Photooxidation Reactions Research Articles

Effect of Hyaluronic Acid on the Activity of Methylene Blue in Photogeneration of 1O2

The effect of a natural polysaccharide (hyaluronic acid (HA)) on the photocatalytic activity of methylene blue (MB) was studied both under model conditions (a tryptophan photooxidation reaction in water) and with in vitro experiments on P. aeruginosa and S. aureus bacterial cultures. It was shown spectrophotometrically that, in the presence of HA, an increase in the optical density of the absorption bands λ = 665 nm and 620 nm—which correspond to the monomeric and dimeric forms of the dye, respectively—was observed in the EAS of the dye, while the ratio of the optical density of these bands remained practically unchanged. When adding HA to MB, the intensity of singlet oxygen 1O2 photoluminescence and the degree of fluorescence polarization of MB increase. The observed effects are associated with the disaggregation of molecular associates of the dye in the presence of HA. The maximum increase in the photocatalytic activity of MB (by 1.6 times) was observed in the presence of HA, with concentrations in a range between 0.0015 wt.% and 0.005 wt.%.

Synthesis, Structure, and Properties of Dion–Jacobson Double‐Layered Perovskites A′SmNb2O7 (A′=Rb, K, Na, Li, H)

AbstractDion‐Jacobson‐type layered perovskite compounds A′SmNb2O7 (A′=Rb, K, Na, Li, H) were synthesized using solid‐state and ion‐exchange methods. While the parent solid‐state product RbSmNb2O7, has previously been studied, the ion‐exchanged compounds were obtained and studied for the first time. The phase and chemical purity of the compounds were confirmed by X‐ray diffraction (XRD) and energy‐dispersive X‐ray spectroscopy (EDX). The crystal structures of RbSmNb2O7 (I2 cm, a=0.54356(1) nm, b=0.53935(1) nm, c=2.1891(5) nm), KSmNb2O7 (I2 cm, a=0.53660(7) nm, b=0.54481(6) nm, c=2.1527(1) nm) and LiSmNb2O7 (B2 cm, a=0.54546(4) nm, b=0.53567(4) nm, c=2.04582(5) nm) were refined using the Rietveld method. Polyhedral distortions in these structures have been studied in detail. The thermal behavior of the compounds has been determined using differential thermal analysis (DTA), revealing that A′=Na, Li and H compounds are metastable hydrates, while A′=Rb and K compounds are stable. The optical band gap, valence band edge, and conduction band edge potentials of the compounds obtained were calculated using diffuse reflection spectroscopy data. A photocatalytic experiment was performed on the degradation of methylene blue under ultraviolet light. All of the samples obtained showed some asctivity in the reaction of dye photooxidation.

Suppressing Effect of Flavonoid Compounds on Lipids Photooxidation of Sheep Red Blood Cells and Oleic Acid Photooxidation

ABSTRACTPhotosensitizers and pigments in raw meat such as porphyrins, riboflavin, and myoglobin after incorporation with light beam prompt the generation of singlet oxygen (1O2) from triplet oxygen (3O2) and cause oxidative rancidity of meat products. In this study, the results of photooxidation reactions of sheep erythrocyte (red blood cell) model as a model rich in hemoglobin and phospholipids bilayer, and oleic acid model were obtained by 1H NMR spectroscopy, TBARS assay, and iodometric titration. In both models, the rate of lipid photooxidation in the presence of hydroalcoholic extracts of Turmeric (Curcuma longa L.) and Cumin (Cuminum cyminum L.) as natural antioxidants, Butyl hydroxytoluene (BHT) as a synthetic antioxidant, and sodium azide (NaN3) as a well‐known 1O2 scavenger were decreased in the order of NaN3 > Turmeric > Cumin > BHT. It was proven that during the photooxidation process, there is a direct association between the amount of flavonoid compounds and 1O2 scavenging.

Heterogeneous synthesis of benzo[f]indole-4,9-diones derivatives using sulfonic resin and photocatalytic study

This research introduces a heterogeneous approach utilizing a resin-bound sulfonic acid catalyst (Dowex®-H) to synthesize benzo[f]indole-4,9-dione derivatives using β-enaminones systems and 2-bromonaphtoquinone. This method facilitates synthesizing a diverse range of compounds with varying substitution patterns, achieving yields of 88 %. The catalyst can be reused for up to five cycles without requiring reactivation. These compounds absorption spectra also show absorption (λmax) around 250–260 nm with a significant transition around 400 nm. Their photocatalytic potential was assessed by the model reaction of benzylamine photooxidation, achieving a yield of over 99 % within 36 h.

Light Absorption Properties of Brown Carbon Aerosol During Winter at a Polluted Rural Site in the North China Plain

Brown carbon aerosols (BrC), a subfraction of organic aerosols, significantly influence the atmospheric environment, climate and human health. The North China Plain (NCP) is a hotspot for BrC research in China, yet our understanding of the optical properties of BrC in rural regions is still very limited. In this study, we characterize the chemical components and light absorption of BrC at a rural site during winter in the NCP. The average mass concentration of PM1 is 135.1 ± 82.3 μg/m3; organics and nitrate are the main components of PM1. The absorption coefficient of BrC (babs,BrC) is 53.6 ± 45.7 Mm−1, accounting for 39.5 ± 10.2% of the total light absorption at 370 nm. Diurnal variations reveal that the babs,BrC and organics are lower in the afternoon, attributed to the evolution of planetary boundary layers. BrC is mainly emitted locally, and both the aqueous phase and the photooxidation reactions can increase babs,BrC. Notably, the babs,BrC is reduced when RH > 65%. During foggy conditions, reactions in the aqueous phase facilitate the formation of secondary components and contribute to the bleaching of BrC. This process ultimately causes a decrease in both the absorption Ångström exponent (AAE) and the mass absorption efficiency (MAE). In contrast, the babs,BrC, along with AAE and MAE, rise significantly due to substantial primary emissions. This study enhances our understanding of the light absorption of BrC in rural polluted regions of the NCP.

Precise Single‐Atom Modification of Hybrid Lead Chlorides for Electron Donor‐Acceptor Effect and Enhanced Photocatalytic Aerobic Oxidation

Hybrid lead halides show significant potential in photocatalysis due to their excellent photophysical properties, but the atomically precise modification of their organic component to achieve synergistic interactions with the lead halide units remains a great challenge. Herein, for the first time, we have employed the crystal engineering strategy to construct a class of single‐atom‐substituted hybrid lead halides with electron donor‐acceptor (D‐A) effect. The lead halide frameworks consist of 1D linear [PbCl]+ chains as inorganic building units and benzoxadiazole/benzothiadiazole/ benzoselenadiazole‐funtionalized dicarboxylates as linkers. The covalent bonding between the organic ligands with electron‐withdrawing groups and the electron‐rich lead halide units not only facilitate the charge separation, but also enhance structural robustness that is critical for photocatalysis. The D‐A structured lead halides serve as highly efficient heterogeneous photooxidation catalysts, including aerobic oxidation of C(sp3)‐H bonds, oxidative coupling of primary amines, oxidation of phenylboronic acids and selective oxidation of sulfides that are demonstrated in 30 examples. Importantly, these photooxidation reactions are able to be driven by natural sunlight and ambient air to afford quantitative yields. Moreover, our lead halide photocatalysts are successful to fix into a photocatalytic flow system, which enables the flow‐type synthesis of high value‐added photooxidation products on a gram scale.

Precise Single-Atom Modification of Hybrid Lead Chlorides for Electron Donor-Acceptor Effect and Enhanced Photocatalytic Aerobic Oxidation.

Hybrid lead halides show significant potential in photocatalysis due to their excellent photophysical properties, but the atomically precise modification of their organic component to achieve synergistic interactions with the lead halide units remains a great challenge. Herein, for the first time, we have employed the crystal engineering strategy to construct a class of single-atom-substituted hybrid lead halides with electron donor-acceptor (D-A) effect. The lead halide frameworks consist of 1D linear [PbCl]+ chains as inorganic building units and benzoxadiazole/benzothiadiazole/ benzoselenadiazole-funtionalized dicarboxylates as linkers. The covalent bonding between the organic ligands with electron-withdrawing groups and the electron-rich lead halide units not only facilitate the charge separation, but also enhance structural robustness that is critical for photocatalysis. The D-A structured lead halides serve as highly efficient heterogeneous photooxidation catalysts, including aerobic oxidation of C(sp3)-H bonds, oxidative coupling of primary amines, oxidation of phenylboronic acids and selective oxidation of sulfides that are demonstrated in 30 examples. Importantly, these photooxidation reactions are able to be driven by natural sunlight and ambient air to afford quantitative yields. Moreover, our lead halide photocatalysts are successful to fix into a photocatalytic flow system, which enables the flow-type synthesis of high value-added photooxidation products on a gram scale.

Porous Bimetallic Ti-MOFs for Photocatalytic Oxidation of Amines in Air.

A family of microporous titanium-containing metal-organic frameworks (denoted as M2Ti-CPCDC, M = Mn, Co, Ni) has been synthesized by using a bimetallic [M2Ti(μ3-O)(COO)6] cluster and a tritopic carbazole-based organic ligand H3CPCDC. M2Ti-CPCDC are stable and display permanent porosity for N2 and CO2 uptake, ranking among the most porous titanium-based metal-organic frameworks. M2Ti-CPCDC crystals exhibit n-type semiconductor behavior. Further catalytic studies demonstrate that all M2Ti-CPCDC materials are applicable for triggering photo-oxidative reactions of amines in air. More specifically, amines with electron-donating groups afford the aldehydes as the main products, while amines bearing electron-withdrawing groups give rise to imines as the main product. Among them, Mn2Ti-CPCDC exhibit the best photocatalytic activity, with conversion of benzylamine up to 99% and selectivity of 99%. Mn2Ti-CPCDC could be recycled in at least three runs while retaining crystallinity and catalytic activity. The reaction mechanism indicates that photoinduced hole (h+), superoxide radical anion (O2·-), and singlet oxygen (1O2) are the main active species involved in the photo-oxidation process.

Exploring the Impact of 1,8-Diioodoctane on the Photostability of Organic Photovoltaics.

Improving the photostability of the light-harvesting blend film in organic photovoltaics is crucial to achieving long-term operational lifetimes that are required for commercialization. However, understanding the degradation factors which drive instabilities is complex, with many variables such as film morphology, residual solvents, and acceptor or donor design all influencing how light and oxygen interact with the blend film. In this work, we show how blend films comprising a donor polymer (PBDB-T) and small molecule acceptor (PC71BM or ITIC) processed with solvent additive (DIO) yield very different film morphologies, device performance, and photostability. We show that DIO is retained approximately 10 times more effectively in ITIC based films compared to PC71BM. Unexpectedly, we see that while high volumes of DIO reduce photostability for encapsulated ITIC devices, when oxygen is introduced DIO can improve the lifetime of PBDB-T:ITIC based cells. Here, the addition of 3% DIO doubles the T 80 compared to ITIC based devices without DIO, suggesting that DIO-induced morphological changes interfere with or reduce photo-oxidative reactions.

BODIPY-Helicene Based Heavy-Atom-Free Photocatalyst for Oxidative Coupling of Amines and Photooxidation of Sulfides.

To develop heavy-atom-free triplet photosensitizers (PSs) based photocatalysts, we designed and synthesized two BODIPY-helicene dyes by fusing the BODIPY core and modified [5]helicene structures. These BODIPY-helicenes structures are twisted and their twisting angles are increased by the developed synthetic method. The BODIPY-helicenes have broad absorption bands over UV-visible region with high triplet conversions and long triplet lifetimes as compared to planar BODIPY dye, PM567. Consequently, these dyes are also highly efficient in generating 1O2 by transferring their triplet energy to 3O2 and importantly. All these are confirmed by dye-sensitised photooxidation reaction, nanosecond transient absorption spectroscopy study, phosphorescence measurement and DFT calculations. Finally, photocatalytic activity of the highest 1O2 generating BODIPY-helicene (4b) was checked. 4b is highly efficient in photocatalytic oxidative coupling of differently substituted amines through aerobatic oxidation using 1O2 generated by its photosensitization. It is also highly efficient photocatalyst for aerobatic oxidation of sulfides to sulfoxides. Importantly, the photocatalyst could be quantitatively recovered and reused for several cycles. All these results confirmed the potential use of the BODIPY-helicenes as PSs for photocatalytic organic reactions and the design strategy will be useful for the future development of heavy-atom-free photocatalyst.

Tensing Flipper: Photosensitized Manipulation of Membrane Tension, Lipid Phase Separation, and Raft Protein Sorting in Biological Membranes.

The lateral organization of proteins and lipids in the plasma membrane is fundamental to regulating a wide range of cellular processes. Compartmentalized ordered membrane domains enriched with specific lipids, often termed lipid rafts, have been shown to modulate the physicochemical and mechanical properties of membranes and to drive protein sorting. Novel methods and tools enabling the visualization, characterization, and/or manipulation of membrane compartmentalization are crucial to link the properties of the membrane with cell functions. Flipper, a commercially available fluorescent membrane tension probe, has become a reference tool for quantitative membrane tension studies in living cells. Here, we report on a so far unidentified property of Flipper, namely, its ability to photosensitize singlet oxygen (1O2) under blue light when embedded into lipid membranes. This in turn results in the production of lipid hydroperoxides that increase membrane tension and trigger phase separation. In biological membranes, the photoinduced segregated domains retain the sorting ability of intact phase-separated membranes, directing raft and nonraft proteins into ordered and disordered regions, respectively, in contrast to radical-based photo-oxidation reactions that disrupt raft protein partitioning. The dual tension reporting and photosensitizing abilities of Flipper enable simultaneous visualization and manipulation of the mechanical properties and lateral organization of membranes, providing a powerful tool to optically control lipid raft formation and to explore the interplay between membrane biophysics and cell function.

Concurrent Photooxidation and Photoreduction of Catechols and Para-Quinones by Chlorophyll Metabolites

Photosynthesis is initiated when the sun’s light induces electron transfer from chlorophyll to plastoquinone, a para-quinone. While photosynthesis occurs in the intact chloroplasts of living plants, similar photochemical reactions between dietary chlorophyll metabolites and quinones are likely and may affect health outcomes. Herein, we continue our studies of the direct photoreduction of para-quinones and ortho-quinones that were generated by the photo-oxidation of catechols. Chlorophyll metabolites, including pheophorbide A, chlorin e6, and pyropheophorbide A, as well as methylene blue were employed as photosensitizers. We detected hydrogen peroxide using horseradish peroxidase following the photo-oxidation of the catechol dopamine, even in the presence of EDTA, a tertiary amine electron donor. Under ambient oxygen, hydrogen peroxide was also detected after the photoreduction of several para-quinones, including 2,3-dimethoxy-5-methyl-p-benzoquinone (CoQ0), methoxy-benzoquinone, and methyl-benzoquinone. The combinations of methylene blue and EDTA or pheophorbide A and triethanolamine as the electron donor in 20% dimethylformamide were optimized for photoreduction of the para-quinones. Chlorin e6 and pyropheophorbide A were less effective for the photoreduction of CoQ0 but were equivalent to pheophorbide A for generating hydrogen peroxide in photo-oxidation reactions with photosensitizers, oxygen, and triethanolamine. We employed dinitrophenylhydrazine to generate intensely colored adducts of methoxy-benzoquinone, methyl-benzoquinone, and 1,4-benzoquinone.

Pyrazine-based supramolecular photosensitizing assemblies as type I photosensitizers for high-efficiency photooxidation reactions

Donor-acceptor thermally activated delayed fluorescent (TADF) materials have been widely used in photocatalytic reactions as organic photosensitizers. However, the construction of TADF photosensitizers via a supramolecular self-assembly approach with the regulation of reactive oxygen species (ROS) is still a big challenge. In this study, a TADF molecule 4,4'-(6-(pyridin-4-yl)quinoxaline-2,3-diyl)bis(N,N-diphenylaniline) (TPA-PQ) by incorporating triphenylamine (TPA) act as donor and 6-(pyridin-4-yl)quinoxaline (PQ) act as an acceptor was designed and synthesized, which exhibited excellent TADF property and strong intramolecular charge transfer. Meanwhile, the TPA-PQ can not only self-assemble to form nanofiber structure in mixed solvent of H2O and THF, but also can be used as a type I photosensitizer to selectively produce superoxide anion radicals (O2•–). More interestingly, the ROS generated from TPA-PQ can be used as photocatalysts for the oxidative hydroxylation of arylboronic acids and aerobic cross dehydrogenation coupling (CDC) reactions with high yields of 92 % and 88 %, respectively. This study presents an innovative and eco-friendly approach to utilize TADF supramolecular structures for the purpose of conducting photocatalyzed organic reactions.

EFFECT OF SNO2 POROUS STRUCTURE ON ITS OPTICAL AND PHOTOELECTROCHEMICAL PROPERTIES IN WATER AND WATER-METHANOL SOLUTIONS

Tin(IV) oxide is a wide-gap semiconductor material that is widely used in photooxidation reactions of organic compounds. However, the relationship between energetic and photoelectrocatalytic properties in the oxidation of small organic molecules has not yet been sufficiently explored. In this work, a series of tin oxides were synthesized using hydrothermal, sol-gel, and template methods. Polystyrene spheres with a size of 250 nm, as well as cetyltrimethylammonium bromide, were used as templates. X-Ray diffraction, low-temperature nitrogen adsorption, X-ray photoelectron spectroscopy, Raman spectroscopy and diffuse reflectance spectroscopy methods were used to study the structure, surface composition, optical and energy characteristics. Using photoelectrochemical methods, the potentials of the conduction band and valence band were determined, and photocurrents in aqueous and aqueous-methanol solutions were studied depending on electrode polarization. It is shown that the preparation method (sol-gel or hydrothermal) does not affect the position of energy bands, while the use of a template during synthesis leads to an increase in the average pore diameter in the samples and an increase in photocurrent values in the presence of methanol. It has been established that for template-synthesized samples, the magnitude of photocurrents in a water-methanol mixture increases with an increase in the valence-band potential. The sample prepared by the hydrothermal method using a template showed the highest photocurrent values both in the background electrolyte (17.3 μA/cm2) and in the presence of methanol (26 μA/cm2), compared to the sample prepared without using a template in the electrolyte with the addition of methanol (7.6 μA/cm2) and without it (7.8 μA/cm2).

An experimental and theoretical study of photo-oxidation reaction of 2-methyl tetrahydrofuran with Cl atom under atmospheric conditions.

Temperature-dependent rate coefficients for the reactions of 2-methyl tetrahydrofuran (MTHF) with Cl atoms in the temperature range of 268-343K at atmospheric pressure were measured using the relative-rate method. Ethylene and propane were used as reference compounds. Quantitative analysis of the post-photolysis reaction mixture was conducted using a gas chromatograph paired with a flame ionization detector (GC-FID). A gas chromatograph connected to a mass spectrometer (GC-MS) was employed for the purpose of qualitative analysis. In the experimental temperature range, the derived Arrhenius expression for the title reaction is represented by the equation cm3 molecule-1s-1. In addition to our experimental findings, we conducted computational calculations employing the CCSD(T)//BHandHLYP/6-31 + G(d,p) level of theory to complement our study. The canonical transition state theory (CTST) was utilized to compute the rate coefficients at 250-400K and 760Torr. The Arrhenius expression for the theoretically calculated "k" values is found to be cm3 molecule-1s-1. The local reactivity parameters, such as Fukui functions ( ), local softness ( ), and global softness ( ) were also calculated theoretically to understand the site-specific reactivity trend of MTHF towards Cl atoms. The atmospheric implications, branching ratios, degradation mechanism, and feasibility of the reaction are discussed in this study.

Iron redox states in closed-basin lakes on early Mars: Its sensitivity to water chemistry, hydrology, and atmospheric composition

Mars has experienced drastic environmental evolution in terms of pH, redox, and desiccation. NASA’s Curiosity rover discovered that the sediments of the Pahrump Hills member of the Murray formation in Gale Crater contained different redox states of Fe oxides. To interpret the observations, understanding the factors that control iron redox states within early Gale lakes on Mars is needed. Here, we present the results of a one-dimensional geochemical model of a closed-basin lake that considers the Fe(II) photo-oxidation reaction. Depending on the source of Fe(II) (groundwater vs. river flow), lake pH, advection rate, and atmospheric composition, we defined four types of chemical profiles in the lake; namely, Fe(II) dominated, Fe(III) dominated, carbonate precipitating, and redox-stratified profiles. The Fe(III) dominated profile corresponds to the end member case in which photo-oxidation effectively oxidizes the supplied Fe(II). The redox-stratified profile, interpreted as an intermediate condition between Fe(III) dominated profile and Fe(II) dominated profile, appears in broad parameter set when Fe(II) is supplied from the groundwater, typically with a low to moderate Fe(II) input flux at acidic to alkaline pH (pH 5–9) conditions; however, the low water flux due to the nature of the groundwater may be unable to explain the measured abundance of Fe oxides in the sediments. Another endmember case, the Fe(II) dominated profile, which would also be expected to generate mixed valence Fe oxides, occurs when the pH is acidic (pH 4–5); nevertheless, the acidic pH is inconsistent with the mineral assemblages of the sediments. Carbonate precipitating profiles were limited to the case in which Fe(II) is supplied by groundwater with high Fe input flux and alkaline pH of 8–9. These results may imply either the Fe(II) input flux was high enough for the redox-stratified case or Fe(II) photo-oxidation was suppressed by turbidity or by dusty/cloudy atmosphere, or possibly that Fe(II) oxides found in the Pahrump Hills member are, at least partly, of detrital origin. Although numerous other factors (ex., effect of lake depth, variable pH throughout the lake water, detailed chemical speciation) remain unconsidered, the diverse profiles in Fe redox resulting from Fe(II) photo-oxidation reaction sheds light on interpreting the variety and the evolution of redox condition on early Mars.

Investigating the Metal-TiO2 Influence for Highly Selective Photocatalytic Oxidation of Methane to Methanol.

Methane conversion to valuable chemicals is a highly challenging and desirable reaction. Photocatalysis is a clean pathway to drive this chemical reaction, avoiding the high temperature and pressure of the syngas process. Titanium dioxide, being the most used photocatalyst, presents challenges in controlling the oxidation process, which is believed to depend on the metal sites on its surface that function as heterojunctions. Herein, we supported different metals on TiO2 and evaluated their activity in methane photooxidation reactions. We showed that Ni-TiO2 is the best photocatalyst for selective methane conversion, producing impressively high amounts of methanol (1.600 μmol·g-1) using H2O2 as an oxidant, with minimal CO2 evolution. This performance is attributed to the high efficiency of nickel species to produce hydroxyl radicals and enhance H2O2 utilization as well as to induce carrier traps (Ti3+ and SETOVs sites) on TiO2, which are crucial for C-H activation. This study sheds light on the role of catalyst structure in the proper control of CH4 photoconversion.

Structure-Activity Relationship of Benzophenazine Derivatives for Homogeneous and Heterogenized Photooxygenation Catalysis.

Singlet oxygen is a powerful oxidant used in various applications, such as organic synthesis, medicine, and environmental remediation. Organic and inorganic photosensitizers are commonly used to generate this reactive species through energy transfer with the triplet ground state of oxygen. We describe here a series of novel benzophenazine derivatives as a promising class of photosensitizers for singlet oxygen photosensitization. In this study, we investigated the structure-activity relationship of these benzophenazine derivatives. Akin to a molecular compass, the southern fragment was first functionalized with either aromatic tertiary amines, alkyl tertiary amines, aromatic sulfur groups, alkyl sulfur groups, or cyclic ethers. Enhanced photophysical properties (in terms of triplet excited-state lifetime, absorption wavelength, triplet state energy, and O2 quenching capabilities) were obtained with cyclic ether and sulfur groups. Conversely, the presence of an amine moiety was detrimental to the photocatalysts. The western and northern fragments were also investigated and slightly undesirable to negligible changes in photophysical properties were observed. The most promising candidate was then immobilized on silica nanoparticles and its photoactivity was evaluated in the citronellol photooxidation reaction. A high NMR yield of 97 % in desired product was obtained, with only a slight decrease over several recycling runs (85 % in the fourth run). These results provide insights into the design of efficient photosensitizers for singlet oxygen generation and the development of heterogeneous systems.

Asymmetric Synthesis of β-Hydroxyphosphonates via a Chemoenzymatic Cascade.

Chiral β-hydroxyphosphonates are essential building blocks for organophosphorus compounds. However, the asymmetric synthesis of these units remains a significant challenge. Herein, we describe a one-pot chemoenzymatic cascade process to access chiral β-hydroxyphosphonates, which combines photo-oxidative chemical reactions and bioreductions. The incorporation of photooxidation in the chemical reaction resulted in up to 92% yield and >99% enantiomeric excess (ee) of β-hydroxyphosphonates in the cascade. In addition, the scale-up of diethyl (S)-(2-hydroxy-2-phenylethyl)phosphonate demonstrates the potential application of this strategy.

Contribution of oxidation reactions to photo-induced damage to cellular DNA.

This review article is aimed at providing updated information on the contribution of immediate and delayed oxidative reactions to the photo-induced damage to cellular DNA/skin under exposure to UVB/UVA radiations and visible light. Low-intensity UVC and UVB radiations that operate predominantly through direct excitation of the nucleobases are very poor oxidizing agents giving rise to very low amounts of 8-oxo-7,8-dihydroguanine and DNA strand breaks with respect to the overwhelming bipyrimidine dimeric photoproducts. The importance of these two classes of oxidatively generated damage to DNA significantly increases together with a smaller contribution of oxidized pyrimidine bases upon UVA irradiation. This is rationalized in terms of sensitized photooxidation reactions predominantly mediated by singlet oxygen together with a small contribution of hydroxyl radical that appear to also be implicated in the photodynamic effects of the blue light component of visible light. Chemiexcitation-mediated formation of "dark" cyclobutane pyrimidine dimers in UVA-irradiated melanocytes is a recent major discovery that implicates in the initial stage, a delayed generation of reactive oxygen and nitrogen species giving rise to triplet excited carbonyl intermediate and possibly singlet oxygen. High-intensity UVC nanosecond laser radiation constitutes a suitable source of light to generate pyrimidine and purine radical cations in cellular DNA via efficient biphotonic ionization.