Primary photophysical and photochemical processes for cerium ammonium nitrate (CAN) in acetonitrile.

Cerium ammonium nitrate (CAN) is an important photolytic source of NO3• radicals in aqueous nitric acid solutions and in acetonitrile. In this work we performed the study of primary photochemical processes for CAN in acetonitrile by means of ultrafast TA spectroscopy and quantum chemical calculations. Photoexcitation of CAN is followed by ultrafast (< 100 fs) intersystem crossing; the vibrationally cooled triplet state decays to pentacoordinated Ce(III) intermediate and NO3• radical with the characteristic time of ca. 40 ps. Quantum chemical (QM) calculations satisfactorily describe the UV-vis spectrum of the triplet state. An important feature of CAN photochemistry in CH3CN is the partial stabilization of the radical complex (RC) [(NH4)2CeIII(NO3)5…NO3•], which lifetime is ca. 2 µs. The possibility of the RC stabilization is supported by the QM calculations.

Primary processes in photophysics and photochemistry of a potential light-activated anti-cancer dirhodium complex.

Photophysics and photochemistry of a potential light-activated cytotoxic dirhodium complex [Rh2(µ-O2CCH3)2(bpy)(dppz)](O2CCH3)2, where bpy = 2,2'-bipyridine, dppz = dipyrido[3,2-a:2',3'-c]phenazine (Complex 1 or Rh2) in aqueous solutions was studied by means of stationary photolysis and time-resolved methods in time range from hundreds of femtoseconds to microseconds. According to the literature, Complex 1 demonstrates both oxygen-dependent (due to singlet oxygen formation) and oxygen-independent cytotoxicity. Photoexchange of an acetate ligand to a water molecule was the only observed photochemical reaction, which rate was increased by oxygen removal from solutions. Photoexcitation of Complex 1 results in the formation of the lowest triplet electronic excited state, which lifetime is less than 10 ns. This time is too short for diffusion-controlled quenching of the triplet state by dissolved oxygen resulting in 1O2 formation. We proposed that singlet oxygen is produced by photoexcitation of weakly bound van der Waals complexes [Rh2…O2], which are formed in solutions. If this is true, no oxygen-independent light-induced cytotoxicity of Complex 1 exists. Residual cytotoxicity deaerated solutions are caused by the remaining [Rh2…O2] complexes.

Multifunctional fluorescent diarylethene: time-resolved study of photochemistry.

A study of luminescence and photochromic properties of (E)-2,3-bis(2,5-dimethylthiophen-3-yl)-5-(4-(pyrrolidin-1-yl)benzylidene)cyclopent-2-en-1-one, which is a diarylethene with a push-pull system between carbonyl and dimethylamino groups, was performed using time-resolved methods. The intramolecular charge transfer (ICT) process as well as 6π-electrocyclization and E-/Z-isomerization contribute to the complex light-induced properties of this molecule. Formation of unexpected short-lived intermediates was detected in the time range from 100 fs to 100 µs. A model based on two processes (additional photocyclization and interconversion between conformers) was proposed to rationalize this result. The key intermediates existing in the picosecond time domain are so-called precursors, which are proposed for both parallel (p) and anti-parallel (ap) isomers of the open form. In general, fast light-induced processes for the fluorescent diarylcyclopentenones are much more complicated than for the parent cyclopentenone-based DAE.

Sulfur-Containing Radical Anions Formed by Photolysis of Thiosulfate: Quantum-Chemical Analysis.

The photochemistry of sodium thiosulfate (S2O32-) in aqueous solutions is rather complicated. Several sulfur-containing radical anions are formed upon photoexcitation. Any of them are rather common (SO3•-, SO2•-, and SO5•-); others are rare (S2O3•-, •S4O63-, and S•-) or never documented (S2O5•-). In order to support the identification of intermediate radical anions, quantum-chemical (QM─quantum mechanical) calculations of the geometric and electronic structures of S2O3•-, S2O5•-, and •S4O63- were performed. Two different approaches, time-dependent density functional theory and complete active space self-consistent field, were applied to identify the method optimal for the reproduction of the experimental electronic absorption spectra. Several of the most commonly used functionals were considered. The best agreement with the experimentally observed spectra of reference compounds (common sulfur-containing anions and radical anions) was achieved for the WB97X-D3 functional. Using this approach, satisfactory agreement between experimental and calculated spectra of S2O3•-, S2O5•-, and •S4O63- was achieved. It was shown that S2O5•- and •S4O63- can exist in two isomeric forms with different spectral properties. These isomers are S2O3O2•-; SO3SO2•- for the case of S2O5•- and (S2O3)2•3-; (S3O32-...SO3•-) for the case of •S4O63-.

Capillary zone electrophoresis as a simple approach for the study of p-arsanilic acid transformation in the process of photolytic degradation.

Arsenic aromatic compounds including p-arsanylic acid (pASA) are still widely used in a number of countries as the feed additives in animal breeding resulting in its entering the environment. Under the influence of oxidizing agents or UV radiation, pASA undergoes transformations leading to generation of inorganic arsenic species that are more mobile and toxic than organic ones. On the one hand, an approach based on the treatment of contaminated waters by UV irradiation seems perspective for their detoxification, but the feasibility of this approach depends on the composition of the products forming as a result of photodegradation. In the present work, a CZE was applied for the study of the pASA degradation process during stationary (308 nm) photolysis in the presence of Fe(III)-oxalate complex. A developed assay allowed controlling the parent compounds and also As-containing products of pASA degradation, presented mainly by arsenate and arsenite ions. It was found that the main inorganic derivatives of the pASA photolytic conversions are presented by arsenate and arsenite ions whose ratio depends on the initial amount of pASA and reaction conditions.

Photochemistry of hexachloroosmate(IV) in ethanol.

The photochemistry of the OsIVCl62- complex in ethanol was studied by means of stationary photolysis, nanosecond laser flash photolysis, ultrafast pump-probe spectroscopy and quantum chemistry. The direction of the photochemical process was found to be wavelength-dependent. Irradiation in the region of the d-d and LMCT bands results in the photosolvation (with the wavelength-dependent quantum yield) and photoreduction of Os(iv) to Os(iii), correspondingly. The characteristic time of photosolvation is ca. 40 ps. Photoreduction occurs in the micro- and millisecond time domains via several Os(iii) intermediates. The nature of intermediates and the possible mechanisms of photoreduction are discussed. We believe that the lability of the photochemically produced Os(iv) and Os(iii) intermediates determines the synthetic potential of OsIVCl62- photochemistry.

Mechanistic study of the trans,cis,cis-[RuCl2(DMSO)2(H2O)2] complex photochemistry in aqueous solutions.

It is known that trans,cis,cis-[RuCl2(DMSO)2(H2O)2] (1a) complexes, which are formed upon dissolution of trans-[RuCl2(DMSO)4] in water, demonstrate light-induced cytotoxicity. The mechanistic study of 1a photochemistry has been performed using ultrafast pump-probe spectroscopy, laser flash photolysis and stationary photolysis. The first stage of 1a photochemistry is the photoexchange of a DMSO ligand to a water molecule; its quantum yield is wavelength-dependent (estimating by values 0.3 and 0.04 upon irradiation at 308 and 430 nm, respectively). The mechanism of photoexchange is complicated involving at least four Ru(ii) intermediates. Two tentative mechanisms of the process are proposed.

Mechanism of photochromic transformations and photodegradation of an asymmetrical 2,3-diarylcyclopentenone.

A mechanistic study of the photochromic properties and photodegradation processes of an asymmetrical diarylcyclopentenone bearing thiophene and benzothiophene units using stationary photolysis, nanosecond laser flash photolysis and time-resolved luminescence was performed. It was found that the light-induced reversible isomerization of (3-(2,5-dimethyltiophen-3-il)-2-(2-methyl-1-benzylthiophen-3-il)cyclopent-2-en-1-one, compound 1) from open to closed form is a common photochromic transformation inherent to diarylethenes, while the photodegradation process proceeds in two ways. The first is a formal 1,2-dyotropic rearrangement, proceeding without the participation of oxygen. The second is the oxygen-dependent mechanism involving the excitation of the open form 1A into the triplet state, quenching of the latter by dissolved oxygen, and oxidation of the initial compound by singlet oxygen.

Short-lived intermediates in photochemistry of an OsCl62- complex in aqueous solutions.

Two mechanisms of OsIVCl62- photolysis were studied by means of quantum chemical calculations in gas and aqueous phases. The difference between these mechanisms is in the nature of the possible Os(iv) key intermediates (KI). According to calculations, the intermediate is an OsIVCl5- complex of square pyramidal coordination geometry. The calculations do not give an opportunity to make an unambiguous choice between the triplet and quintet multiplicities of OsIVCl5-. The calculated CASSCF/IMCP-SR1 transition energies for 5OsIVCl5- are lower than for 3OsIVCl5-, while the calculated XMC-QDPT2/SBKJC spectra for the triplet state are in better agreement with the experimental absorption spectrum of the KI than for the quintet state.

A cis,fac-[RuCl2(DMSO)3(H2O)] complex exhibits ultrafast photochemical aquation/rearrangement.

It is known that both cis,fac-[RuCl2(DMSO)3(H2O)] (1a) and trans,cis,cis-[RuCl2(DMSO)2(H2O)2] (2a) complexes, which are formed on the dissolution of trans and cis-isomers of [RuCl2(DMSO)4] in water, demonstrate light-induced anticancer activity. The first stage of 1a photochemistry is its transformation to 2a occurring with a rather high quantum yield, 0.64 ± 0.17. The mechanism of the 1a → 2a phototransformation was studied by means of nanosecond laser flash photolysis and ultrafast pump-probe spectroscopy. The reaction occurs in the picosecond time range via the formation and decay of two successive intermediates interpreted as Ru(ii) complexes with different sets of ligands. A tentative mechanism of phototransformation is proposed.

Mechanistic Aspects of Photoinduced Rearrangement of 2,3-Diarylcyclopentenone Bearing Benzene and Oxazole Moieties.

Photoinduced rearrangement of diarylethenes to naphthalenes or isoelectronic benzoannulated heterocycles is a novel reaction in preparative organic photochemistry. Recently it was shown that unsymmetrical diarylethenes containing benzene and oxazole derivatives efficiently undergo this transformation leading to amide derivatives of naphthalene. Mechanistic study of skeletal rearrangement for a typical representative of these compounds, namely 3-(5-methyl-2-phenyl-1,3-oxazol-4-yl)-2-phenylcyclopent-2-en-1-one, was performed by stationary and laser flash photolysis as well as density functional theory (DFT) calculations. The mechanism of the rearrangement was found to comprise several thermal stages. Both singlet and triplet states of the initial compound can be transformed to the reaction product, which results in the dependence of the quantum yield vs concentration of dissolved oxygen. Three reactive intermediates were registered in the laser flash photolysis experiment; the predicted structures were in accordance with DFT calculations of the electronic absorption spectra. In addition to the previously proposed mechanism of skeletal rearrangement based on a sigmatropic shift of hydrogen, two new parallel pathways based on formation of a carbanion/carbocation were determined.

Primary photophysical and photochemical processes for hexachloroosmate(iv) in aqueous solution.

The photoaquation of the OsIVCl62- complex was studied by means of stationary photolysis, nanosecond laser flash photolysis and ultrafast kinetic spectroscopy. The OsIVCl5(OH)2- complex was found to be the only reaction product. The quantum yield of photoaquation is rather low and wavelength-dependent. No impact of redox processes on photoaquation was revealed. The total characteristic lifetime of the process is about 80 ps. Three intermediates were recorded in the femto- and picosecond time domains and assigned to different Os(iv) species. The nature of intermediates and possible mechanisms of photoaquation are discussed.

Photosensitized Degradation of Amitriptyline and Its Active Metabolite Nortriptyline in Aqueous Fulvic Acid Solution.

Amitriptyline is a frequently prescribed tricyclic antidepressant. Although amitriptyline and its active metabolite, nortriptyline, have been widely detected in natural waters, their environmental fate due to photodegradation is poorly understood. Here we describe a study conducted to investigate the photodegradation of amitriptyline and its active metabolite under simulated sunlight. Neither amitriptyline nor nortriptyline underwent direct photodegradation, but rapid photosensitized degradation did occur in fulvic acid (FA) solutions. The photodegradation of amitriptyline and nortriptyline followed pseudo-first-order kinetics with rate constants 0.24 and 0.16 h, respectively, at pH 8.0 in air-saturated FA solutions. The photodegradation of the substrates increased markedly with pH. The deprotonation of amitriptyline and nortriptyline facilitated the availability of nonbonding electrons on nitrogen (N-electrons). The excited triplet state of FA (FA*) was verified as the main reactive species responsible for the photosensitized degradation. An electron transfer mechanism for the interaction between substrates and FA* was proposed on the basis of a series of quenching experiments, kinetic model and photoproducts determination. Demethylation at the α-carbon of amine and hydroxylation were two primary photochemical processes initiated by the electron transfer reaction in the air-saturated FA solution; these were followed by generation of demethyl amine and mono-hydroxylation isomers. Our results suggest that indirect photodegradation is an important elimination process for amitriptyline and its active metabolite in natural waters.

Photochemical transformation of an iron(III)-arsenite complex in acidic aqueous solution.

Surface complexation between arsenious acid anions (As(III)) and ferric (hydr)oxides in water is important for the transformation and transfer of inorganic arsenic species. The mechanisms of formation and the photochemistry of dissolved Fe(III)-As(III) complexes in acidic aqueous solution are still unclear. Here, the photooxidation of As(III) in the presence of Fe(III) ions in acidic media has been investigated by laser flash and steady-state photolysis. At low arsenite concentrations (<1 mM), As(III) is oxidized by the ˙OH radical generated by photolysis of the FeOH(2+) complex. At higher arsenite concentrations (>10 mM), photoactive Fe(III)-As(III) complexes are formed (ϕ≈ 0.012). At all arsenite concentrations, a white FeAsO4 colloid is formed during As(III) photolysis in the presence of Fe(III) ions. Solid Fe(III)-As(III) complexes have been prepared and characterized, and the photochemical transformation of As(III) into As(V) in solid Fe(III)-As(III) complexes has been confirmed. These findings are important for a better understanding of the evolution of As(III) species under environmental conditions and should provide guidance for detoxification of As(III)-polluted water systems.

Experimental determination and QSAR analysis of the rate constants for SO5•- reactions with aromatic micropollutants in water.

S(IV)-based systems used for advanced oxidation processes (AOPs) have been constructed for the degradation of organic contaminants via oxysulfur radicals, including SO3•-, SO4•-, and SO5•-. Although SO5•- is proposed as an active species in AOPs processes, research on the reactivity of SO5•- has remained unclear. In this work, 53 target aromatic micropollutants (AMPs), including 13 phenols, 27 amines, and 13 PPCPs were selected to determine the second-order reaction rate constants for SO5•- using the competitive kinetics method, in which the [Formula: see text] values, observed at pH 4 ranged from (2.44 ± 0.00) × 105 M-1 s-1 to (4.41 ± 0.28) × 107 M-1 s-1. Quantitative structure-activity relationship (QSAR) models for the oxidation of AMPs by SO5•- were developed based on 40 [Formula: see text] values of amines and phenols, and their molecular descriptors, using the stepwise multiple linear regression method. This comprehensive model exhibited the excellent goodness-of-fit (Radj2 = 0.802), robustness (QLOO2 = 0.749), and predictability (Qext2 = 0.656), and the one-electron oxidation potential (Eox), energy of the highest occupied molecular orbital energy (EHOMO), and most positive net atomic charge on the carbon atoms (qC+) were considered the most influential descriptors for the comprehensive model, indicating that SO5•- oxidizes pollutants via single electron transfer reaction and exhibits a strong oxidation capacity, especially for pollutants containing electron-donating groups. Moreover, the [Formula: see text] values of 13 PPCPs were predicted using this comprehensive model, which suggested the practical application significance of the QSAR model. This study emphasizes the direct oxidation capacity of SO5•-, which is important to evaluate and simulate AOPs based on S(IV).

Laser flash photolysis and quantum chemical studies of UV degradation of pharmaceutical drug chloramphenicol: Short-lived intermediates, quantum yields and mechanism of photolysis.

Using methods of time-resolved and stationary photolysis, HPLC-MS and quantum-chemical calculations by the DFT method, the mechanism of direct UV photolysis of the antibiotic chloramphenicol (CAP) was established. For the first time, short-lived intermediates formed during photolysis were detected. The primary photoprocess is the cleavage of the ß-C-C bond relative to the aromatic system with the formation of 4-nitrobenzylalcohol radical and residual aliphatic radical. The first radical in deoxygenated solutions predominantly transforms into para-nitrobenzaldehyde and its secondary photolysis products. In the presence of oxygen, the aromatic radical and para-nitrobenzaldehyde are transformed into para-nitrosobenzoic and para-nitrobenzoic acids as a result of reaction with reactive oxygen species (ROS). Formation of ROS is provoked by reactions of aliphatic radical with dissolved oxygen, so this radical is very important for CAP degradation. The quantum yield of direct photolysis of CAP is ∼3% and does not depend on the presence of dissolved oxygen and on the change of the excitation wavelength in the range of 254-308 nm. Obtained data are important for further understanding of the transformation pathways of CAP and similar PPCP in natural and wastewaters under the action of sunlight and artificial UV radiation.

Laser flash photolysis study of photocatalytic properties of pillared interlayered clays and Fe,Al-silica mesoporous catalysts.

Laser flash photolysis was applied to determine the primary photochemical processes over iron-containing clay (montmorillonite KSF), pillared interlayered clays (PILCs) and mesoporous mesophase iron silicate materials (MMMs). For KSF, the homogeneous photochemical reaction of Fe(III) leached from the clay material resulted in the formation of OH radicals, which were monitored by means of their reaction with methyl viologen dication (MV(2+)). For PILCs and MMMs, no leaching of Fe(III) to the solution nor hydroxyl radical formation were observed. Nevertheless, these catalysts were found to exhibit a sufficient effect on phenol photoionization. The increase in quantum yields of PhO radicals is caused by the effect of PILCs and MMMs and is explained by heterogeneous processes on the surface of catalyst particles.

A mechanistic study of the photodegradation of herbicide 2,4,5-trichlorophenoxyacetic acid in aqueous solution.

Photodegradation of herbicide 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in aqueous solution was investigated by stationary (254 nm) and nanosecond laser (266 nm) flash photolysis techniques. It was shown that in the primary photochemical step both photoionization (which generates a hydrated electron-radical cation pair) and heterolytic cleavage of a C-Cl bond takes place. The major products of substitution of one of the chlorine atoms in the 2-, 4- or 5-position by a hydroxyl group as well as the products of hydroxylation of the benzene ring in 3- and 6-positions were identified by HPLC and LC-MS methods. The complexation of 2,4,5-T with ß- and γ-cyclodextrins (ß(γ)CD) was investigated. The influence of such complexation on the quantum yield of herbicide photolysis and on the ratio of photodegradation products was determined.

Interaction between graphene oxide and acetaminophen in water under simulated sunlight: Implications for environmental photochemistry of PPCPs.

In recent years, graphene oxide (GO) as a new carbon material has been widely investigated as adsorbent and catalyst. However, effects of GO on the micro-pollutants such as pharmaceuticals and personal care products (PPCPs) under sunlight remains unclear. In this study, the degradation of PPCPs in a simulated sunlight-GO photocatalytic system was systematically investigated. Specifically, GO rapidly degrade 95% of acetaminophen (APAP) within 10 min under simulated sunlight irradiation (λ ≥ 350 nm). The influencing factors such as APAP concentration, pH, GO dosage, water matrixes (Cl-, NO3-, HCO3-, SO42-, Ca2+, Fe3+and fulvic acid) were investigated. At a GO dosage of 100 mg L-1 and an initial pH of 7, the APAP (5 µM) photodegradation kinetic constant kobs was calculated to be 0.4547 min-1. In practical applications, the GO photocatalysis system still degrade over 90% APAP within 60 min in real surface water. The electron spin resonance and radical scavenging experiments revealed that the dominated active species for degrading APAP was photogenerated holes (h+), while other mechanisms (1O2 and O2•-/HO2•) played a minor role. Furthermore, the photochemical transformation of some other typical PPCPs were comparatively studied to reveal the relationship between degradation kinetics and molecular structure. Based on descriptive variables including molar refractive index parameter, octanol-water partition coefficient, dissociation constant and dipole moment, a quantitative structural-activity relationship (QSAR) model for predicting pseudo-first-order rate constants was established with a high significance (R2 = 0.996, p < 0.05). This study helps to understand the interaction between GO and PPCPs and its effects on the photochemical transformation of PPCPs in water.

Direct UV photodegradation of nalidixic acid in aqueous solutions: A mechanistic study.

Mechanism of direct UV photolysis of nalidixic acid (NA), a model quinolone antibiotic, was revealed using a combination of steady-state photolysis coupled with high resolution LC-MS and DFT quantum-chemical calculations. Both quantum yields of photodegradation and detailed identification of final products were performed for the first time for two main forms of NA: neutral and anionic. The quantum yield of NA photodegradation is 0.024 and 0.0032 for the neutral and anionic forms in the presence of dissolved oxygen and 0.016/0.0032 in deoxygenated solutions, respectively. The main process is photoionization with the formation of a cation radical, which undergoes transformation into three different neutral radicals and further into final photoproducts. It is shown that the triplet state does not play a role in the photolysis of this compound. The main products of photolysis are the products of the loss of carboxyl, methyl and ethyl groups in the NA molecule, as well as the dehydrogenation of the ethyl group. The results obtained may be important for understanding the fate of pyridine herbicides in the processes of disinfection by UV and in natural waters under the action of sunlight.