Structurally regular arrangement induced fluorescence enhancement and specific recognition for glutathione of a pyrene chalcone derivative.

Glutathione (GSH) is an important antioxygen and free radical scavenger in the organism. Level of GSH in vivo is associated with many diseases and specific recognition for GSH is very important. Here, a pyrene chalcone derivative 1 1-(2-hydroxyphenyl)-3-(1-pyrenyl)-2-propen-1-one as specific probe for GSH was developed. The probe can give rise to rapid blue fluorescence enhancement for GSH based on Michael addition reaction in pure PBS solution with high sensitivity, fast response rate and high specificity. The compound also can be applied for GSH detection in HeLa cell. Simultaneously, the compound exhibits blue fluorescence emission enhancement in methanol-water (1:1, v/v) solution with fluorescence quantum yield being 0.45 due to the competition of water molecules for hydrogen bonds between hydroxyl and carbonyl and the formation of structurally regular rodlike crystals, which allows regulating fluorescence emission by different solvent condition.

Structural, energetic, and UV-Vis spectral analysis of UVA filter 4-tert-butyl-4'-methoxydibenzoylmethane.

The growing awareness of the harmful effects of ultraviolet (UV) solar radiation has increased the production and consumption of sunscreen products, which contain organic and inorganic molecules named UV filters that absorb, reflect, or scatter UV radiation, thus minimizing negative human health effects. 4-tert-Butyl-4'-methoxydibenzoylmethane (BMDBM) is one of the few organic UVA filters and the most commonly used. BMDBM exists in sunscreens in the enol form which absorbs strongly in the UVA range. However, under sunlight irradiation tautomerization occurs to the keto form, resulting in the loss of UV protection. In this study we have performed quantum chemical calculations to study the excited-state molecular structure and excitation spectra of the enol and keto tautomers of BMDBM. This knowledge is of the utmost importance as the starting point for studies aiming at the understanding of its activity when applied on human skin and also its fate once released into the aquatic environment. The efficiency of excitation transitions was rationalized based on the concept of molecular orbital superposition. The loss of UV protection was attributed to the enol → keto phototautomerism and subsequent photodegradation. Although this process is not energetically favorable in the singlet bright state, photodegradation is possible because of intersystem crossing to the first two triplet states.

Interaction of LED light with coinitiator-containing composite resins: effect of dual peaks.

OBJECTIVES: Recently the colour stability of composite resins has been an issue due to the emphasis on the aesthetics of restored teeth. The purpose of the present study was to investigate how dual-peak LED units affect the polymerization of coinitiator-containing composite resins. MATERIALS AND METHODS: Five composite resins [coinitiator-containing: Aelite LS Posterior (AL), Tetric EvoCeram (TE), and Vit-l-escence (VI); only CQ-containing: Grandio (GD) and Filtek Z350 (Z3)] were light cured using four different light-curing units (LCUs). Among them, Bluephase G2 (BP) and G-light (GL) were dual-peak LED LCUs. Microhardness, polymerization shrinkage, flexural, and compressive properties were measured. RESULTS: BP and GL had no consistent effect on the microhardness of AL, TE, and VI on the top and bottom surfaces of resin specimens. Among the specimens, AL and VI showed the least (9.86-10.41 µm) and greatest (17.58-19.21 µm) polymerization shrinkage, respectively. However, the effect of BP and GL on the shrinkage of specimens was not consistent. Among the specimens, GD showed the greatest flexural properties [strength (FS) and modulus (FM)] and TE showed the lowest flexural and compressive properties [strength (CS) and modulus (CM)]. In same resin product, maximum FS and CS differences due to the different LCUs were 10.3-21.0% and 3.6-9.2%, respectively. Furthermore, the influences of BP and GL on FS and CS were not consistent. CONCLUSION: The tested dual-peak LED LCUs had no consistent synergic effect on the polymerization of coinitiator-containing composite resins as compared with QTH and single-peak LED LCUs. CLINICAL SIGNIFICANCE: The dual-peak LED LCUs achieve a similar degree of polymerization in coinitiator-composite resins as QTH and single-peak LED LCUs did. Choice of LCU does not appear to be a determinant of the light curing of coinitiator-composite resins.

Measuring sunscreen protection against solar-simulated radiation-induced structural radical damage to skin using ESR/spin trapping: development of an ex vivo test method.

The in vitro star system used for sunscreen UVA-testing is not an absolute measure of skin protection being a ratio of the total integrated UVA/UVB absorption. The in vivo persistent-pigment-darkening method requires human volunteers. We investigated the use of the ESR-detectable DMPO protein radical-adduct in solar-simulator-irradiated skin substitutes for sunscreen testing. Sunscreens SPF rated 20+ with UVA protection, reduced this adduct by 40-65% when applied at 2 mg/cm(2). SPF 15 Organic UVA-UVB (BMDBM-OMC) and TiO(2)-UVB filters and a novel UVA-TiO(2) filter reduced it by 21, 31 and 70% respectively. Conventional broad-spectrum sunscreens do not fully protect against protein radical-damage in skin due to possible visible-light contributions to damage or UVA-filter degradation. Anisotropic spectra of DMPO-trapped oxygen-centred radicals, proposed intermediates of lipid-oxidation, were detected in irradiated sunscreen and DMPO. Sunscreen protection might be improved by the consideration of visible-light protection and the design of filters to minimise radical leakage and lipid-oxidation.

Microencapsulation of a cyclodextrin complex of the UV filter, butyl methoxydibenzoylmethane: in vivo skin penetration studies.

Lipid microparticles loaded with the complex between hydroxypropyl-ß-cyclodextrin (HP-ß-CD) and the sunscreen agent, butyl methoxydibenzoylmethane (BMDBM) were evaluated for their effect on the UV filter percutaneous penetration. The microparticles were prepared by the melt emulsification technique using tristearin as lipidic material and hydrogenate phosphatidylcholine as the surfactant. Human skin penetration was investigated in vivo by the tape stripping technique, a minimal invasive procedure based on the progressive removal of the upper cutaneous layers (stratum corneum) with adhesive tape strips. The amount of sunscreen fixed to each strip was determined by HPLC after solvent extraction. The recovery of the UV filter from spiked adhesive tapes was >94.4% and the precision of the method was better than 7.6% relative standard deviation. Non-encapsulated BMDBM, its complex with HP-ß-CD, the lipid microparticles loaded with the sunscreen alone or the BMDBM/HP-ß-CD complex were introduced into oil-in-water emulsions and applied to human volunteers. Compared to the cream with the non-encapsulated sunscreen agent (percentage of the applied dose penetrated, 9.7%±2.5), the amount of BMDBM diffusing into the stratum corneum was increased by the formulations containing the BMDBM/HP-ß-CD complex (17.1%±3.2 of the applied dose) or the microparticles loaded with BMDBM only (15.1%±2.7 of the applied dose). On the contrary, a significant decrease in the level of UV filter penetrated into the stratum corneum was achieved by the cream containing the microencapsulated BMDBM/HP-ß-CD complex (percentage of the applied dose penetrated, 6.0%±1.5). The reduced BMDBM percutaneous penetration attained by the latter system should enhance the UV filter efficacy and limit potential toxicological risks.

Identification and stability of a new bichalcone in Achyrocline satureioides spray dried powder.

A new chemical structure, the 4,2',4",2'''-tetrahydroxy-6',6'''-dimethoxy-4'-O-4'''- bichalcone, named achyrobichalcone was isolated and identified from an Achyrocline satureioides spray-dried powder (SDP80). The thermal and photo stability of this new compound as well as that of the main polyphenols present in the spray dried powder, quercetin, luteolin, 3-O-metylquercetin and the corresponding kinetics of degradation are reported. In the long-term testing (30 +/- 2 degrees C/75 +/- 5% RH, 12 months), the total polyphenols contained in SDP80 demonstrated to be stable, remaining higher than 90% after a 12 month exposure. The photo stability testing revealed that all polyphenols were stable for 48 h when SDP80 was conditioned in amber or transparent flasks and exposed to UV-C radiation (light express LE UV, 254 nm, 30W). In contrast, when unprotected, the polyphenols demonstrated to be sensitive to both, thermal stress testing (80 +/- 2 degrees C), for 14 days and to UV-C radiation. Luteolin showed to be the most stable against UVC light and 3-O-methylquercetin against temperature. The achyrobichalcone demonstrated to be the more unstable against both, temperature and light. The kinetics of polyphenol thermal degradation (80 +/- 2 degrees C, 49 days) and photodegradation (UV-C radiation, 96 h) followed, 2nd and 1st order reaction, respectively.

Effect of different photo-initiators and light curing units on degree of conversion of composites.

The aim of this study was to evaluate: (i) the absorption of photo-initiators and emission spectra of light curing units (LCUs); and (ii) the degree of conversion (DC) of experimental composites formulated with different photo-initiators when activated by different LCUs. Blends of BisGMA, UDMA, BisEMA and TEGDMA with camphorquinone (CQ) and/ or 1-phenyl-1,2-propanedione (PPD) were prepared. Dimethylaminoethyl methacrylate (DMAEMA) was used as co-initiator. Each mixture was loaded with 65 wt% of silanated filler particles. One quartz-tungsten-halogen - QTH (XL 2500, 3M/ESPE) and two lightemitting diode (LED) LCUs (UltraBlue IS, DMC and UltraLume LED 5, Ultradent) were used for activation procedures. Irradiance (mW/cm²) was calculated by the ratio of the output power by the area of the tip, and spectral distribution with a spectrometer (USB 2000). The absorption curve of each photo-initiator was determined using a spectrophotometer (Varian Cary 5G). DC was assessed by Fourier transformed infrared spectroscopy. Data were submitted to two-way ANOVA and Tukey's test (5%). No significant difference was found for DC values when using LED LCUs regardless of the photo-initiator type. However, PPD showed significantly lower DC values than composites with CQ when irradiated with QTH. PPD produced DC values similar to those of CQ, but it was dependent on the LCU type.

Effect of different photo-initiators and light curing units on degree of conversion of composites

The aim of this study was to evaluate: (i) the absorption of photo-initiators and emission spectra of light curing units (LCUs); and (ii) the degree of conversion (DC) of experimental composites formulated with different photo-initiators when activated by different LCUs. Blends of BisGMA, UDMA, BisEMA and TEGDMA with camphorquinone (CQ) and/ or 1-phenyl-1,2-propanedione (PPD) were prepared. Dimethylaminoethyl methacrylate (DMAEMA) was used as co-initiator. Each mixture was loaded with 65 wt percent of silanated filler particles. One quartz-tungsten-halogen - QTH (XL 2500, 3M/ESPE) and two lightemitting diode (LED) LCUs (UltraBlue IS, DMC and UltraLume LED 5, Ultradent) were used for activation procedures. Irradiance (mW/cm²) was calculated by the ratio of the output power by the area of the tip, and spectral distribution with a spectrometer (USB 2000). The absorption curve of each photo-initiator was determined using a spectrophotometer (Varian Cary 5G). DC was assessed by Fourier transformed infrared spectroscopy. Data were submitted to two-way ANOVA and Tukey's test (5 percent). No significant difference was found for DC values when using LED LCUs regardless of the photo-initiator type. However, PPD showed significantly lower DC values than composites with CQ when irradiated with QTH. PPD produced DC values similar to those of CQ, but it was dependent on the LCU type.

In vitro photosensitization initiated by camphorquinone and phenyl propanedione in dental polymeric materials.

Documentation is scarce on the photobiological effects of photoinitiators present in dental light curable materials. The aim of this study was to determine cellular effects of the photoinitiators camphorquinone (CQ) and phenyl propanedione (PPD) and to investigate whether these substances produced reactive oxygen species after low and high doses of optical radiation (between 0 and 17J/cm(2)). Rat salivary gland cells in vitro were exposed to visible blue light and/or UVA. Hematoporphyrin (HP), a photosensitizer used in medicine, and the UVA-filter 2-methoxy-4-hydroxy-benzophenone (B-3) were used as reference substances. It was found that PPD produced hydrogen peroxide, but not singlet oxygen, upon light irradiation. CQ produced neither hydrogen peroxide nor singlet oxygen. Cell death by necrosis and apoptosis was induced by irradiation in the presence of CQ, PPD and HP. Doses higher than 6J/cm(2) UVA and blue visible light from a source similar to clinically applied sources, induced apoptosis even in the absence of photosensitizers added. A reciprocity relationship was found between radiant exposure (at constant irradiance) and concentration of photoinitiators. In conclusion, the oral cells under investigation were light sensitive, and the sensitivity increased in presence of photoinitiators. PPD acted by mechanisms that included reactive oxygen species and CQ probably by formation of free radicals.

Efficient sonochemical synthesis of novel 3,5-diaryl-4,5-dihydro-1H-pyrazole-1-carboximidamides.

An ultrasound-assisted preparation of a series of novel 3,5-diaryl-4,5-dihydro-1H-pyrazole-1-carboximidamides that proceeds via the efficient reaction of chalcones with aminoguanidine hydrochloride under clean conditions is described.

Solvent free synthesis of 1,3-diaryl-2-propenones catalyzed by commercial acid-clays under ultrasound irradiation.

This paper presents a novel solvent free method of synthesis of trans-chalcones. The method was based on ultrasound irradiation of the reagents (aryl methyl ketones and aryl aldehydes) in presence of commercial acid-montmorillonites as catalysts. The trans-chalcones were synthesized in high yields (85-95%) and excellent selectivity in a short reaction time.

Co-loading of a photostabilizer with the sunscreen agent, butyl methoxydibenzoylmethane in solid lipid microparticles.

The sunscreen agent, butyl methoxydibenzoylmethane (BMDBM), one of the most widely used UV-A filter, undergoes decomposition under sunlight exposure, which is a limiting factor on its overall performance. To reduce the sunscreen photodegradation, this study investigates the incorporation into solid lipid microparticles (SLMs) of BMDBM together with the photostabilizer, 4-methylbenzylidene camphor (MBC). The microparticles were produced by the melt dispersion technique using various lipid materials (tristearin, glyceryl behenate, and stearic acid) and hydrogenated phosphatidylcholine as the surfactant. The highest retention capacity for BMDBM and MBC was achieved with tristearin microparticles. These SLMs were characterized by scanning electron microscopy and powder X-ray diffraction analyses. The BMDBM and MBC loading was 10.4 and 10.1%, respectively. The efficacy of the SLMs was evaluated after their introduction in a conventional cream (oil-in-water emulsion). The light-induced decomposition of BMDBM was decreased by encapsulation into the SLMs (the extent of degradation was 33.8 +/- 5.5% for unencapsulated BMDBM/MBC and 25.3 +/- 4.2% for BMDBM-loaded microparticles in conjunction with free MBC). Moreover, the co-loading of the MBC stabilizer in the SLMs produced a further reduction of the photodegradation of the UV-A filter (the BMDBM loss was 16.9 +/- 5.9%) compared with the microparticles containing BMDBM without MBC. Therefore, incorporation in lipid microparticles of BMDBM together with the MBC photostabilizer is more effective in enhancing the UV-A filter photostability than the SLMs loaded with BMDBM alone.

Influence of photoinitiator type on the rate of polymerization, degree of conversion, hardness and yellowing of dental resin composites.

OBJECTIVES: To evaluate the degree of conversion (DC), maximum rate of polymerization (Rpmax), Knoop hardness (KHN) and yellowing (b-value) of resin composites formulated with phenylpropanedione (PPD), camphorquinone (CQ), or CQ/PPD at different concentrations. The hypotheses tested were (i) PPD or CQ/PPD would produce less Rpmax and yellowing than CQ alone without affecting DC and KHN, and (ii) Rpmax, DC, and KHN would be directly related to the absorbed power density (PDabs). METHODS: CQ/amine, PPD/amine and CQ/PPD/amine were used at low, intermediate and high concentrations in experimental composites. Photoinitiator absorption and halogen-light emission were measured using a spectrophotometer, Rp with differential scanning calorimetry (DSC), DC with DSC and FTIR, KHN with Knoop indentation; and color with a chromameter. The results were analyzed with two-way analysis of variance (ANOVA)/Student-Newman-Keul's test (p<0.05). Correlation tests were carried out between PDabs and each of DC, Rpmax and KHN. RESULTS: The PDabs increased with photoinitiator concentration and PPD samples had the lowest values. In general, maximum DC was comparable at intermediate concentration, while Rpmax and KHN required higher concentrations. DC was similar for all photoinitiators, but Rpmax was lower with PPD and CQ/PPD. PPD produced the lowest KHN. Yellowing increased with photoinitiator concentration. PPD did not reduce yellowing at intermediate and/or high concentrations, compared to CQ-formulations. PDabs showed significant correlations with DC, Rpmax and KHN. CONCLUSION: PPD or CQ/PPD reduced Rpmax in experimental composites without affecting the DC. The use of PPD did not reduce yellowing, but reduced KHN. DC, Rpmax and KHN were dependent on PDabs.

Photopolymerization of N,N-dimethylaminobenzyl alcohol as amine co-initiator for light-cured dental resins.

OBJECTIVE: The present study was carried out in order to assess the suitability of N,N-dimethylaminobenzyl alcohol (DMOH) as co-initiator of camphorquinone (CQ) and 1-phenyl-1,2-propanedione (PPD) in light-cured dental resins. METHODS: DMOH was synthesized and used as co-initiator for the photopolymerization of a model resin based on {2,2-bis[4-(2-hydroxy-3-methacryloxyprop-1-oxy)phenyl]propane} (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA). Experimental formulations containing CQ or PPD in combination with DMOH at different concentrations were studied. The photopolymerization was carried out by means of a commercial light-emitting diode (LED) curing unit. The evolution of double bonds consumption versus irradiation time was followed by near-infrared spectroscopy (NIR). The photon absorption efficiency (PAE) of the photopolymerization process was calculated from the spectral distribution of the LED unit and the molar absorption coefficient distributions of PPD and CQ. RESULTS: DMOH is an efficient photoreducer of CQ and PPD resulting in higher polymerization rate and higher double bond conversion compared with dimethylaminoethylmethacrylate. The PAE for PPD was higher than that for CQ. However, the polymerization initiated by PPD progressed at a lower rate and exhibited lower values of final conversion compared with the resins containing CQ. This observation indicates that the lower polymerization rate of the PPD/amine system should be explained in terms of the mechanism of generating primary radicals by PPD, which is less efficient compared with CQ. SIGNIFICANCE: The DMOH/benzoyl peroxide redox system, has recently been proposed as a more biocompatible accelerator for the polymerization of bone cements based on poly(methyl methacrylate), because cytotoxity tests have demonstrated that DMOH possesses better biocompatibility properties compared with traditional tertiary amines. The results obtained in the present study reveal the suitability of the CQ/DMOH initiator system for the polymerization of light-cured dental composites.

Substitution and solvent effects in the chalcones isomerization barrier of flavylium photochromic systems.

Useful application of photochromic compounds as optical memories implies the existence of a large kinetic barrier between the forms interconverted by light. In the case of flavylium salts, the ground state isomerization barrier between the photoisomerizable chalcone isomers is shown to correlate with the electron donating ability of the substituents, measured by their effects in the (1)H NMR chemical shifts of the aromatic protons. Substitution with electron donating groups in ring A lowers the barrier while substitution at ring B has the opposite effect. However, in water, the observed increase is higher than expected in the case of compound 4',9-dihydroxychalcone when compared with the analogous 4'-dimethylamino-9-hydroxychalcone, containing a better electron donating group in the same position. Our interpretation is that the water network is providing an efficient pathway to form tautomers. In acetonitrile, unlike water, the expected order is indeed observed: E(a)(4',9-dihydroxychalcone) = 60 kJ mol(-1) < E(a) (4'-dimethylamino-9-hydroxychalcone) = 69 kJ mol(-1).

Interactions between different solar UVB/UVA filters contained in commercial suncreams and consequent loss of UV protection.

A systematic investigation of two well-known and popular commercial suncreams reveals significant degradation when exposed to simulated UV sunlight at an irradiance corresponding to natural sunlight. We have examined the photochemistry of two widely used sunscreen active agents in pure solvents separately and together (in solution), and in neat form, as well as their photochemistry when present in the actual suncream emulsion (as thin films on a glass substrate) since their combination typically produces suncreams with high sun protection factors (SPF): (1a) octyl methoxycinnamate (OMC; octinoxate) and (2a) 4-tert-butyl-4'-methoxydibenzoylmethane (also known as avobenzone and Parsol 1789), present in the two suncream formulations in combination with others (one also contained TiO2). Intermediates and/or photoproducts were identified by UV/visible spectroscopy, HPLC and liquid chromatographic/mass spectral methods, and by both 1H and 13C-NMR techniques. Structural assignments of the substrates produced were aided by examining model systems {viz. ethyl cinnamate (1b) and dibenzoylmethane (2b)} of the two sunscreen active agents. Irradiation of the cinnamates and the diketones together led to a [2 + 2] photocycloaddition process yielding cinnamate dimers and cyclobutylketone photoadducts that subsequently fragmented into substituted oxopentanoates and oxobutanoates. Similar findings were observed when the two active agents were simultaneously present in the same suncream emulsion.

Encapsulation in lipospheres of the complex between butyl methoxydibenzoylmethane and hydroxypropyl-beta-cyclodextrin.

The aim of this study was to investigate the incorporation into lipospheres of the complex between hydroxypropyl-beta-cyclodextrin (HP-beta-CD) and the sunscreen agent, butyl methoxydibenzoylmethane (BMDBM) and to examine the influence of this system on the sunscreen photostability. The formation of the inclusion complex was confirmed by thermal analysis and powder X-ray diffraction. Lipid microparticles loaded with free BMDBM or its complex with HP-beta-CD were prepared using tristearin as the lipid material and hydrogenated phosphatidylcholine as the emulsifier. The obtained lipospheres were characterized by scanning electron microscopy and differential scanning calorimetry. The microparticle size (15-40 microm) was not affected by the presence of the complex. Release of BMDBM from the lipospheres was lower when it was incorporated as inclusion complex rather than as free molecule. Unencapsulated BMDBM, its complex with HP-beta-CD, the sunscreen-loaded lipospheres or the lipoparticles containing the BMDBM/HP-beta-CD complex, were introduced into a model cream (oil-in-water emulsion) and irradiated with a solar simulator. The photodegradation studies showed that all the examined systems achieved a significant reduction of the light-induced decomposition of the free sunscreen agent (the BMDBM loss decreased from 28.9 to 17.3-15.2%). However, photolysis experiments performed during 3 months storage of the formulations, demonstrated that the photoprotective properties of the HP-beta-CD complex and of BMDBM alone-loaded lipospheres decreased over time, whereas the microencapsulated HP-beta-CD/BMDBM complex retained its photostabilization efficacy. Therefore, incorporation in lipid microparticles of BMDBM in the cyclodextrin complex form is more effective in enhancing the sunscreen photostability than the complex alone or the liposphere-entrapped free BMDBM.

Effect of ultrasound in enantioselective hydrogenation of 1-phenyl-1,2-propanedione: comparison of catalyst activation, solvents and supports.

The enantioselective hydrogenation of 1-phenyl-1,2-propanedione was carried out over Pt/Al2O3, Pt/SiO2, Pt/SF (silica fiber), Pt/C catalysts modified with cinchonidine under ultrasonic irradiation. The initial rate, regioselectivity and enantioselectivity were investigated for different catalyst pretreatments, solvents and ultrasonic powers. The ultrasound effects were very catalyst dependent. The sonication significantly enhanced enantioselectivity and activity of the Pt/SF (silica fiber) catalyst. For the other Pt supported catalysts the reaction rate, enantioselectivity and regioselectivity increased moderately. The choice of solvent influenced the impact of ultrasound effect, namely in mesitylene, which has the lowest vapor pressure, the highest ultrasound enhancement was observed. The effect of sonication on catalysts surface was studied by transmission electron microscopy and scanning electron microscopy (SEM). No significant change in the metal particle size distribution due to sonication was observed. However, in the case of the Pt/SF catalyst, acoustic irradiation induced morphological changes on the catalyst particle surface (SEM), which might be the cause for enhancement of the initial reaction rate and enantioselectivity.

Evaluation of the photostability of different UV filter combinations in a sunscreen.

Development of photostable sunscreens is extremely important to preserve the UV protective capacity and to prevent the reactive intermediates of photounstable filter substances behaving as photo-oxidants when coming into direct contact with the skin. Thus, the objective of this study was to evaluate the photostability of four different UV filter combinations in a sunscreen by using HPLC analysis and spectrophotometry. The formulations that were investigated included four different UV filter combinations often used in SPF 15 sunscreens. The UV filter combinations were: octyl methoxycinnamate (OMC), benzophenone-3 (BP-3) and octyl salicylate (OS) (formulation 1); OMC, avobenzone (AVB) and 4-methylbenzilidene camphor (MBC) (formulation 2); OMC, BP-3 and octocrylene (OC) (formulation 3); OMC, AVB and OC (formulation 4). In the photostability studies, 40 mg of each formulation were spread onto a glass plate and left to dry before exposure to different UVA/UVB irradiation. Exposed samples were then immersed in isopropanol and the dried film dissolved ultrasonically. The filter components in the resulting solution were quantified by HPLC analysis with detection at 325 nm and by spectrophotometry. In this study, the four UV filter combinations showed different photostability profiles and the best one was formulation 3 (OMC, BP-3 and OC), followed by formulations 4, 1 and 2. In addition, OC improved the photostability of OMC, AVB and BP-3.

Unexpected photolysis of the sunscreen octinoxate in the presence of the sunscreen avobenzone.

A major concern raised about photostability studies of sunscreen products is that the photodegradation of sunscreens does not readily translate into changes in product performance. This study examines the correlation between photochemical degradation of sunscreen agents and changes in protection provided by sunscreen films. Films of a commercial sunscreen product containing avobenzone, oxybenzone and octinoxate were irradiated using a fluorescent UV-A phototherapy lamp with additional UV-B blocking filter. Periodically, during irradiation the transmittances of the films were measured and samples collected for chemical analysis of the sunscreen agents using high-performance liquid chromatography techniques. The results show that UV-induced changes in UV transmittance of sunscreen films correlate with changes in concentration of sunscreen agents. In a parallel experiment, we also irradiated a thin film of the same product in the cavity of an electron spin resonance (ESR) spectrometer. We report the concomitant photolysis of avobenzone and octinoxate that predominates over expected E/Z photoisomerization and that irradiation of a film of this product produced free radicals detected by ESR spectroscopy that persisted even after exposure had ended.