Search Results (30)

This study investigates the formation and toxicity of disinfection by-products (DBPs) arising from the reactions between individual reactive chlorine species (RCS) and dissolved organic matter (DOM) during water treatment. Individual chlorine radicals (Cl^•) and dichloride radicals (Cl₂^•−) were selectively generated with a laser flash photolysis technique, and their interactions with Suwannee River natural organic matter (SRNOM) were analyzed. Results demonstrated a biphasic pattern of DBP formation, where initial increases in RCS exposure enhanced DBP concentrations and toxicities, followed by subsequent decreases at higher RCS exposure. Variations among DBP classes, including trichloromethanes, chloroacetic acids, and chloroacetaldehydes, highlighted the complexity of RCS-DOM interactions. Toxicity assessments further indicated chloroacetonitriles and chloroacetic acids as major toxicity contributors at varying RCS exposures. This study highlights the impact of RCS exposure levels to DBP formation and toxicities, providing mechanistic insights for optimizing parameters in RCS-mediated advanced oxidation processes (AOPs) for safer water treatment. Full article

Antimicrobial fragrances, commonly found in household and personal care products, are frequently detected in water bodies, yet their environmental fate and transformation mechanisms remain inadequately explored. This study investigates the photochemical transformation of cinnamaldehyde (CA), a representative antimicrobial fragrance, and its consequence for toxicological effects. The results showed that under UV irradiation, 94.6% CA was eliminated within 60 min, with a degradation rate of 0.059 min⁻¹. Laser flash photolysis, quenching experiments, and electron paramagnetic resonance spectra identified O₂^•− and ³CA^* as the important species, contributing 29.4% and 33.6%, respectively, to the transformation process. Additionally, singlet oxygen (¹O₂), hydroxyl radicals (^•OH), and solvated electrons (e_aq⁻) were involved in mediating the oxidation reactions. These species facilitated photoionization and oxidation, resulting in the formation of five major transformation products, including cis-cinnamyl aldehyde, cinnamic acid, styrene, 1aH-indeno [1,2-b]oxirene), and 1-Oxo-1H-indene. Most of these products were persistent, and exhibited considerable ecotoxicological risks. Specifically, the cinnamic acid and 1-Oxo-1H-indene caused severe skin irritation, while cinnamic acid induced significant eye irritation. Notably, the transformation products demonstrated sensitizing effects on human skin. This study underscores the overlooked ecotoxicological risks associated with the photochemical transformation of antimicrobial fragrances, revealing their potential to generate potent allergens and other harmful byproducts. Full article

Photooxidation imposes structural damage on proteins, and the amino acid tryptophan (Trp) is a key target for protein oxidation. The Trp radical cation (Trp^•⁺), as an oxidative product, can be reduced by plant phenols (φ-OH), a category of dietary phytochemicals essential for human health. This work is intended to investigate the efficacy of φ-OH regeneration of Trp from Trp^•⁺ as a function of φ-OH concentration and environmental pH. We have examined, by using laser flash photolysis, six different kinds of φ-OH in the aqueous system consisting of Trp and riboflavin as a photosensitizer. Taking syringic acid (Syr) as an example, upon systematically varying the pH from 2 to 10, the partition of Syr phenolate, Syr-O²⁻, increases from 0% to 70% and, accordingly, the rate of Trp regeneration increases from 4.8 × 10⁶ M⁻¹·s⁻¹ to 1.7 × 10⁸ M⁻¹·s⁻¹. It is found that the regeneration rate correlates with the driving force of the electron transfer (ET) reaction between φ-OH and Trp^•+, which can be well accounted for by Marcus’s ET theory (R² = 0.89). The λ = 0.43 ± 0.08 eV for the reorganization energy for ET from the plant phenols to the Trp^•⁺. The effects of φ-OH concentration, environmental pH, and ET driving force on the Trp regeneration reaction herein revealed are significant for enlightening further study of protein (anti)oxidation. Full article

This communication aims to comprehensively elucidate the intricate mechanism governing the interaction between the excited triplet state of 4-Carboxybenzophenone (CB*) and the anionic form of 2-Naphthalene Sulfonate (NpSO₃⁻), employing the 337 nm Nanosecond Laser Flash Photolysis technique for this investigation. When the CB is selectively excited by a 337 nm laser, two primary processes become possible: (i) energy transfer from ³CB* to NpSO₃⁻ and (ii) electron transfer from NpSO₃⁻ to ³CB*. The dynamics of these interactions are explored through experimental observations of transient absorption spectra and the analysis of respective kinetic traces. The primary process dominating in the ³(CB...NpSO₃⁻)* system is identified as triplet energy transfer from excited ³CB* to ³(NpSO₃⁻), as demonstrated by characteristic spectral features observed at 410–420 nm. Comparisons are made with a similar system studied by Yamaji and co-workers, ³(BP^•−...NpO^•)*, revealing differences in the priority of primary process occurrences. These findings contribute to a deeper understanding of the intricate interactions between excited molecules and ground-state donors, aiding in the comprehension of mechanisms governing these reactions. Full article

The subject of this study is the interaction between 5,10,15,20-tetrakis (4-sulfonatophenyl)–porphyrin (TSPP), a potential photosensitizer for photodynamic therapy (PDT) and radiotherapy, and human serum albumin (HSA), a crucial protein in the body. The main objective was to investigate the binding mechanisms, structural changes, and potential implications of these interactions for drug delivery and therapeutic applications. Spectroscopic techniques and computational methods were employed to investigate the mechanism and effects of TSPP binding by HSA. The results suggest the possibility of simultaneous binding of three TSPP ions at binding sites of different affinity within albumin. The estimated values of the binding constant K_b for these sites were in the range of 0.6 to 6.6 μM⁻¹. Laser flash photolysis indicated the stabilization of TSPP in the HSA structure, which resulted in prolonged lifetimes of the excited states (singlet and triplet) of porphyrin. Circular dichroism analysis was used to assess the changes in the secondary and tertiary structures of HSA upon TSPP binding. An analysis of the molecular docking results allowed us to identify the preferred TSPP binding sites within HSA and provided information on the specific interactions of amino acids involved in the stabilization of TSPP–HSA complexes. The estimated free energy of the binding of porphyrin at the three most favorable docking sites found in the HSA structure that was considered native were in the range of −80 to −41 kcal/mol. Finally, thermal unfolding studies showed that TSPP increased the stability of the secondary structure of albumin. All these findings contribute to the understanding of the interactions between TSPP and HSA, offering valuable insights for the development of novel cancer therapy approaches. Full article

The triplet excited state reactivity towards phenolic hydrogen of the α-diketones benzil and 2,2′-furil in the ionic liquid 1-n-butyl-3-methyl imidazolium hexafluorophosphate [bmim.PF₆] was investigated employing the nanosecond laser flash photolysis technique. Irradiation (λ_max = 355 nm) of benzil yields its triplet excited state with λ_max at 480 nm and τ_T = 9.6 μs. Under the same conditions, 2,2′-furil shows a triplet-triplet absorption spectrum with bands at 380, 410, 450, and 650 nm and τ_T = 1.4 μs. Quenching rate constants (k_q) of the reaction between benzil triplet and substituted phenols ranged from 1.4 × 10⁷ L mol⁻¹ s⁻¹ (para-chlorophenol) to 1.8 × 10⁸ L mol⁻¹ s⁻¹ (para-methoxyphenol). A new transient was formed in all cases, assigned to the benzil ketyl. Similar results were obtained for the quenching of 2,2′-furil triplet by phenols, for which k_q ranged from 1.9 × 10⁸ L mol⁻¹ s⁻¹ (para-chlorophenol) to 2.2 × 10⁸ L mol⁻¹ s⁻¹ (para-methoxyphenol). The 2,2′-furil ketyl radical was also observed in all cases (λ_max = 380 nm). The quenching rate constants are almost independent of the substituent and diffusion-controlled (k_q ~ 10⁸ L mol⁻¹ s⁻¹). The proposed mechanism for the phenolic hydrogen abstraction by benzil and 2,2′-furil triplet may involve a proton-coupled electron transfer reaction, ultimately leading to the radical pair ketyl/aryloxyl. Full article

In this investigation, a multifunctional visible-light TX-based photosensitizer containing a siloxane moiety (TXS) was designed with a good overall yield of 54%. The addition of a siloxane moiety enabled the incorporation of a TX photosensitizer into a siloxane network by photoinduced sol–gel chemistry, thus avoiding its release. Both liquid ¹H and solid-state ²⁹Si NMR measurements undeniably confirmed the formation of photoacids resulting from the photolysis of the TXS/electron acceptor molecule (Iodonium salt), which promoted the photoinduced hydrolysis/condensation of the trimethoxysilane groups of TXS, with a high degree of condensation of its inorganic network. Notably, the laser flash photolysis, fluorescence, and electron paramagnetic resonance spin-trapping (EPR ST) experiments demonstrated that TXS could react with Iod through an electron transfer reaction through its excited states, leading to the formation of radical initiating species. Interestingly, the TXS/Iod was demonstrated to be an efficient photoinitiating system for free-radical (FRP) and cationic (CP) polymerization under LEDs@385, 405, and 455 nm. In particular, whatever the epoxy monomer mixtures used, remarkable final epoxy conversions were achieved up to 100% under air. In this latter case, we demonstrated that both the photoinduced sol–gel process (hydrolysis of trimethoxysilane groups) and the cationic photopolymerization occurred simultaneously. Full article

The irradiation of 2-aryl-4-(E-3′-aryl-allylidene)-5(4H)-oxazolones 1 with blue light (456 nm) in the presence of [Ru(bpy)₃](BF₄)₂ (bpy = 2,2′-bipyridine, 5% mol) gives the unstable cyclobutane-bis(oxazolones) 2 by [2+2]-photocycloaddition of two oxazolones 1. Each oxazolone contributes to the formation of 2 with a different C=C bond, one of them reacting through the exocyclic C=C bond, while the other does so through the styryl group. Treatment of unstable cyclobutanes 2 with NaOMe/MeOH produces the oxazolone ring opening reaction, affording stable styryl-cyclobutane bis(amino acids) 3. The reaction starts with formation of the T₁ excited state of the photosensitizer ³[Ru*(bpy)₃]²⁺, which reacts with S₀ of oxazolones 1 through energy transfer to give the oxazolone T₁ state ³(oxa*)-1, which is the reactive species and was characterized by transient absorption spectroscopy. Measurement of the half-life of ³(oxa*)-1 for 1a, 1b and 1d shows large values for 1a and 1b (10–12 μs), while that of 1d is shorter (726 ns). Density functional theory (DFT) modeling displays strong structural differences in the T₁ states of the three oxazolones. Moreover, study of the spin density of T₁ state ³(oxa*)-1 provides clues to understanding the different reactivity of 4-allylidene-oxazolones described here with respect to the previously reported 4-arylidene-oxazolones. Full article

The excited triplet state of a molecule (T₁) is one of the principal intermediate products in various photochemical processes due to its high reactivity and relatively long lifetime. The T₁ quantum yield (${\phi }_{\mathrm{T}}$) is one of the most important characteristics in the study of photochemical reactions. It is of special interest to determine the ${\phi }_{\mathrm{T}}$ of various photoactive compounds (photosensitizer, PS) used in photodynamic therapy (PDT). PDT is an effective medical technique for the treatment of serious diseases, such as cancer and bacterial, fungal and viral infections. This technique is based on the introduction of a PS to a patient’s organism and its further excitation by visible light, producing reactive oxygen species (ROS) via electron or energy transfer from the PS T₁ state to the biological substrate or molecular oxygen. Therefore, information on the ${\phi }_{\mathrm{T}}$ value is fundamental in the search for new and effective PSs. There are various experimental methods to determine ${\phi }_{\mathrm{T}}$ values; however, these methods demonstrate a high discrepancy between ${\phi }_{\mathrm{T}}$ values. This stimulates the analysis of various factors that can affect the determined ${\phi }_{\mathrm{T}}$. In this study, we analyze the effect of the intensity profile of the exciting laser pulse on the calculation of the ${\phi }_{\mathrm{T}}$ value obtained by the Laser Flash Photolysis technique. The φ_T values were determined by analyzing the variation of a sample transient absorption in the function of the exciting laser pulse intensity, in combination with the spectral and kinetic PS characteristics obtained in nonlinear optical experiments by solving the rate equations of a five-level-energy diagram. Well-studied PSs: meso-tetra(4-sulfonatophenyl) (TPPS₄) porphyrins, its zinc complex (ZnTPPS₄) and the zinc complex of meso-tetrakis(N-methylpyridinium-4-yl) (ZnTMPyP) were chosen as test compounds to evaluate the proposed model. The ${\phi }_{\mathrm{T}}$ values were determined through a comparison with the ${\phi }_{\mathrm{T},\mathrm{T}\mathrm{M}\mathrm{P}\mathrm{y}\mathrm{P}}$ = 0.82 of meso-tetrakis(N-methylpyridinium-4-yl) (TMPyP), used as a standard. The obtained results (${\phi }_{\mathrm{T},{\mathrm{T}\mathrm{P}\mathrm{P}\mathrm{S}}_4}=0.75\pm 0.02$, ${\phi }_{\mathrm{T},\mathrm{Z}\mathrm{n}\mathrm{T}\mathrm{M}\mathrm{P}\mathrm{y}\mathrm{P}}=0.90\pm 0.03)$, and ${\phi }_{\mathrm{T},{\mathrm{Z}\mathrm{n}\mathrm{T}\mathrm{P}\mathrm{P}\mathrm{S}}_4}=0.89\pm 0.03$) are highly compatible with the medium ${\phi }_{\mathrm{T}}$ values obtained using the known methods. Full article

In the present study, we investigated the photooxidation of the biomimetic model of C-terminal methionine, N-Acetyl-Methionine (N-Ac-Met), sensitized by a 3-Carboxybenzophenone (3CB) excited triplet in neutral and basic aqueous solutions. The short-lived transient species that formed in the reaction were identified and quantified by laser flash photolysis and the final stable products were analyzed using liquid chromatography coupled with high-resolution mass spectrometry (LC-MS) and tandem mass spectrometry (MSMS). Based on these complementary methods, it was possible to calculate the quantum yields of both competing reactions, and the deprotonation was found to be favored over decarboxylation (for neutral pH: ϕ_-H = 0.23 vs. ϕ_-CO2 = 0.09, for basic pH: ϕ_-H = 0.23 vs. ϕ_-CO2 = 0.05). Findings on such a model system, which can possibly mimic the complex protein environment, are important in understanding complicated biological systems, for example, the studied compound, N-Ac-Met, can, to some extent, mimic the methionine in the C-terminal domain of β-amyloid, which is thought to be connected with the pathogenesis of Alzheimer’s disease. Full article

Under photoirradiation, Sc₃N@I_h-C₈₀ reacted readily with disilirane 1, silirane 4, and digermirane 7 to afford the corresponding 1:1 adducts, whereas Sc₃N@D_5h-C₈₀ was recovered without producing those adducts. Based on these results, we described a novel method for the exclusive separation of I_h and D_5h isomers of Sc₃N@C₈₀. The method includes three procedures: selective derivatization of Sc₃N@I_h-C₈₀ using 1, 4, and 7, facile HPLC separation of pristine Sc₃N@D_5h-C₈₀ and Sc₃N@I_h-C₈₀ derivatives, and thermolysis of Sc₃N@I_h-C₈₀ derivatives to collect pristine Sc₃N@I_h-C₈₀. In addition, laser flash photolysis experiments were conducted to elucidate the reaction mechanism. Decay of the transient absorption of ³Sc₃N@I_h-C₈₀^* was observed to be enhanced in the presence of 1, indicating the quenching process. When Sc₃N@D_5h-C₈₀ was used, the transient absorption was much less intensive. Therefore, the quenching of ³Sc₃N@D_5h-C₈₀^* by 1 could not be confirmed. Furthermore, we applied time-dependent density functional theory (TD-DFT) calculations of the photoexcited states of Sc₃N@C₈₀ to obtain insights into the reaction mechanism. Full article

Oxidation of methionine (Met) is an important reaction that plays a key role in protein modifications during oxidative stress and aging. The first steps of Met oxidation involve the creation of very reactive and short-lived transients. Application of complementary time-resolved radiation and photochemical techniques (pulse radiolysis and laser flash photolysis together with time-resolved CIDNP and ESR techniques) allowed comparing in detail the one-electron oxidation mechanisms initiated either by ^●OH radicals and other one-electron oxidants or the excited triplet state of the sensitizers e.g., 4-,3-carboxybenzophenones. The main purpose of this review is to present various factors that influence the character of the forming intermediates. They are divided into two parts: those inextricably related to the structures of molecules containing Met and those related to external factors. The former include (i) the protection of terminal amine and carboxyl groups, (ii) the location of Met in the peptide molecule, (iii) the character of neighboring amino acid other than Met, (iv) the character of the peptide chain (open vs cyclic), (v) the number of Met residues in peptide and protein, and (vi) the optical isomerism of Met residues. External factors include the type of the oxidant, pH, and concentration of Met-containing compounds in the reaction environment. Particular attention is given to the neighboring group participation, which is an essential parameter controlling one-electron oxidation of Met. Mechanistic aspects of oxidation processes by various one-electron oxidants in various structural and pH environments are summarized and discussed. The importance of these studies for understanding oxidation of Met in real biological systems is also addressed. Full article

Reactive oxygen species comprise oxygen-based free radicals and non-radical species such as peroxynitrite and electronically excited (singlet) oxygen. These reactive species often have short lifetimes, and much of our understanding of their formation and reactivity in biological and especially medical environments has come from complimentary fast reaction methods involving pulsed lasers and high-energy radiation techniques. These and related methods, such as EPR, are discussed with particular reference to singlet oxygen, hydroxy radicals, the superoxide radical anion, and their roles in medical aspects, such as cancer, vision and skin disorders, and especially pro- and anti-oxidative processes. Full article

Exposure to sun radiation causes great oxidative stress and activates a numerous of defense mechanisms in living systems, such as the synthesis of antioxidants. Resveratrol (RSV), a naturally occurring stilbene molecule, has antioxidant properties and is synthesized in large amounts when plants are under high oxidative stress. Likewise, under UV and visible radiation, biomolecules are oxidized, losing their physiological properties and, therefore, avoiding the harmful effects of solar radiation is crucial in order to preserve the functionality of cellular components. In proteins, one essential component that is often susceptible to degradation is the amino acid histidine (His), which can be modified via several oxidizing mechanisms. In this article, we evaluate the photoprotection capacity of RSV in photosensitized oxidation of His, which is initiated with a one-electron transfer reaction, yielding the His radical cation (His^•+). The photoprotective properties of RSV are evaluated using kinetics analysis during steady-state irradiation and laser flash photolysis experiments. The experimental results reveal that the presence of RSV in the solution causes an evident decrease of the His consumption initial rates as a result of a reaction between His^•+ and RSV that recovers the amino acid. In addition, we conclude that during its antioxidant action, RSV is consumed being a sacrificial antioxidant. Full article

Within the reactive oxygen species (ROS) generated by cellular metabolisms, hydroxyl radicals (HO^•) play an important role, being the most aggressive towards biomolecules. The reactions of HO^• with methionine residues (Met) in peptides and proteins have been intensively studied, but some fundamental aspects remain unsolved. In the present study we examined the biomimetic model made of Ac-Met-OMe, as the simplest model peptide backbone, and of HO^• generated by ionizing radiation in aqueous solutions under anoxic conditions. We performed the identification and quantification of transient species by pulse radiolysis and of final products by LC-MS and high-resolution MS/MS after γ-radiolysis. By parallel photochemical experiments, using 3-carboxybenzophenone (CB) triplet with the model peptide, we compared the outcomes in terms of short-lived intermediates and stable product identification. The result is a detailed mechanistic scheme of Met oxidation by HO^•, and by CB triplets allowed for assigning transient species to the pathways of products formation. Full article