Abstract
Dioctyl 4-methoxybenzylidenemalonate (DOMBM) is an effective stabilizer for photolabile 4-tert-butyl-4′-methoxydibenzoylmethane (BMDBM). DOMBM is superior to the most widely used UV-B absorber, octyl methoxycinnamate (OMC), at preserving its UV-B absorbance in the presence of BMDBM. The energy levels of the lowest excited singlet (S1) and triplet (T1) states of DOMBM were determined by measuring fluorescence and phosphorescence spectra in ethanol at 77 K. The energy level of the T1 state of DOMBM is lower than that of BMDBM and is higher than that of OMC. The triplet-triplet energy transfer from BMDBM to DOMBM was demonstrated by measuring the electron paramagnetic resonance (EPR) and time-resolved phosphorescence spectra. The phosphorescence and EPR signals of DOMBM are too weak to be observed through the direct excitation in ethanol at 77 K. The phosphorescence spectrum was observed by using external heavy atom effects of ethyl iodide. The EPR spectrum was observed by using benzophenone as a triplet sensitizer. The fluorescence quantum yield of DOMBM is small in ethanol at room temperature. Only the fast component, due to the heat released from the excited state of DOMBM, was observed in the time-resolved thermal lensing experiments at room temperature. These results show that the quantum yield of the S1 → T1 intersystem crossing is negligible and the deactivation process is predominantly internal conversion to the ground state for DOMBM.
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United Nations Environment Programme Environmental Effects Assessment Panel, Environmental effects of ozone depletion and its interactions with climate change: progress report, 2011, Photochem. Photobiol. Sci, 2012, 11, 13–27.
N. R. Attard and P. Karran, UVA photosensitization of thiopurines and skin cancer in organ transplant recipients, Photochem. Photobiol. Sci., 2012, 11, 62–68.
G. P. Pfeifer and A. Besaratinia, UV wavelength-dependent DNA damage and human non-melanoma and melanoma skin cancer, Photochem. Photobiol. Sci., 2012, 11, 90–97.
Y. Matsumura and H. N. Ananthaswamy, Toxic effects of ultraviolet radiation on the skin, Toxicol. Appl. Pharmacol., 2004, 195, 298–308.
T. M. Hughes, J. A. Martin, V. J. Lewis and N. M. Stone, Allergic contact dermatitis to drometrizole trisiloxane in a sunscreen with concomitant sensitivities to other sun screens, Contact Dermatitis, 2005, 52, 226–227.
W. Schwack and T. Rudolph, Photochemistry of dibenzoyl methane UVA filters, Part 1, J. Photochem. Photobiol., B, 1995, 28, 229–234.
N. M. Roscher, M. K. O. Lindemann, S. B. Kong, C. G. Cho and P. Jiang, Photodecomposition of several compounds commonly used as sunscreen agents, J. Photochem. Photobiol., A, 1994, 80, 417–421.
J. M. Allen, C. J. Gossett and S. K. Allen, Photochemical formation of singlet molecular oxygen in illuminated aqueous solutions of several commercially available sunscreen active ingredients, Chem. Res. Toxicol., 1996, 9, 605–609.
L. F. Alves, R. Gargano, S. K. B. Alcanfor, L. A. S. Romeiro and J. B. L. Martins, A chromophoric study of 2-ethylhexyl p-methoxycinnamate, Chem. Phys. Lett., 2011, 516, 162–165.
B. K. Paul and N. Guchhait, A computational insight into the photophysics of a potent UV absorber Tinuvin P: critical evaluation of the role of charge transfer interaction and topological properties of the intramolecular hydrogen bonding, Comput. Theor. Chem., 2011, 966, 250–258.
K. Morabito, K. G. Steeley, N. C. Shapley, C. Mello, D. Li, P. Calvert and A. Tripathi, Proximal effects of ultraviolet light absorbers and polymer matrix in the photostability of β-carotene, Dyes Pigm., 2012, 92, 509–516.
A. Kikuchi and M. Yagi, Direct observation of the intermolecular triplet–triplet energy transfer from UV-A absorber 4-tert-butyl-4′-methoxydibenzoylmethane to UV-B absorber octyl methoxycinnamate, Chem. Phys. Lett., 2011, 513, 63–66.
A. Kikuchi, H. Saito, M. Mori and M. Yagi, Photoexcited triplet states of new UV absorbers, cinnamic acid 2-methylphenyl esters, Photochem. Photobiol. Sci., 2011, 10, 1902–1909.
A. Kikuchi, S. Yukimaru, N. Oguchi, K. Miyazawa and M. Yagi, Excited triplet state of a UV-B absorber, octyl methoxycinnamate, Chem. Lett., 2010, 39, 633–635.
V. Lhiaubet-Vallet, M. Marin, O. Jimenez, O. Gorchs, C. Trullas and M. A. Miranda, Filter–filter interactions. Photostabilization, triplet quenching and reactivity with singlet oxygen, Photochem. Photobiol. Sci., 2010, 9, 552–558.
C. Bonda, A. Pavlovic, K. Hanson and C. Bardeen, Singlet quenching proves faster is better for photostability, Cosmet. Toiletries, 2010, 125, 40–48.
R. Farkas, V. Lhiaubet-Vallet, J. Corbera, M. Törincsi, O. Gorchs, C. Trullas, O. Jiménez, M. A. Miranda and L. Novak, Synthesis of new 2-(2′-hydroxyaryl)benzotriazoles and evaluation of their photochemical behavior as potential UV-filters, Molecules, 2010, 15, 6205–6216.
J. Kockler, M. Oelgemöller, S. Robertson and B. D. Glass, Photostability of sunscreens, J. Photochem. Photobiol., C, 2012, 13, 91–110.
D. Dondi, A. Albini and N. Serpone, Interactions between different solar UVB/UVA filters contained in commercial suncreams and consequent loss of UV protection, Photochem. Photobiol. Sci., 2006, 5, 835–843.
C. A. Bonda, The Photostability of Organic Sunscreen Actives: A Review, in Sunscreens, ed. N. A. Shaath, Taylor & Francis, Boca Raton, 2005, pp. 321–349.
C. Paris, V. Lhiaubet-Vallet, O. Jiménez, C. Trullas, M. Á. Miranda, A blocked diketo form of avobenzone: photostability, photosensitizing properties and triplet quenching by a triazine-derived UVB-filter, Photochem. Photobiol., 2009, 85, 178–184.
S. Scalia and M. Mezzena, Photostabilization effect of quercetin on the UV filter combination, butyl methoxydibenzoylmethane–octyl methoxycinnamate, Photochem. Photobiol., 2010, 86, 273–278.
C. Mendrok-Edinger, K. Smith, A. Janssen and J. Vollhardt, The quest for avobenzone stabilizers and sunscreen photostability, Cosmet. Toiletries, 2009, 124, 47–54.
B. Herzog, M. Wehrle and K. Quass, Photostability of UV absorber systems in sunscreens, Photochem. Photobiol., 2009, 85, 869–878.
E. Damiani, W. Baschong and L. Greci, UV-Filter combinations under UV-A exposure: Concomitant quantification of over-all spectral stability and molecular integrity, J. Photochem. Photobiol., B, 2007, 87, 95–104.
E. Damiani, L. Rosati, R. Castagna, P. Carloni and L. Greci, Changes in ultraviolet absorbance and hence in protective efficacy against lipid peroxidation of organic sunscreens after UVA irradiation, J. Photochem. Photobiol., B, 2006, 82, 204–213.
E. Chatelain and B. Gabard, Photostabilization of butyl methoxydibenzoylmethane (avobenzone) and ethylhexyl methoxycinnamate by bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S), a new UV broadband filter, Photochem. Photobiol., 2001, 74, 401–406.
R. M. Sayre, J. C. Dowdy, A. J. Gerwig, W. J. Shields and R. V. Lloyd, Unexpected photolysis of the sunscreen octinoxate in the presence of the sunscreen avobenzone, Photochem. Photobiol., 2005, 81, 452–456.
N. A. Shaath, Ultraviolet filters, Photochem. Photobiol. Sci., 2010, 9, 464–469.
S. Schauder and H. Ippen, Contact and photocontact sensitivity to sunscreens: Review of a 15-year experience and of the literature, Contact Dermatitis, 1997, 37, 221–232.
S. P. Huong, V. Andrieu, J.-P. Reynier, E. Rocher, J.-D. Fourneron, The photoisomerization of the sunscreen ethylhexyl p-methoxy cinnamate and its influence on the sun protection factor, J. Photochem. Photobiol., A, 2007, 186, 65–70.
S. Pattanaargson, N. Hongchinnagorn, P. Hirunsupachot, Y. Sritana-anant, UV absorption and photoisomerization of p-methoxycinnamate grafted silicone, Photochem. Photobiol., 2004, 80, 322–325.
S. Pattanaargson, T. Munhapol, P. Hirunsupachot and P. Luangthongaram, Photoisomerization of octyl methoxycinnamate, J. Photochem. Photobiol., A, 2004, 161, 269–274.
W. Johncock, Sunscreen interactions in formulations, Cosmet. Toiletries, 1999, 114, 75–82.
Z. R. Grabowski and A. Grabowska, The Förster cycle reconsidered, Z. Phys. Chem., 1976, 101, 197–208.
A. Kikuchi, N. Oguchi and M. Yagi, Optical and electron paramagnetic resonance studies of the excited states of 4-tert-butyl-4′-methoxydibenzoylmethane and 4-tert-butyl-4′-methoxydibenzoylpropane, J. Phys. Chem. A, 2009, 113, 13492–13497.
M. Montalti, A. Credi, L. Prodi and M. T. Gandolfi, Handbook of photochemistry, Tayler & Francis, Boca Raton, 3rd edn, 2006.
P. Kottis and R. Lefebvre, Calculation of the electron spin resonance line shape of randomly oriented molecules in a triplet state. I. The Δm = 2 transition with a constant linewidth, J. Chem. Phys., 1963, 39, 393–403.
S. Niizuma, L. Kwan and N. Hirota, E.P.R. and, zero-field odmr studies of the T1 states of halogen-containing benzonitriles, anisoles and anilines, Mol. Phys., 1978, 35, 1029–1046.
G. Kothandaraman and D. S. Tinti, PMDR studies of intramolecular spin–orbit perturbations on the triplet state properties of substituted benzenes, Chem. Phys. Lett., 1973, 19, 225–230.
S. A. Boorstein and M. Gouterman, Theory for zero-field splittings in aromatic hydrocarbons. III, J. Chem. Phys., 1963, 39, 2443–2452.
W. T. Raynes, Spin splittings and rotational structure of nonlinear molecules in doublet and triplet electronic states, J. Chem. Phys., 1964, 41, 3020–3032.
N. J. Turro, V. Ramamurthy and J. C. Scaiano, Modern Molecular Photochemistry of organic molecules, Unversity Science Books, Sausalito, 2010.
G. Rossbroich, N. A. Garcia and S. E. Braslavsky, Thermal-lensing measurements of singlet molecular oxygen (1Δg): quantum yields of formation and lifetimes, J. Photochem., 1985, 31, 37–47.
T. Suzuki, U. Okuyama and T. Ichimura, Double proton transfer reaction of 7-azaindole dimer and complexes studied by time-resolved thermal lensing technique, J. Phys. Chem. A, 1997, 101, 7047–7052.
M. W. Wolf, R. E. Brown and L. A. Singer, Deactivation of benzophenone triplets via exciplex formation. Evidence for dual reaction pathways, J. Am. Chem. Soc., 1977, 99, 526–531.
J. V. Morris, M. A. Mahaney and J. R. Huber, Fluorescence quantum yield determinations. 9,10-Diphenylanthracene as a reference standard in different solvents, J. Phys. Chem., 1976, 80, 969–974.
T. M. Karpkird, S. Wanichweacharungruang and B. Albinsson, Photophysical characterization of cinnamates, Photochem. Photobiol. Sci., 2009, 8, 1455–1460.
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Oguchi-Fujiyama, N., Miyazawa, K., Kikuchi, A. et al. Photophysical properties of dioctyl 4-methoxybenzylidenemalonate: UV-B absorber. Photochem Photobiol Sci 11, 1528–1535 (2012). https://doi.org/10.1039/c2pp25101a
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DOI: https://doi.org/10.1039/c2pp25101a