Photochemical Behavior Research Articles

Algae mediated photodegradation of fluroquinolone antibiotic: Ofloxacin

Algae mediated photodegradation of fluroquinolone antibiotic: Ofloxacin

New insight into catechol photochemistry: the role of different monomer and dimer configurations in radiation-less decay of the S1 electronic excited state.

The equilibrium geometries of the ground and first electronic excited states as well as the radiation-less deactivation channels of catechol in its monomer and dimer configurations were investigated using the standard linear-response and the spin-flipped TDDFT, multireference CASSCF as well as the similarity transformed equation-of-motion coupled cluster built with the domain-based local pair natural orbitals (DLPNO-STEOM-CCSD) methods. For the monomer, it was found that there is a new conical intersection geometry that can explain why catechol exhibits different photochemical behavior. This deactivation pathway involves almost simultaneously, an excited state intramolecular proton transfer between the two O atoms and an O-H bond breaks at the proton that is not between the two O atoms. From an energy balance point of view, these geometries are not associated with high potential barriers, so radiation-less relaxation can be achieved through these geometries. For the cyclohexane solvent, the lowest CI geometry shows an energy gap of about 4 kcal mol-1 lower than that found for acetonitrile, making the relaxation even more easier. In the case of catechol dimer structures, several so-called dimer-type CI geometries were found where both monomers exhibit substantial geometric distortions together with the formation of a weaker C-C bond between the two catechol monomers. These CI geometries are energetically more favorable and, in the case of aggregation processes, more likely to decay the excited states of the catechol through these radiation-less deactivation channels than those found for the monomer.

A study of the photochemical behaviour and relaxation mechanisms of anti–syn isomerisation around quinazolinone –N–NCreated by potrace 1.16, written by Peter Selinger 2001-2019]]> bonds†

High-resolution NMR experiments revealed that differently substituted quinazolinone-based Schiff bases undergo anti to syn isomerisation on exposure to ultraviolet light in DMSO solution. The degree anti to syn conversion varied significantly upon substitution (between 5% and 100%) and also showed two noteworthy features: that relaxation back to the anti-form goes far faster (by at least 3 orders of magnitude) when the C6 rings B and C have ortho-OH substituents, and that relaxation can also be significantly sped up by addition of acid. Two possible mechanisms explaining the differences in relaxation process have been proposed: (I) the interaction of the azomethine hydrogen with the carbonyl oxygen results in slower reversion to the anti-form and/or (II) suppression of conjugation of the N3 lone pair with the NCH double bond by protonation and/or internal H-bonding. Both of these mechanisms have been analysed theoretically.

Theoretical regulation of ESIPT behavior by varying the π-expansion of proton acceptor for substituted hydroxyl fluorenes

Theoretical regulation of ESIPT behavior by varying the π-expansion of proton acceptor for substituted hydroxyl fluorenes

Polyploidy promotes divergent evolution across the leaf economics spectrum and plant edaphic niche in the Dianthus broteri complex

Abstract The evolution of the leaf economics spectrum (LES) is known to be constrained by genetic relatedness but also promoted at small geographical and phylogenetic scales. In those cases, we hypothesized that polyploidy would play a prominent role as an outstanding source of functional divergence and adaptive potential. We registered leaf‐level nutrient, water‐ and light‐economy‐related traits from the LES as well as edaphic properties in the four cytotypes of the autopolyploid Dianthus broteri complex (2×, 4×, 6× and 12×). We analysed the effect of ploidy level on the integration of the LES network, checked if concerted evolution occurred between LES and soil niche and tested the influence of phylogeny on the variables. Alternative evolutionary models for both sets of traits were compared. We found higher divergence of polyploids (especially 6× and 12×) compared to diploids in the LES and soil niche, but these traits are not coevolving. 6× and 12× showed opposite ecological strategies regarding resource use and higher uncoupling of the LES network. Early divergence of traits prevailed in both LES and edaphic niche (supported by better fitted evolutionary models with one optimum per cytotype), but post‐polyploidization processes played an important role for the photochemical behaviour. Synthesis. Our results indicated shifts in ecological strategies across Dianthus broteri cytotypes and suggested a powerful role of polyploidy in overcoming constraints for the evolution of plant functional traits.

Photo-electrochemical enhanced mechanism enables a fast-charging and high-energy aqueous Al/MnO2 battery

Photo-electrochemical enhanced mechanism enables a fast-charging and high-energy aqueous Al/MnO2 battery

The transformation of Benzophenone-3 in natural waters and AOPs: The roles of reactive oxygen species and potential environmental risks of products

The transformation of Benzophenone-3 in natural waters and AOPs: The roles of reactive oxygen species and potential environmental risks of products

Tuning C-Phycocyanin Photoactivity via pH-Mediated Assembly-Disassembly.

Environment-triggered protein conformational changes have garnered wide interest in both fundamental research, for deciphering in vivo acclimatory responses, and practical applications, for designing stimuli-responsive probes. Here, we propose a protein-chromophore regulatory mechanism that allows for manipulation of C-phycocyanin (C-PC) from Spirulina platensis by environmental pH and UV irradiation. Using small-angle X-ray scattering, a pH-mediated C-PC assembly-disassembly pathway, from monomers to nonamers, was unraveled. Such flexible protein matrices impart tunability to the embedded tetrapyrroles, whose photochemical behaviors were found to be modulated by protein assembly states. UV irradiation on C-PC triggers pH-dependent singlet oxygen (1O2) generation and conformational changes. Intermolecular photo-crosslinking occurs at pH 5.0 via dityrosine species, which bridges solution-based C-PC oligomers into unprecedented dodecamers and 24-mers. These supramolecular assemblies impart C-PC at pH 5.0, which significantly enhanced 1O2 yield, fluorescence, and photostability relative to those at other pH values, a finding that makes C-PC appealing for tumor-targeted photodynamic therapy.

Electrochemical Investigation and Molecular Docking Techniques on the Interaction of Acridinedione Dyes with Water-Soluble Nonfluorophoric Simple Amino Acids.

Electrochemical studies of resorcinol-based acridinedione (AD) dyes with nonfluorophoric simple amino acids, glycine, alanine, and valine, were carried out in water. AD probes are classified into photoinduced electron transfer (PET) and non-PET-based dyes, wherein the electrochemical properties and photophysical and photochemical behavior vary significantly based on the nature of substituent groups and the nature of the solute. The oxidation potential of PET dye (ADR1) to that of non-PET-based dye (ADR2) differs significantly such that the addition of amino acids results in a shift of the oxidation peak to a less positive potential and the reduction peak to a lesser negative potential. The extent of shift of oxidation and reduction potential in PET dye is more pronounced than that of non-PET dye on the addition of valine rather than glycine. The variation in the shift is attributed to the presence of an electron-donating moiety (OCH3) group in the ninth position of ADR1 dye. Consequently, the quenching of fluorescence is observed in ADR2 with non fluorophoric amino acids that are authenticated by the shift of the anodic and cathodic peaks toward a lesser positive potential. Molecular docking (MD) studies of PET and non-PET dye with amino acids portray that neither hydrophobic interactions nor electrostatic or weak interactions such as van der Waals and pi–pi interactions govern the electrochemical nature of dye on the addition of amino acids. Furthermore, the formation of a conventional hydrogen bond between dye and amino acid is established from MD studies. The existence of dye–water–amino acid competitive hydrogen-bonding interactions is presumably well-oriented throughout the aqueous phase as observed through photophysical studies which support our electrochemical investigation.

Halide salts induced the photodegradation of a fat-burning compound 2, 4-dinitrophenol by iron-montmorillonite

Halide salts induced the photodegradation of a fat-burning compound 2, 4-dinitrophenol by iron-montmorillonite

The Role of Graphene Monolayers in Enhancing the Yield of Bacteriorhodopsin Photostates for Optical Memory Applications

Bacteriorhodopsin (bR) is a photoactive protein that has gained increasing importance as a tool for optical memory storage due to its remarkable photochemical and thermal stability. The two stable photostates (bR and Q) obtained during the bR photocycle are appropriate to designate the binary bit 0 and 1, respectively. Such devices, however, have limited success due to a low quantum yield of the Q state. Many studies have used genetic and chemical modification as optimization strategies to increase the yield of the Q state. Nonetheless, this compromises the overall photochemical stability of bR. This paper introduces a unique way of stabilizing the conformations of bacteriorhodopsin and, thereby, the bR and Q photostates through adsorption onto graphene. All-atom molecular dynamics (MD) simulations with NAMD and CHARMM force fields have been used here to understand the interactive events at the interface of the retinal chromophore within bR and a single-layer graphene sheet. Based on the stable RMSD (~4.5 Å), secondary structure, interactive van der Waals energies (~3000 kcal/mol) and electrostatic energies (~2000 kcal/mol), it is found that the adsorption of bR onto graphene can stabilize its photochemical behavior. Furthermore, the optimal adsorption distance for bR is found to be ~4.25 Å from the surface of graphene, which is regulated by a number of interfacial water molecules and their hydrogen bonds. The conformations of the key amino acids around the retinal chromophore that are responsible for the proton transport are also found to be dependent on the adsorption of bR onto graphene. The quantity and lifetime of the salt bridges also indicate that more salt bridges were formed in the absence of graphene, whereas more were broken in the presence of it due to conformational changes. Finally, the analysis on the retinal dihedrals (C11 = C12-C13 = C14, C12-C13 = C14-C15, C13 = C14-C15 = NZ and C14-C15 = NZ-CE) show that bacteriorhodopsin in the presence of graphene exhibits increased stability and larger dihedral energy values.

Photochemistry of Heteroleptic 1,4,5,8-Tetraazaphenanthrene- and Bi-1,2,3-triazolyl-Containing Ruthenium(II) Complexes.

Diimine metal complexes have significant relevance in the development of photodynamic therapy (PDT) and photoactivated chemotherapy (PACT) applications. In particular, complexes of the TAP ligand (1,4,5,8-tetraazaphenanthrene) are known to lead to photoinduced oxidation of DNA, while TAP- and triazole-based complexes are also known to undergo photochemical ligand release processes relevant to PACT. The photophysical and photochemical properties of heteroleptic complexes [Ru(TAP)n(btz)3-n]2+ (btz = 1,1'-dibenzyl-4,4'-bi-1,2,3-triazolyl, n = 1 (1), 2 (2)) have been explored. Upon irradiation in acetonitrile, 1 displays analogous photochemistry to that previously observed for [Ru(bpy)(btz)2]2+ (bpy = 2,2'-bipyridyl) and generates trans-[Ru(TAP)(btz)(NCMe)2]2+ (5), which has been crystallographically characterized, with the observation of the ligand-loss intermediate trans-[Ru(TAP)(κ2-btz)(κ1-btz)(NCMe)]2+ (4). Complex 2 displays more complicated photochemical behavior with not only preferential photorelease of btz to form cis-[Ru(TAP)2(NCMe)2]2+ (6) but also competitive photorelease of TAP to form 5. Free TAP is then taken up by 6 to form [Ru(TAP)3]2+ (3) with the proportion of 5 and 3 observed to progressively increase during prolonged photolysis. Data suggest a complex set of reversible photochemical ligand scrambling processes in which 2 and 3 are interconverted. Computational DFT calculations have enabled optimization of geometries of the pro-trans 3MCcis states with repelled btz or TAP ligands crucial for the formation of 5 from 1 and 2, respectively, lending weight to recent evidence that such 3MCcis states play an important mechanistic role in the rich photoreactivity of Ru(II) diimine complexes.

Photochemical characterization of paddy water during rice cultivation: Formation of reactive intermediates for As(III) oxidation

Photochemical characterization of paddy water during rice cultivation: Formation of reactive intermediates for As(III) oxidation

Progress in ice/snow environmental photochemical behavior of organic pollutants

Progress in ice/snow environmental photochemical behavior of organic pollutants

Photochemical Behavior of Microbial Extracellular Polymeric Substances in the Aquatic Environment.

Microbially derived extracellular polymeric substances (EPSs) occupy a large portion of dissolved organic matter (DOM) in surface waters, but the understanding of the photochemical behaviors of EPS is still very limited. In this study, the photochemical characteristics of EPS from different microbial sources (Shewanella oneidensis, Escherichia coli, and sewage sludge flocs) were investigated in terms of the production of reactive species (RS), such as triplet intermediates (3EPS*), hydroxyl radicals (•OH), and singlet oxygen (1O2). The steady-state concentrations of •OH, 3EPS*, and 1O2 varied in the ranges of 2.55-8.73 × 10-17, 3.01-4.56 × 10-15, and 2.08-2.66 × 10-13 M, respectively, which were within the range reported for DOM from other sources. The steady-state concentrations of RS varied among different EPS isolates due to the diversity of their composition. A strong photochemical degradation of the protein-like components in EPS isolates was identified by excitation emission matrix fluorescence with parallel factor analysis, but relatively, humic-like components remained stable. Fourier-transform ion cyclotron resonance mass spectrometry further revealed that the aliphatic portion of EPS was resistant to irradiation, while other portions with lower H/C ratios and higher O/C ratios were more susceptible to photolysis, leading to the phototransformation of EPS to higher saturation and lower aromaticity. With the phototransformation of EPS, the RS derived from EPS could effectively promote the degradation of antibiotic tetracycline. The findings of this study provide new insights into the photoinduced self-evolution of EPS and the interrelated photochemical fate of contaminants in the aquatic environment.

Photochemical Properties of a Mononuclear Mn(I) Triscarbonyl Complex in Water: An Insight into Different Oxidation States

Abstract This study reports the photochemical behavior of fac‐[Mn(phen)CO3(4MeImH)]+ in neutral aqueous solution. The complex presents two 4MeImH linkage isomers, adjacent (A) and remote (R), which coexist in solution although with marked stability differences. In water, the steric effect converts A into an aqua‐complex while R remains stable. Photolysis of the mixture followed by UV‐vis, infrared (IR), nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), and cyclic voltammetry showed changes in the coordination sphere and oxidation state of each Mn center. Upon light irradiation, the mixture behaves as an antenna system to absorb light, producing the {Mn(II)(phen.−)}+ moieties and releasing CO, which provides open sites for water coordination. Upon successive irradiation, the EPR spectra showed an increasing signal at g=2.0 corresponding to Mn(II) centers, a phenanthroline anion (2.0046) that vanishes at longer irradiation time, and an increasing component (gx∼9.85 and gy∼3.9) corresponding to Mn(IV). This makes the spectroscopic properties, excited state character, and dynamics of fac‐[Mn(phen)(CO)3(4MeImH)]+ significantly different from those of all manganese complexes studied so far.

Photodegradation of microplastics mediated by different types of soil: The effect of soil components

Photodegradation of microplastics mediated by different types of soil: The effect of soil components

A novel transformation pathway of p-arsanilic acid in water by colloid ferric hydroxide under UVA light.

Iron species that occur in natural surface water could affect the photochemical behavior of pollutants. Complexation between iron species and polycarboxylate or heavy metals has been widely reported, where the ligands could be oxidized via ligand-to-metal charge transfer (LMCT) by light inducement. Such complexation and photochemical reactions might also occur for low valance metal-containing organic compounds, which is worthy of investigation. This work studied the phototransformation of p-arsanilic acid (ASA), an organic arsenic compound that is widely used as a feed additive in the poultry industry, by colloidal ferric hydroxide (CFH) using black light lamps (λ = 365 nm) as the light source. The results revealed the contribution to ASA transformation at circumneutral conditions by CFH through an LMCT process, which is the same as that for As(III). The complexation between ASA and CFH was investigated using UV-vis spectroscopy. The estimated equilibrium constant for the CFH-ASA complex was log Kf271 = 4.22. The analysis of the photoproducts found the generation of both inorganic and organic arsenic. Our findings confirmed the similarities in the photochemical mechanisms of ASA and As(III) in the presence of CFH. The results help in further understanding the fate of organoarsenicals in the surface water environment.

Infrared absorption spectra of phenoxide anions isolated in solid argon

Abstract Phenoxide anions (PhO−) and phenoxy radicals (PhO) were generated by the electron bombardment of a phenol/argon sample during matrix deposition. Further irradiation of the matrix sample at 365 nm led to the detachment of the electron from PhO− and afforded its neutral counterpart PhO in solid Ar. In a separate experiment, the photolysis of a phenol/Ar matrix at 160 nm mainly afforded PhO, phenyl (Ph) radicals, and various open‐chain ketenes, but no PhO−. The Infrared (IR) lines of PhO− were assigned on the basis of the observed photochemical behaviors and the prediction of the vibrational wavenumbers with the corresponding IR intensities predicted by the B3LYP/aug‐cc‐pVTZ theory.

Interfacial photoreactions of Cr(VI) and oxalate on lepidocrocite surface under oxic and acidic conditions: Reaction mechanism and potential implications for contaminant degradation in surface waters

Interfacial photoreactions of Cr(VI) and oxalate on lepidocrocite surface under oxic and acidic conditions: Reaction mechanism and potential implications for contaminant degradation in surface waters