bleaching of the virgin hair [4]. According to Hoting et al. [5–7],
Correspondence: Wanping Zhang, School of Perfume and Aroma Technol- different hairs were bleached or photo-yellowed by different wave-
ogy, Shanghai Institute of Technology, Shanghai 201418, China. Tel.: length of radiation. For instance, natural blond hair and black hair
+8613817282682; fax: +86 60873373; e-mail: zhwanp@126.com were bleached by UVA and visible light, respectively.
BHBM OMC
B
Based on the researches of hair photo-degradation mechanisms,
functional additives, mainly including chemical filters and natural
plant extracts, were applied in hair care to weaken photodamage.
However, they act in different ways. UV filters absorb ultraviolet
light, whereas plant extracts are inactive free radicals. As there is a
trend of using natural plant extracts in cosmetics, more natural
plant extracts were studied in hair protection. However, high purity
plant extracts are difficult to get and many of them cost much con-
trast to UV filters. Therefore, more and more UV filters are being
researched. However, studies of the adsorption behaviours of UV fil-
ters were left out. Comparison of different structures of filters for
hair’s protection was also less frequently addressed in literatures.
This work aimed to analyse the adsorption behaviours and
photoprotective effects of chemical organic filters. Four UV filters
with different structures (Fig. 1) were selected to determine their
adsorption kinetics and adsorption isotherms on human hair. C
Photoprotective effects against protein degradation, lipid peroxida-
tion and tryptophan decomposition of the hair fibres were
evaluated.
Materials
Natural black hair tresses (20 cm in length) were collected from
volunteers aged between 19 and 25. Organic UV filters, Uvinul
MC80 (OMC, octylmethoxycinnamate) and benzophenone-3 were
provided by BASF. Butylmethoxydibenzoylmethane (BMBM) and
octyl salicylate were obtained from Alsland. The caprylic/capric
triglyceride (GTCC) was purchased from BASF. Bovine serum D
albumin (BSA), methanol, ethanol, thiobarbituric acid and trichlo-
roacetic acid were a kind gift of Tansoole. The water used
throughout the experiments was deionized. All other reagents
were of analytical grade and which were used without further
purification.
Hair treatments
The 20-cm-long virgin hair tresses (i.e. hairs with no chemical and
physical damage) were used. The hair tresses were prepared with
modified procedures described in the literature [8]. Briefly, the hair
sample was washed with 3% sodium dodecyl sulphate (SDS) solu-
tion to remove the dust and possible contaminants, and then
immersed in the anhydrous diethyl ether for 12 h to remove Figure 2 Kinetic curves of UV filters adsorption on human hair at different
grease. Finally, the sample was rinsed with running water, air- initial concentrations, (A) BMBM, (B) OMC, (C) benzophenone-3, (D) octyl
dried and stored for the subsequent experiments. salicylate at 50°C.
C0 mmol/L BMBM OMC Benzophenone-3 Octyl salicylate BMBM OMC Benzophenone-3 Octyl salicylate
C0 mmol/L BMBM OMC Benzophenone-3 Octyl salicylate BMBM OMC Benzophenone-3 Octyl salicylate
A
Results and discussion
t 1 t
¼ þ ð2Þ
Qt k2 Qe 2 Qe
C
where k1 and k2 are the rate constants of adsorption for the first
order and pseudo-second order, respectively; Qe and Qe are the
amounts of UV filters adsorbed on dry hair at equilibrium and time,
respectively.
The rate constants for first order and pseudo-second order along
with the correlation coefficients were derived (Table I) by fitting the
experimental data to Eqns (1) and (2). It was found that the experi-
mental data of all of these UV filters are better matched to the
pseudo-second-order kinetics model.
Adsorption kinetics generally follows a first-order adsorption
model and is mainly determined by adsorbate diffusion. By con-
trast, the pseudo-second-order adsorption process takes external
surface adsorption and intraparticle diffusion, among other factors,
into consideration [14]. Thus, adsorption of UV filters on the hair
D surface was determined by the speed of molecular diffusion towards
the scale edge of the hair cuticle, non-homogeneity of the UV filter
and physical surface adsorption.
Table III Qualitative and quantitative composition of hair-care formulation In this study, the Freundlich adsorption model is selected. The
derived equations by fitting the experimental data along with the
correlation coefficients (R2) are presented in Table II.
Proportion (%w/w) The initial adsorption amount of each UV filter slowly increased
with increasing concentration and then quickly intensified until
INCI component A B C D E equilibrium was achieved. The adsorption capacity of 2% BMBM
was higher than that of the other UV filters. This initial adsorption
is believed to occur principally through hydrogen bond interactions
BMBM 2 0 0 0 0 between the carboxyl and amino groups of the hair surface and
OMC 0 2 0 0 0
the hydroxyl group of the UV filter. Thus, adsorption capacities
Benzophenone-3 0 0 2 0 0
Octyl salicylate 0 0 0 2 0 mainly depend on the force of hydrogen bond interactions in this
GTCC 6 6 6 6 6 region. Hydroxyl groups are more efficient than ester groups at
Cetearyl Alcohol & Cocoglucoside water 1 1 1 1 1 forming hydrogen bonds with amino acids in hair, and higher
To To To To To polarities of hydrogen bonds increase the adsorption capacity of
100 100 100 100 100 hair. The adsorption isotherms are noticeably influenced by temper-
ature, as noted in Fig. 3. The adsorption capacity of the UV filters
is lower at 50°C than at 40°C, which implies that adsorption is
most likely an endothermic process.
Figure 4 Increase in hair protein degradation of A, B, C, D and E samples Figure 5 Increase in lipidic peroxidation of A, B, C, D and E samples with
with 36 and 72 h UV irradiation. (a) placebo formulation containing BMBM, 36 and 72 h UV irradiation. (a) placebo formulation containing BMBM, (b)
(b) placebo formulation containing OMC, (c) placebo formulation containing placebo formulation containing OMC, (c) placebo formulation containing
benzophenone-3, (d) placebo hair-care formulation containing octyl salicy- benzophenone-3, (d) placebo hair-care formulation containing octyl salicy-
late, (e) placebo hair-care formulation. Means that do not share a letter are late, (e) placebo hair-care formulation. Means that do not share a letter are
significantly different. significantly different.
Table V Lipid peroxides of A, B, C, D and E samples with and without irra- Table VI Fluorescence intensity values obtained at 360 nm of A, B, C, D
diation for 36 and 72 h and E samples with and without irradiation for 36 and 72 h
A B C D E A B C D E
Percentage of increase in lipid peroxidation with respect to non-irradiation sample. Percentage of conservation of trp with respect to non-irradiation sample.
and 72 h. Protein degradation in hair fibres after 36 and 72 h of Increased percentages of peroxides are shown in Table V. Group
UV radiation was significantly decreased by treatment with octyl E showed approximately 90.7% and 119.1% increases after 36 and
salicylate and benzophenone-3. These results suggest conservation 72 h of irradiation, respectively. These results indicate serious hair
of the fibres. Similarly, protection against protein degradation by B damage. Group D showed peroxide increased of 50.1% and 87.4%
was significant after 36 h (86.2%) and 72 h (165.1%) of UV irradi- after 36 and 72 h UV irradiation, respectively; this result suggests
ation. The protective effects of A were also demonstrated, but these that octyl salicylate presents significant protective effects on hair
effects are not significant. Therefore, UVB filters provide better lipids. The fibres were significantly improved by B after 72 h of
photoprotection than UVA filters [21]. irradiation. The protective effects of the treatments showed the
order D > C > B > A > E. The results obtained with the given for-
mulations indicate higher levels of UV protection attributed to the
Lipid peroxidation composition of octyl salicylate. Protein degradation (Fig. 4) and
Hair contains 1.9–5% internal lipid, which exists among cortex peroxide formation (Fig. 5) followed similar trends; these findings
cells, cuticle cells and the intercellular space [22, 23]. Studies indicate that proteins and lipids from fibres are similarly affected
showed that the internal lipid of hair has a certain relationship when treated with UV irradiation [4].
with the moisture content of hair [24]. Metabolite of lipid peroxida-
tion, as well as ordinary oil, is malondialdehyde (MDA). Content of Tryptophan decomposition
MDA is measured by thiobarbituric acid (TBA) assay [10, 25].
Measurements were performed on different treated fibres showed in Amino acids are sensitive to UV radiation. Studies showed that the
Table V and Fig. 5. decrease of aromatic amino acid, tyrosine phenylalanine and tryp-
Conclusions
The adsorption behaviour of UV filters on hair surface revealed
complex characteristics. It is found that the adsorption kinetics of
Figure 6 Fluorescence intensity of A, B, C, D and E samples with and with-
the filters is comparable with a pseudo-second-order kinetic model
out UV irradiation. (a) placebo formulation containing BMBM, (b) placebo and that their adsorption isotherms match the Freundlich adsorp-
formulation containing OMC, (c) placebo formulation containing benzophe- tion model. The amount of UV filter adsorption was not linearly
none-3, (d) placebo hair-care formulation containing octyl salicylate, (e) pla- proportional to the initial filter concentration. The effect of temper-
cebo hair-care formulation. Means that do not share a letter are significantly ature on the adsorption of UV filters onto hair surface tends to sug-
different. gest that the whole process is an endothermic one.
UV filters have effect on protecting hair from photodamage. Lipi-
tophan are related to photo-yellowing of hair. Of all amino acids, dic peroxidation and protein degradation of hair are significantly
tryptophan is the one most easily to degrade. Therefore, it is com- reduced in the benzophenone-3, octyl salicylate and OMC-treated
monly used to evaluate fibre’s damage degree. Tryptophan decom- samples, which suggests an improved integrity of the fibres. How-
position of hair at different UV exposure times was measured using ever, tryptophan degradation is not significantly reduced.
the fluorescence method. Tryptophan was detected at 280 and
360 nm for excitation and emission wavelengths [11]. The results
Acknowledgements
for the different hair fibres are detailed in Table VI and Fig. 6.
The fluorescence intensity of E decreased from 83.1 a.u. to 53.5 Our research was partially supported to publish by School of Per-
a.u. (35.57%) after 72 h of UV irradiation, as shown in Fig. 6. The fume and Aroma Technology, Shanghai Institute of Technology
fluorescence intensity of B improved from 82.66 a.u. to 60.31 a.u. and Analytical Laboratory, the Shanghai Institute of Technology.
References
1. Signori, V. Review of the current under- 6. Hoting, E. and Zimmermann, M. Photo- 11. Delgado-Andrade, C., Rufian-Henares, J.A.,
standing of the effect of ultraviolet and visi- chemical alterations in human hair. Jimenez-Perez, S. et al. Tryptophan determi-
ble radiation on hair structure and options Part III: investigations of internal lipids. nation in milk-based ingredients and dried
for photoprotection. J. Cosmet. Sci. 55, 95– J. Soc. Cosmet. Chem. 47, 201–211 sport supplements by liquid chromatography
113 (2003). (1996). with fluorescence detection. Food Chem. 98,
2. Jeon, S.Y., Pi, L.Q. and Lee, W. Comparison 7. Hoting, E., Zimmermann, M. and H€ ocker, H. 580–585 (2006).
of hair shaft damage after UVA and UVB Photochemical alterations in human hair. 12. Robbins, C.R. and Robbins, C.R. Chemical
irradiation. J. Cosmet. Sci. 59, 151–156 II: analysis of melanin. J. Soc. Cosmet. Chem. and Physical Behavior of Human Hair.
(2008). 46, 181–190 (1995). Springer, New York (2002).
3. Fernandez, E., Barba, C., Alonso, C. et al. 8. Kamath, Y.K., Dansizer, C.J. and Weig- 13. Paria, S. and Khilar, K.C. A review on
Photodamage determination of human hair. mann, H.D. Surface wettability of human experimental studies of surfactant adsorption
J. Photochem. Photobiol. B 106, 101–106 hair. III. Role of surfactants in the surface at the hydrophilic solid–water interface. Adv.
(2012). deposition of cationic polymers. J. Appl. Colloid Interface Sci. 110, 75–95 (2004).
4. Fernandez, E., Martınez-Teipel, B., Armen- Polym. Sci. 30, 937–953 (1985). 14. Ran, G., Zhang, Y., Song, Q. et al. The
gol, R. et al. Efficacy of antioxidants in 9. Santos Nogueira, A.C. and Joekes, I. Hair adsorption behavior of cationic surfactant
human hair. J. Photochem. Photobiol. B 117, color changes and protein damage caused onto human hair fibers. Colloids Surf. B 68,
146–156 (2012). by ultraviolet radiation. J. Photochem. Photo- 106–110 (2009).
5. Hoting, E., Zimmermann, M. and Hilter- biol. B 74, 109–117 (2004). 15. Ghaedi, M. and Mosallanejad, N. Study of
haus-Bong, S. Photochemical alterations in 10. Alonso, C., Barba, C., Rubio, L. et al. An competitive adsorption of malachite green
human hair. I: artificial irradiation and ex vivo methodology to assess the lipid per- and sunset yellow dyes on cadmium hydrox-
investigations of hair proteins. J. Soc. Cos- oxidation in stratum corneum. J. Photochem. ide nanowires loaded on activated carbon. J.
met. Chem. 46, 85–99 (1995). Photobiol. B 97, 71–76 (2009). Ind. Eng. Chem. 20, 1085–1096 (2014).
16. Lin, S., Song, Z., Che, G. et al. Adsorption 19. Yuen, C.W.M., Kan, C.W. and Cheng, S.Y. 23. Braida, D., Dubief, C., Lang, G. et al. Cera-
behavior of metal–organic frameworks for Evaluation of keratin fibre damages. Fibers mide: a new approach to hair protection
methylene blue from aqueous solution. Micro- Polym. 8, 414–420 (2007). and conditioning. Cosmet. Toiletries 109,
porous Mesoporous Mater. 193, 27–34 (2014). 20. Willis, D., Moore, A.R., Frederick, R. et al. 49–57 (1994).
17. Zhang, R. and Somasundaran, P. Advances Heme oxygenase: a novel target for the 24. Nishimura, K., Nishino, M., Inaoka, Y. et al.
in adsorption of surfactants and their mix- modulation of inflammatory response. Nat. Interrelationship between the hair lipids and
tures at solid/solution interfaces. Adv. Colloid Med. 2, 87–93 (1996). the hair moisture. Nippon Koshobin Kagakkai-
Interface Sci. 123, 213–229 (2006). 21. Chandra, M.P. and Janus, J. Hair photodam- shi 13, 134–139 (1989).
18. Dario, M.F., Pahl, R., de Castro, J.R. et al. age-measurements and prevention, J. Soc. 25. Benaiges, A., Fern andez, E., Martınez-Tei-
Efficacy of Punica granatum L. hydroalco- Cosmet. Chem. 44, 109–122 (1993). pel, B. et al. Hair efficacy of botanical
holic extract on properties of dyed hair 22. Shaw, D.A. The extraction, quantification, extracts. J. Appl. Polym. Sci. 128, 861–
exposed to UVA radiation. J. Photochem. and nature of hair lipid. Int. J. Cosmet. Sci. 868 (2013).
Photobiol. B 120, 142–147 (2013). 1, 291–302 (1979).