UVA Absorber Research Articles

Synthesis of an AVB@ZnTi-LDH composite with synergistically enhance UV blocking activity and high stability for potential application in sunscreen formulations

1-(4-(1,1-Dimethylethyl)phenyl)-3-(4-methoxyphenyl)-1,3-propanedione (known as Avobenzone/AVB), widely used throughout the world as a highly effective UVA absorber, can prevent the progression of photoaging in skin, and is also known for the disadvantage of having a reduced capability to absorb UVA when exposed to sunlight for long periods. To address this challenge, ZnTi-CO3-LDH with a two-dimensional layered structure was used to improve stability and synergistically enhance UV absorption of AVB. A novel AVB loaded ZnTi-CO3-LDH (AVB@ZnTi-LDH) material was synthesized by reconstruction method and the loading content (LC) was about 46.8% investigated by high-performance liquid chromatography (HPLC). A possible mechanism for the binding of AVB with the ZnTi-LDH surface was proposed. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations were used to confirm further the coordination between Zn on the layer and the oxygen atom of the carbonyl group of AVB. UV absorption and critical wavelength of AVB@ZnTi-LDH were superior to those of AVB and ZnTi-LDH precursors. Compared with pure AVB, the photodegradation rate was reduced from 15.06% to 4.06%. Especially in titanium dioxide, the decomposition rate was reduced from 29.75% to 7.92%. Furthermore, pure AVB often reacts with multivalent metal ions to induce an unpleasant color (light yellow to reddish brown), which is greatly mitigated with AVB@ZnTi-LDH. In this study, avobenzone was combined with hydrotalcite to prepare an organic-inorganic composite with excellent UV resistance and better stability, the composite has great promise for application in sunscreen cosmetics.

Influence of the Solvent Environment on the Ultrafast Relaxation Pathways of a Sunscreen Molecule Diethylamino Hydroxybenzoyl Hexyl Benzoate.

The excited-state dynamics of photoexcited diethylamino hydroxybenzoyl hexyl benzoate (DHHB), a UVA absorber widely used in sunscreen formulations, are studied with transient electronic and vibrational absorption spectroscopy methods in four different solvents. In the polar solvents methanol, dimethyl sulfoxide (DMSO), and acetonitrile, strong stimulated emission (SE) is observed at early time delays after photoexcitation at a near-UV wavelength of λex = 360 nm, and decays with time constants of 420 fs in methanol and 770 fs in DMSO. The majority (∼95%) of photoexcited DHHB returns to the ground state with time constants of 15 ps in methanol and 25 ps in DMSO. In the nonpolar solvent cyclohexane, ∼ 98% of DHHB photoexcited at λex = 345 nm relaxes to the ground state with a ∼ 10 ps time constant, and the SE is weak. DHHB preferentially adopts an enol form in its ground S0 state, but excited state absorption (ESA) bands seen in TEAS are assigned to both the S1-keto and S1-enol forms, indicating a role for ultrafast intramolecular excited state hydrogen transfer (ESHT). This ESHT is inhibited by polar solvents. The two S1 tautomers decay with similar time scales to the observed recovery of ground state population. For molecules that avoid ESHT, torsion around a central C-C bond minimizes the S1-enol energy, quenches the SE, and is proposed to lead to a conical intersection with the S0 state that mediates the ground state recovery. A competing trans-enol isomeric photoproduct is observed as a minor competitor to parent recovery in polar solvents. Evidence is presented for triplet (T1) enol production in polar solvents, and for T1 quenching by octocrylene, a common UVB absorber sunscreen additive. The T1 keto form is observed in cyclohexane solution.

Short-lived and Nonphosphorescent Triplet state of Mexoryl SX, a UV-A Sunscreen

Mexoryl SX (terephthalylidene-3,3′-dicamphor-10,10′-disulfonic acid, Ecamsule) is a water-soluble UV-A absorber. The near-IR phosphorescence spectrum of singlet oxygen generated by photosensitization with Mexoryl SX was not observed in air-saturated water. On the other hand, the time-resolved near-IR phosphorescence spectrum was observed in oxygen-saturated phosphate buffer (pH 7.4). The quantum yield of the singlet oxygen generation (ΦΔ) was determined to be 0.0021 ± 0.0005. The ability of Mexoryl SX as a photosensitizer is quite low. The question arises as to the quite low ΦΔ value. No phosphorescence was detectable from Mexoryl SX in ethanol at 77 K. We elucidated the nature of the lowest excited triplet (T1) state of Mexoryl SX using a time-resolved EPR technique, because this technique is powerful for the study of short-lived and nonphosphorescent T1 molecules. The strong time-resolved EPR signals were observed. This fact shows that a considerable proportion of the lowest excited singlet (S1) state molecules undergoes intersystem crossing (ISC) to the T1 state and the deactivation process of the T1 state is mainly radiationless. The observed zero-filed splitting parameters, T1 lifetime, and S1 → T1 ISC anisotropy suggest that the T1 state can be regarded as a 3nπ*–3ππ* mixing state in character and the two unpaired electrons in the T1 state do not localize on (4-methylbenzylidene)camphor, a closely related component. Although the shorter T1 lifetime (47 ns) prevents T1 state quenching by ground-state oxygen, the 3nπ* character may contribute something to the low ΦΔ value.

2-Hydroxy-4-methoxybenzophenone Enhances the Suppression of Superoxide Anion Radicals Generated via UVA-induced Photosensitizing by t-Butyl Methoxydibenzoylmethane.

4-tert-Butyl-4'-methoxydibenzoylmethane (BMDM) is widely used throughout the world as a highly effective UVA absorber that can prevent the progression of photoaging in skin. However, due to its low photostability, BMDM is also known for the disadvantage of having a reduced capability to absorb UVA during prolonged exposure to sunlight. Although many studies have been carried out to overcome this disadvantage of BMDM, little attention has been paid to how the radicals generated from BMDM during UV exposure influence the skin. Therefore, the purpose of this study was twofold: One goal was to clarify the influence of radicals on human skin using cytotoxicity as a parameter. The second was to propose a solution that could reduce the radical formation while taking photostability into consideration. Using ESR spin trapping and superoxide dismutase (SOD) treatment, the radicals produced by the UV exposure of BMDM were shown to be superoxide anion radicals (•O2-). HaCaT keratinocytes exposed to UVA in the presence of BMDM showed a significant reduction in cell viability, indicating that the radicals produced from BMDM have a harmful influence on the skin. UVA exposure coincidently led to a reduction of UVA absorbance by BMDM. Interestingly, 2-hydroxy-4-methoxybenzophenone (Benzophenone-3; BP3) reduced both the radical formation and the cytotoxicity resulting from the UVA-exposure of BMDM, while also restoring its UVA absorbance. In conclusion, the results show that BMDM and BP3 is an effective combination to reduce the influence of UVA-exposed BMDM on the skin and to prevent the loss of UVA absorbance by BMDM during UV exposure.

Photophysical properties of hexyl diethylaminohydroxybenzoylbenzoate (Uvinul A Plus), a UV-A absorber.

Hexyl diethylaminohydroxybenzoylbenzoate (DHHB, Uvinul A Plus) is a photostable UV-A absorber. The photophysical properties of DHHB have been studied by obtaining the transient absorption, total emission, phosphorescence and electron paramagnetic resonance spectra. DHHB exhibits an intense phosphorescence in a hydrogen-bonding solvent (e.g., ethanol) at 77 K, whereas it is weakly phosphorescent in a non-hydrogen-bonding solvent (e.g., 3-methylpentane). The triplet-triplet absorption and EPR spectra for the lowest excited triplet state of DHHB were observed in ethanol, while they were not observed in 3-methylpentane. These results are explained by the proposal that in the benzophenone derivatives possessing an intramolecular hydrogen bond, intramolecular proton transfer is an efficient mechanism of the very fast radiationless decay from the excited singlet state. The energy level of the lowest excited triplet state of DHHB is higher than those of the most widely used UV-B absorbers, octyl methoxycinnamate (OMC) and octocrylene (OCR). DHHB may act as a triplet energy donor for OMC and OCR in the mixtures of UV-A and UV-B absorbers. The bimolecular rate constant for the quenching of singlet oxygen by DHHB was determined by measuring the near-IR phosphorescence of singlet oxygen. The photophysical properties of diethylaminohydroxybenzoylbenzoic acid (DHBA) have been studied for comparison. It is a closely related building block to assist in interpreting the observed data.

Triplet–triplet energy transfer between UV absorbers in solutions at room temperature

Abstract The triplet–triplet energy transfer between UV absorbers at room temperature has not been reported in scientific literature, although sunscreens are used at room temperature. In the present study, the bimolecular rate constants of the triplet–triplet energy transfer from a UV-A absorber, menthyl anthranilate (MA, tradename Meradimate), to typical UV-B absorbers, octocrylene (OCR, tradename Parsol 340) and octyl methoxycinnamate (OMC, tradename Parsol MCX), have been determined through the measurements of the triplet–triplet absorption of MA in solutions (acetonitrile, ethanol, and isododecane) at room temperature. These triplet–triplet energy-transfer processes are almost diffusion-controlled processes. The bimolecular rate constants of intermolecular triplet–triplet energy transfer from MA to OCR and OMC in acetonitrile were determined to be (0.9 ± 0.3) × 1010 mol−1 dm3 s−1 and (1.1 ± 0.2) × 1010 mol−1 dm3 s−1, respectively. The quenching rate constants of the triplet-state MA by OCR and OMC are comparable to that of the triplet-state MA by ground-state oxygen. There is a possibility that OCR and OMC reduce the generation of singlet oxygen by photosensitization with MA in fluid solutions. This is the first report of the direct observation of the intermolecular triplet–triplet energy transfer between UV absorbers at room temperature.

Development and evaluation of topical microemulsion of dibenzoylmethane for treatment of UV induced photoaging

Dibenzoylmethane (DBM), a phytochemical agent, occurring as a minor constituent in the root extracts of liquorice has a potential for anti-photoaging effects. It acts as a UVA absorber that filters out and prevents the penetration of UV radiations into various cell components. In this study, DBM loaded o/w microemulsion (ME) was developed and evaluated for anti-photoaging effect in mice. The ME was evaluated for various physicochemical characteristics, stability, ex-vivo skin permeation studies and in vivo evaluation in mice model of UV-radiation induced photodamage. The mean globule size of DBM loaded ME was found to be 35.550 ± 4.879 nm. The mean cumulative amount permeated/area and skin retention of DBM in 24 h from the ME was 6.81 and 5.16 folds higher, respectively as compared to the conventional cream of DBM. In vivo anti-photoaging effect on mice skin was evaluated in terms of visual scoring, pinch test, biochemical estimations and histopathological studies. Results clearly demonstrated the promising efficacy of ME formulation in preventing wrinkles, lesions and other macroscopic and microscopic changes associated with chronic UV exposure. Hence, it can be concluded that DBM ME can be used effectively used as sunscreen agent to protect against the damaging effect of UV rays.

The adsorption behaviour and photoprotection effect of UV filter absorbed on the surface of human hair.

Butyl methoxydibenzoylmethane (BMBM, an UVA absorber, the maximum absorptive wavelength is about 360 nm), octylmethoxycinnamate (OMC, an UVB filter, the maximum absorptive wavelength is about 310 nm), benzophenone-3 (an UVA and UVB filter, the maximum absorptive wavelength is about 288 and 323 nm) and octyl salicylate (an UVB filter, the maximum absorptive wavelength is about 307 nm) are four types of UV filters. This report presents the adsorption behaviours and effects of these filters on hair cuticles. Adsorption amounts of each UV filter on the hair surface were determined via the depletion method, and the photoprotective effects of these filters were identified by various methods, including protein degradation, tryptophan degradation and lipid peroxidation in hair exposed to irradiation. Results showed that adsorption of UV filters occurred fairly rapidly and reached equilibrium after approximately 1 h. The rate and amount of adsorption increased with increasing initial concentration. The adsorption amount of each UV filter was plotted against its equilibrium concentration. The adsorption capacity of 2% BMBM was higher than that of the other UV filters. Lipid peroxidation and protein degradation of hair were significantly reduced in samples treated with benzophenone-3, octyl salicylate and OMC. Tryptophan degradation was not significantly improved in any of the treatments. The adsorption kinetics of the filters is comparable with a pseudo-second-order kinetic model and that their adsorption isotherms match the Freundlich adsorption model. Adsorption followed an endothermic process. UV filters have effect on protecting hair from photodamage. The effect of UVB filters is better than UVA filters.

Energy-donor phosphorescence quenching study of triplet–triplet energy transfer between UV absorbers

The intermolecular triplet–triplet energy transfer from a photounstable UV-A absorber, 4-tert-butyl-4′-methoxydibenzoylmethane (BMDBM), to UV-B absorbers, 2-ethylhexyl 4-methoxycinnamate (octyl methoxycinnamate, OMC), octocrylene (OCR) and dioctyl 4-methoxybenzylidenemalonate (DOMBM) has been observed using a 355nm laser excitation in rigid solutions at 77K. The decay curves of the energy-donor phosphorescence in the presence of the UV-B absorbers deviate from the exponential decay at the initial stage of the decay. The Stern–Volmer formulation is not valid in rigid solutions because molecular diffusion is impossible. The experimental results indicate that the rate constant of triplet–triplet energy transfer from BMDBM to the UV-B absorbers, kT–T, decreases in the following order: kT–T (BMDBM–DOMBM)>kT–T (BMDBM–OMC)≥kT–T (BMDBM–OCR). The presence of DOMBM enhances the photostability of the widely used combination of UV-A and UV-B absorbers, BMDBM and OCR. The effects of the triplet–triplet energy transfer on the photostability of BMDBM are discussed.

A cyclic merocyanine UV-A absorber: mechanism of formation and crystal structure

The product of the reaction of 3-(3-methoxypropylamino)cyclohex-2-en-1-one and diethylsulfate has been crystallized and its structure has been determined by X-ray crystallography. The study allowed insight into the formation mechanism of cyclic merocyanine UV absorbers. X-ray diffraction analysis of the merocyanine product made it possible to define the E/Z-stereoconfiguration.

Triplet–Triplet Energy Transfer from a UV‐A Absorber Butylmethoxydibenzoylmethane to UV‐B Absorbers

The phosphorescence decay of a UV-A absorber, 4-tert-butyl-4'-methoxydibenzolymethane (BMDBM) has been observed following a 355 nm laser excitation in the absence and presence of UV-B absorbers, 2-ethylhexyl 4-methoxycinnamate (octyl methoxycinnamate, OMC) and octocrylene (OCR) in ethanol at 77 K. The lifetime of the lowest excited triplet (T1) state of BMDBM is significantly reduced in the presence of OMC and OCR. The observed quenching of BMDBM triplet by OMC and OCR suggests that the intermolecular triplet-triplet energy transfer occurs from BMDBM to OMC and OCR. The T1 state of OCR is nonphosphorescent or very weakly phosphorescent. However, we have shown that the energy level of the T1 state of OCR is lower than that of the enol form of BMDBM. Our methodology of energy-donor phosphorescence decay measurements can be applied to the study of the triplet-triplet energy transfer between UV absorbers even if the energy acceptor is nonphosphorescent. In addition, the delayed fluorescence of BMDBM due to triplet-triplet annihilation was observed in the BMDBM-OMC and BMDBM-OCR mixtures in ethanol at 77 K. Delayed fluorescence is one of the deactivation processes of the excited states of BMDBM under our experimental conditions.

Synthesis of (cinnamate-zinc layered hydroxide) intercalation compound for sunscreen application

BackgroundZinc layered hydroxide (ZLH) intercalated with cinnamate, an anionic form of cinnamic acid (CA), an efficient UVA and UVB absorber, have been synthesized by direct method using zinc oxide (ZnO) and cinnamic acid as the precursor.ResultsThe resulting obtained intercalation compound, ZCA, showed a basal spacing of 23.9 Å as a result of cinnamate intercalated in a bilayer arrangement between the interlayer spaces of ZLH with estimated percentage loading of cinnamate of about 40.4 % w/w. The UV–vis absorption spectrum of the intercalation compound showed excellent UVA and UVB absorption ability. Retention of cinnamate in ZLH interlayers was tested against media usually came across with sunscreen usage to show low release over an extended period of time. MTT assay of the intercalation compound on human dermal fibroblast (HDF) cells showed cytotoxicity of ZCA to be concentration dependent and is overall less toxic than its precursor, ZnO.Conclusions(Cinnamate-zinc layered hydroxide) intercalation compound is suitable to be used as a safe and effective sunscreen with long UV protection effect.

Excited states of menthyl anthranilate: a UV-A absorber

The photophysical properties of menthyl anthranilate (MA), a UV-A absorber, have been studied through measurements of UV absorption, fluorescence, triplet-triplet absorption and time-resolved thermal lens in ethanol at room temperature and/or 77 K. The phosphorescence and time-resolved electron paramagnetic resonance spectra have also been observed in ethanol at 77 K. The energy levels of the lowest excited singlet (S(1)) state and triplet (T(1)) state were determined. The quantum yields of fluorescence, phosphorescence and S(1) → T(1) intersystem crossing (ISC) were also determined. From the data on the lifetime and quantum yield, the rate constants of the radiative decay, internal conversion and ISC of the excited states of MA were determined. The exceptionally high ISC quantum yield of MA shows that the deactivation processes of the S(1) state of MA are different from those of most UV absorbers such as cinnamate, salicylate, 2-hydroxybenzophenone, benzotriazole and dibenzoylmethane derivatives, where the internal conversion rates of the S(1) states are much faster than the ISC rates. The observed T(1) lifetime and zero-field splitting parameters suggest that the T(1) state of MA possesses almost pure (3)ππ* character.

Convenient Synthesis of a Novel Flavonoid with Extended π‐System: Active Agent for UVA Protection

Flavonoid derivative with extended cinnamic acid moiety was synthesized using Baker‐Venkataraman reaction. The compound shows interesting UV absorption properties which make it a good UVA absorber. A bathochromic shift of 18 nm was observed when the size of cinnamic acid segment was increased by one styrylogous extension.

Photoexcited triplet states of new UV absorbers, cinnamic acid 2-methylphenyl esters

Phosphorescence spectra of nonphosphorescent or very weakly phosphorescent new UV absorbers, 2-methylphenyl cinnamate (MePC), 2-methylphenyl 4-methoxycinnamate (MePMC) and 2-methylphenyl 4-ethoxycinnamate (MePEC) have been observed by using external heavy atom effects of ethyl iodide in ethanol at 77 K. The lowest excited triplet (T(1)) energies of these new UV absorbers are lower than those of a widely used UV-A absorber, 4-tert-butyl-4'-methoxydibenzoylmethane (BM-DBM), in both keto and enol forms. The intermolecular triplet-triplet energy transfer from photolabile BM-DBM to MePMC was observed by measuring the time-resolved phosphorescence spectra. Electron paramagnetic resonance spectra have been observed for the T(1) states of these new UV absorbers in ethanol at 77 K by using benzophenone as a triplet sensitizer. The observed T(1) lifetimes, zero-field splitting (ZFS) parameters and molecular orbital calculations of the ZFS parameters suggest that T(1) states of these new UV absorbers posses mainly (3)ππ* character. The deactivation processes of the lowest excited singlet (S(1)) states are predominantly fluorescence and internal conversion to the ground (G) states in MePMC and MePEC, while the main deactivation process of the S(1) state of MePC is internal conversion to the G state. The molar absorption coefficients of MePMC and MePEC in the UV-A and UV-B regions are larger than that of most widely used UV-B absorber, octyl methoxycinnamate.

Direct observation of the intermolecular triplet–triplet energy transfer from UV-A absorber 4- tert-butyl-4′-methoxydibenzoylmethane to UV-B absorber octyl methoxycinnamate

Triplet energy transfer (TET) is an important photostabilization process for organic UV absorbers, such as 4- tert-butyl-4′-methoxydibenzoylmethane (BM-DBM) and octyl methoxycinnamate (OMC). To characterize interactions between UV absorbers as TET the interactions between BM-DBM and OMC have been studied through measurements of EPR and time-resolved phosphorescence spectra. The EPR B min signals and the phosphorescence of OMC were observed through the selective excitation of BM-DBM at 365 nm in EtOH at 77 K. These results indicate that the intermolecular TET occurs from BM-DBM to OMC. This is the first report of the experimental evidence of the TET between the organic UV absorbers.

Photostability of the sunscreening agent 4- tert-butyl-4′-methoxydibenzoylmethane (avobenzone) in solvents of different polarity and proticity

The most widely used UVA absorber in broad-spectrum sunscreens is 4- tert-butyl-4′-methoxydibenzoylmethane (avobenzone). However, the photostability of avobenzone is solvent-dependent. The aim of this work was to investigate the photostability of avobenzone in solvents of different polarity and proticity. Four solvents were employed, namely, cyclohexane, ethyl acetate, dimethylsulfoxide and methanol. The cause of the instability of avobenzone in these solvents was determined by means of UV spectroscopy, high performance liquid chromatography, gas chromatography–mass spectrometry and nuclear magnetic resonance spectroscopy. The effect of oxygen on the photo-instability was also determined. Avobenzone was found to lose absorption efficacy as a result of photoisomerisation from the enol to the keto form and/or photodegradation to form photoproducts that absorb principally in the UVC region, depending on the solvent. It was found to be essentially photostable in the polar protic solvent methanol but photoisomerised in the polar aprotic solvent dimethylsulfoxide. In the nonpolar solvent cyclohexane, it photodegraded appreciably. Both photoisomerisation and photodegradation occurred to a similar extent in the moderately polar aprotic solvent ethyl acetate. Photoisomerisation occurred only in the presence of oxygen whereas photodegradation occurred irrespective of oxygen. This knowledge is important in order to achieve the correct formulation for sunscreens incorporating avobenzone.

Sunscreens containing the broad‐spectrum UVA absorber, Mexoryl® SX, prevent the cutaneous detrimental effects of UV exposure: a review of clinical study results

UVA exposure of human skin mainly produces reactive oxygen species (ROS) leading to DNA, cell and tissue damage. It alters immune function, pigmentation and it is certainly responsible for a large part of photoaging changes. Moreover UVA is implicated in the etiology of several photodermatoses. As a consequence, to provide adequate protection, sunscreens or skin care products for daily use protective products need UVA absorbers combined with UVB ones. To assess the efficacy of sunscreens containing a broad-spectrum UVA absorber the Mexoryls SX or ecamsule and to compare formulations with and without it through a large number of clinical studies in human volunteers and patients. The following assessments were conducted: *Prevention of excessive pigmentation induced by UV exposure in Caucasian and Asian skins using a method that measures pigmentation protection factors (PPF). *Efficacy against DNA damage by measurement of pyrimidine dimer formation and p53 protein accumulation. *Protection of immune system using delayed type hypersensitivity (DTH) reactions to recall antigens, isomerization of urocanic acid (UCA), alteration of Langerhans cells (LC) density, morphology and function. *Reduction of epidermal and dermal alterations induced by repeated UVA or UV solar simulated radiation (SSR) using histology or immunohistology. *Prevention of the polymorphous light eruption (PMLE) in patients prone to develop this disease. Mexoryls SX-containing formulations showed a dose-dependent level of protection against pigmentation. For a same sun protection factor (SPF) the higher the UVA protection was, the higher was the PPF. Pyrimidine dimer formation and p53 accumulation were significantly reduced by formulations with Mexoryls SX. In the studies looking at the suppression of DTH reactions to recall antigens by the different UV spectra, the LC alterations and the cis UCA formation, Mexoryls SX formulations always showed a higher protective potency than sunscreen without it even when the protection against erythema was similar (products with same SPF). Mexoryls SX formulations also prevented or significantly decreased to minimal, ferritin, tenascin and lysozyme expression induced by repeated UVA or SSR exposure. It also reduced the enhancement of collagenase 2 mRNA expression induced by SSR exposure. Finally PMLE study demonstrated that UVA protection was essential for the prevention of this photodermatose. Mexoryls SX formulated in sunscreens or daily use products have been shown to be an effective UV absorber, leading to an increased efficacy of these products against a large number of biological damage induced by UVA, SSR or sun exposure.

The effects of manganese doping on UVA absorption and free radical generation of micronised titanium dioxide and its consequences for the photostability of UVA absorbing organic sunscreen components.

The effect of manganese doping on the free radical generation rate, free radical scavenging and UVA absorption properties of micronised sunscreen grade titania has been studied with respect to enhancement of the UVA photostability of test sunscreen formulations containing the organic UVA absorber Parsol 1789. Manganese doping has been shown to increase the UVA:UVB absorption ratio of titania, reduce free radical generation rates by over 90%, and provide free radical scavenging behaviour. Adding manganese-doped titania to a test formulation incorporating Parsol 1789 shows that manganese doping increases UVA attenuation stability by up to 3 times the amount achieved by comparable commercial undoped titania materials. HPLC data shows this to be related to an improved stabilisation of the organic sunscreen components. Manganese doped titania shows improved efficacy over undoped titania in sunscreen formulations containing organic UV absorbers.

Illumination of human keratinocytes in the presence of the sunscreen ingredient Padimate-O and through an SPF-15 sunscreen reduces direct photodamage to DNA but increases strand breaks

On illumination with simulated sunlight, the UVB-absorbing sunscreen chemical 2-ethylhexyl-4-dimethylaminobenzoate (Padimate-O) generates excited species which inflict non-ligatable strand breaks on DNA in vitro and it also becomes mutagenic to yeast in vivo. Padimate-O is known to penetrate human skin but its effects on human cells are not clear. Here, we first simulate the sunlight which penetrates human skin and use it to illuminate human keratinocytes. The DNA damage observed in terms of UV-endonuclease-sensitive sites (ESS) and direct strand breaks per kilobase (kb) of DNA per joule per square metre agrees well with that predicted from action spectra based on monochromatic light. Using plasmid DNA in vitro, we find a very similar pattern of results. Next, we simulate the spectrum that results when the incident light is first attenuated by a film of sunscreen (SPF-15; 2 mg/cm 2) containing benzophenone-3 (a UVA absorber), octyl methoxycinnamate (a UVB absorber), and Padimate-O. If the sunscreen is not in contact with keratinocytes it reduces direct DNA damage from sunlight (ESS). However, any Padimate-O in contact with the cells substantially increases indirect damage (strand breaks) even though the film of sunscreen reduces direct photodamage. We estimate that applying an SPF-15 sunscreen which contains Padimate-O to human skin followed by exposure to only 5 minimum erythemal doses (MED) of sunlight could, while suppressing the formation of ESS, increase strand breaks in cells under the epidermis by at least 75-fold compared to exposure to 1 MED in the absence of sunscreen.