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The widespread distribution of antibiotics in natural waters is a great threat to human health. Photocatalytic degradation is an environmentally friendly technology to remediate antibiotic-polluted waters, driven by endless solar energy. Herein, a Z-scheme Ag 2 S-Ag-In 2 O 3 heterostructure photocatalyst is prepared to remove antibiotics under environmental conditions. Under natural sunlight (light intensity: ∼78 mW/cm 2 ) irradiation, the optimal Ag 2 S-Ag-In 2 O 3 (10-ASAIO) exhibits considerable performance for decomposing diverse antibiotics, including norfloxacin (NOR), tetracycline hydrochloride, sulfisoxazole, ciprofloxacin, chlortetracycline hydrochloride, and ofloxacin. The NOR photodegradation rate constant of 10-ASAIO reaches 0.025 min -1 , which is 12.50, 5.00, and 6.25 times higher than that of In 2 O 3 (0.002 min -1 ), Ag-In 2 O 3 (0.005 min -1 ), and Ag 2 S-In 2 O 3 (0.004 min -1 ), respectively. This performance of the 10-ASAIO photocatalyst for decomposing NOR under natural sunlight exceeds most of the previously reported photocatalysts under a xenon lamp. Particularly, due to the intermittency of natural sunlight, a light-emitting diode (LED) lamp (light intensity: 5.1 mW/cm 2 ) is also used as a light source, and 72.20% of NOR can be degraded with irradiation for 12 h. The effects of many water characteristics (water bodies, coexisting inorganic anions, pH, and humic acid) on the degradation performance of 10-ASAIO have been investigated, which exhibits stable degradation efficiency in variable aquatic environments. A 10-ASAIO catalyst-coated frosted glass sheet is fabricated to settle the problem of recovery of powder photocatalysts, and the immobilized catalyst shows outstanding activity and stability to decompose NOR. The photocatalytic mechanism and pathway of degrading NOR over 10-ASAIO have also been systemically investigated and proposed. The ecotoxicity (phytotoxicity and biotoxicity) of the 10-ASAIO photocatalyst and treated NOR solution have been tested by their toxic effects on cabbage seeds and Staphylococcus aureus ( S. aureus ). This work provides a feasible photocatalytic system for environmental pollutant remediation under natural sunlight or an LED lamp.

Antibiotic residues have been found in several aquatic ecosystems as a result of the widespread use of antibiotics in recent years, which poses a major risk to both human health and the environment. At present, photocatalytic degradation is the most effective and environmentally friendly method. Titanium silicon molecular sieve (TS-1) has been widely used as an industrial catalyst, but its photocatalytic application in wastewater treatment is limited due to its small pores and few active sites. In this paper, we report a method for preparing multistage porous TS-1 with a high specific surface area by alkali treatment. In the photocatalytic removal of CIP (ciprofloxacin) antibiotic wastewater experiments, the alkali-treated catalyst showed better performance in terms of interfacial charge transfer efficiency, which was 2.3 times higher than that of TS-1 synthesized by the conventional method, and it was found to maintain better catalytic performance in the actual water source. In addition, this research studied the effects of solution pH, contaminant concentration, and catalyst dosage on CIP degradation, while liquid chromatography-mass spectrometry (LC-MS) was used to identify intermediates in the degradation process and infer possible degradation pathways and the toxicity of CIP, and its degradation product was also analyzed using ECOSAR 2.2 software, and most of the intermediates were found to be nontoxic and nonharmful. Finally, a 3:5:1 artificial neural network model was established based on the experiments, and the relative importance of the influence of experimental conditions on the degradation rate was determined. The above results confirmed the feasibility and applicability of photocatalytic treatment of wastewater containing antibiotics using visible light excitation alkali post-treatment TS-1, which provided technical support and a theoretical basis for the photocatalytic treatment of wastewater containing antibiotics.

Water-soluble phthalocyanine (Pc) derivatives have been regarded as potential G-quadruplex (G4) nucleic acid-targeting ligands for anticancer therapy and have been extensively studied as effective photosensitizers for photodynamic therapy (PDT). Understanding how photosensitizers interact with nucleic acids and the subsequent photolytic reactions is essential for deciphering the initial steps of PDT, thereby aiding in the development of new photosensitizing agents. In this study, we found that red-light irradiation of a mixture of a Zn(II) Pc derivative and an all-parallel G4 DNA leads to catalytic and selective photodegradation of the DNA by reactive oxygen species (ROS) generated from the Zn(II) Pc derivative bound to DNA through a reaction mechanism similar to that of an enzyme reaction. This finding provides a novel insight into the molecular design of a photosensitizer to enhance its PDT efficacy., (© 2024 Wiley-VCH GmbH.)

UV photodissociation of α-alanine was studied by parahydrogen matrix isolation infrared spectroscopy. The temporal behavior of Fourier transform infrared spectra revealed that UV irradiation at 213 nm yielded the HOCO radical as a direct photoproduct from the S 2 excited state. The concentration of HOCO quickly approached a steady state due to secondary photodissociation of HOCO to produce CO 2 + H or CO + OH. On the other hand, no photoproducts were detected by S 1 excitation at 266 nm. Irradiation of fully deuterated α-alanine at 213 nm yielded ∼2 times more cis -DOCO radicals than the lower energy isomer trans -DOCO, indicating that the conformation of the hydroxyl group is fairly well-preserved upon photodissociation of α-alanine. The present study suggests that HOCO may be a good tracer species in the search for amino acids in interstellar space.

In this report, chitosan/zinc oxide (CS/ZnO) nanocomposite was synthesized using Sida acuta and assessed their antibacterial and photocatalytic properties. The formation of CS/ZnO nanocomposite was preliminary confirmed by colour change and UV-visible spectroscopy. The crystalline peaks related to CS and ZnO in CS/ZnO nanocomposite were demonstrated by XRD. Morphological analysis through FE-SEM and TEM showed a rod like appearance for ZnO NPs and agglomerated grains with rod shaped morphology was observed for the CS/ZnO nanocomposite. The peaks around 400-800 cm -1 in the IR spectrum of nanocomposite indicated the vibrations of metal-oxygen (ZnO), whereas bands at 1659 cm -1 and 1546 cm -1 indicated the presence of amine groups, which confirms the CS in the synthesized CS/ZnO nanocomposite. The CS/ZnO nanocomposite exhibited remarkable growth inhibition activity against B. subtilis and E. coli with 22 ± 0.3 and 16.5 ± 0.5 mm zone of inhibitions. In addition, CS/ZnO nanocomposite treated cotton fabrics also exhibited antibacterial activity against B. subtilis and E. coli. Furthermore, the ZnO NPs and nanocomposite showed time depended photodegradation activity and revealed 76% and 91% decomposition of CR under sunlight irradiation. In conclusion, our study revealed that the functionalization of biopolymer CS to the inorganic ZnO enhances the bio and catalytic properties., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The initial objective of our work was to synthesize a series of 2-amino-4H-pyran-3-carbonitriles to be tested for their antifungal activities against economically relevant phytopathogenic fungi. Fourteen compounds were prepared in up to 94% yield and shown percentages of Botrytis cinerea inhibition above 70%. Despite the promising biological results, we observed that stock solutions prepared for biological tests showed color changing when kept for a few days on the laboratory bench, under room conditions, illuminated by common LED daylight tubes (4500-6000 k). This prompted us to investigate the possible photo-induced degradation of our compounds. FT-IR ATR experiments evidenced variations in the expected bands for functional of -amino-4H-pyran-3-carbonitriles stored under LED daylight. Following, HPLC-UV analysis showed reductions in the intensity of chromatographic peaks of 2-amino-4H-pyran-3-carbonitriles, and but not for solutions kept in the dark. A solution of (E)-2-amino-8-(4-nitrobenzylidene)-4-(4-nitrophenyl)-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile underwent 84.4% of conversion after 72 h of exposure to continuous LED daylight in a BOD chamber, and the reaction product was isolated in 36% yield and characterized as (E)-7-cyano-5-(4-nitrobenzylidene)-8-(4-nitrophenyl)bicyclo[4.2.0]oct-1(6)-ene-7-carboxamide (7*). Despite freshly prepared solutions of 2-amino-4H-pyran-3-carbonitriles produced antifungal activities, these solutions lost biological activity when left on the bench for a week. Besides, compound 7* formed from photo-induced degradation of 7 also showed no antifungal activity. With this, we hope to bring two contributions: (1) production of cyclobutenes through photochemical reactions of 2-amino-4H-pyran-3-carbonitriles can be carried out through exposure to simple white LED daylight; (2) biological applications of such 2-amino-4H-pyran-3-carbonitriles may be impaired by their poor photostability., (© 2021. The Author(s), under exclusive licence to European Photochemistry Association, European Society for Photobiology.)

Cartap applied widely in agricultural crops and tea plants is readily degraded into nereistoxin, resulting in a longer residual period and higher exposure risk to humans. The photolysis kinetics of cartap and nereistoxin in water and tea beverages was firstly investigated to explore the effect and mechanism of pesticide residue removal. Cartap and nereistoxin could be effectively photolyzed by ultraviolet and their photolysis rate increased with light intensity increasing. The photolysis percentage of cartap and nereistoxin in different solutions under ultraviolet irradiation of 200 W mercury lamp reached 81.8%-100.0% within 6 h. Relative to water solution, the water-soluble components in tea had an inhibition effect on the photodegradation of cartap and nereistoxin. This research provided a reference for the development of effective methods for the removal of cartap and its metabolite in water and tea beverages., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

There is a current concern, among the scientific community, on the pollutants classified as "persistent organic pollutants (POPs)". Pharmaceuticals and personal care products (PPCPs) belong to this family of contaminants; therefore, it is necessary to find more efficient techniques able to achieve their removal from the environment. This study focuses on two different pharmaceuticals: carbamazepine and atenolol, chosen for their widespread use and their different chemical and medical properties. In this work, an organic dye, acetylated riboflavin, has been used in combination with visible light to achieve the photodegradation of these two POPs in <2 h. Moreover, photophysical experiments demonstrated the involvement of the singlet and triplet excited states of acetylated riboflavin and the generated singlet oxygen in the removal of these drugs. Besides, a detailed UFLC-MS-MS analysis of the photoproducts confirmed the oxidation of the drugs. Finally, a plausible mechanism has been postulated., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

This article reports the synthesis of a novel ternary Visible-Light-Driven (VLD) photocatalyst and antibacterial agent. The two-dimensional graphitic carbon nitride nanosheets (g-C 3 N 4 NSs) and 7% molybdenum doped zinc oxide nanoparticles (Mo doped ZnO NPs) were used for the synthesis of the 65% g-C 3 N 4 hybridized with 7% Mo doped ZnO novel ternary nanocomposite (Mo doped ZnO/g-C 3 N 4 ternary NC). The synthesis process, as well as the structures, morphologies, photocatalytic and antibacterial properties of the synthesized ternary NC and constituents, were investigated by using several spectroscopic and microscopic techniques. It was revealed through the Transmission Electron Microscopy (TEM) characterization of the synthesized NC that the Mo doped ZnO NPs were found uniformly embedded upon the well-stacked g-C 3 N 4 NSs. It was further discovered by the bandgap analysis that the light absorbance ability of the ternary NC exists in the visible region of the light spectrum. The photocatalytic degradation of the methylene blue (MB) by the use of novel ternary NC in an aqueous medium was analyzed while using Ultra Violet-Visible (UV-Visible) spectroscopy. Trapping experiments of active species during the photodegradation and Electron Spin Resonance (ESR) experiment revealed that the superoxide and hydroxyl radicals were the leading species liable for MB deterioration. The ternary NC exhibited superior photocatalytic performance as compared with binary doped or hybridized nanomaterials (NMs) and mono photocatalysts due to the facility of effective migration and separation of the charge carriers across the (Mo doped ZnO NPs)/g-C 3 N 4 NSs interface of the heterojunction. The increased generation of the reactive oxygen species (ROS), O 2- , and • OH radicals the photogenerated charge carriers within the Mo doped ZnO/g-C 3 N 4 NC were found responsible for its enhanced antibacterial performance., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The present work describes the synthesis of polyvinylpyrrolidone (PVP) assisted Fe-BiOI based Fe/Bi-povidone‑iodine (Fe/Bi-P-I) micro-flowers based composite and its photocatalytic and antibacterial applications. The Fe/Bi-P-I micro-flowers-based composite material was synthesized using a simple co-precipitation method. The prepared Fe/Bi-P-I micro-flowers-based composite materials were characterized using various characterization techniques and tested against photocatalytic degradation of rhodamine B (RhB) dye and antibacterial analysis. The PVP or povidone‑iodine provides more exposure of reactive sites and oxygen vacancies, which leads to a high separation rate of photoinduced charge carriers, and migration, thereby 100% of photodegradation efficiency at 1 mg/L initial concentration of RhB dye towards the synthesized P-Fe-BiOI based micro-flowers composite. Interestingly, Povidone-Iodine in Fe/Bi-P-I micro-flowers-based composite might be advantageous for antimicrobial activity against both gram-negative (E. coli), and gram-positive (S. aureus) bacterial strains. Therefore, the prepared Fe/Bi-P-I micro-flowers-based composite improved both photocatalytic degradation of organic pollutants as well as high antimicrobial activity. The method of synthesizing the Bi/Fe-P-I micro flower composite in the present study is novel, facile, and economically viable., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Photodegradation of the aqueous solutions of acetylsalicylic acid, in the absence (ASA) and the presence of excipients (ASE), is demonstrated by the photoluminescence (PL). A shift of the PL bands from 342 and 338 nm to 358 and 361-397 nm for ASA and ASE in solid state and as aqueous solutions was reported. By exposure of the solution of ASA 0.3 M to UV light, a decrease in the PL band intensity was highlighted. This behavior was revealed for ASA in the presence of phosphate buffer (PB) having the pH equal to 6.4, 7, and 8 or by the interaction with NaOH 0.3 M. A different behavior was reported in the case of ASE. In the presence of PB, an increase in the intensity of the PL band of ASE simultaneously with a change of the ratio between the intensities of the bands at 361-364 and 394-397 nm was highlighted. The differences between PL spectra of ASA and ASE have their origin in the presence of salicylic acid (SAL). The interaction of ASE with NaOH induces a shift of the PL band at 405-407 nm. Arguments for the reaction of ASA with NaOH are shown by Raman scattering and FTIR spectroscopy.

Photoactivatable protecting groups (PPGs) are useful for a broad range of applications ranging from biology to materials science. In chemical biology, induction of biological processes via photoactivation is a powerful strategy for achieving spatiotemporal control. The importance of cysteine, glutathione, and other bioactive thiols in regulating protein structure/activity and cell redox homeostasis makes modulation of thiol activity particularly useful. One major objective for enhancing the utility of photoactivatable protecting groups (PPGs) in living systems is creating PPGs with longer wavelength absorption maxima and efficient two-photon (TP) absorption. Toward these objectives, we developed a carboxyl- and dimethylamine-functionalized nitrodibenzofuran PPG scaffold (cDMA-NDBF) for thiol photoactivation, which has a bathochromic shift in the one-photon absorption maximum from λmax = 315 nm with the unfunctionalized NDBF scaffold to λmax = 445 nm. While cDMA-NDBF-protected thiols are stable in the presence of UV irradiation, they undergo efficient broad-spectrum TP photolysis at wavelengths as long as 900 nm. To demonstrate the wavelength orthogonality of cDMA-NDBF and NDBF photolysis in a biological setting, caged farnesyltransferase enzyme inhibitors (FTI) were prepared and selectively photoactivated in live cells using 850-900 nm TP light for cDMA-NDBF-FTI and 300 nm UV light for NDBF-FTI. These experiments represent the first demonstration of thiol photoactivation at wavelengths above 800 nm. Consequently, cDMA-NDBF-caged thiols should have broad applicability in a wide range of experiments in chemical biology and materials science.

In order to solve two issues of chlorine-resistant bacteria (CRB) and disinfection byproducts (DBPs) in tap water after the chlorine-containing treatment process, an innovative core-sheath nanostructured Cu/Cu 2 O-ZnO-Fe 3 O 4 was designed and synthesized. The fabrication mechanism of the materials was then systematically analyzed to determine the component and valence state. The properties of CRB inactivation together with trichloroacetic acid (TCAA) photodegradation by Cu/Cu 2 O-ZnO-Fe 3 O 4 were investigated in detail. It was found that Cu/Cu 2 O-ZnO-Fe 3 O 4 displayed excellent antibacterial activity with a relatively low cytotoxicity concentration due to its synergism of nanowire structure, ion release, and reactive oxygen species generation. Furthermore, the Cu/Cu 2 O-ZnO-Fe 3 O 4 nanocomposite also exhibited outstanding photocatalytic degradation activity on TCAA under simulated sunlight irradiation, which was verified to be dominated by the surface reaction through kinetic analysis. More interestingly, the cell growth rate of Cu/Cu 2 O-ZnO-Fe 3 O 4 was determined to be 50% and 10% higher than those of Cu/Cu 2 O and Cu/Cu 2 O-ZnO after 10 h incubation, respectively, manifesting a weaker cytotoxicity. Therefore, the designed Cu/Cu 2 O-ZnO-Fe 3 O 4 could be a promising agent for tap water treatment.

Recently, sunscreen-based drug photocages have been introduced to provide UV protection to photoactive drugs, thus increasing their photosafety. Here, combined experimental and theoretical studies performed on a photocage based on the commercial UVA filter avobenzone (AB) and on the photosensitizing non-steroidal anti-inflammatory drug ketoprofen (KP) are presented unveiling the photophysical processes responsible for the light-triggered release. Particular attention is paid to solvent stabilization of the drug and UV filter excited states, respectively, which leads to a switching between the triplet excited state energies of the AB and KP units. Most notably, we show that the stabilization of the AB triplet excited state in ethanol solution is the key requirement for an efficient photouncaging. By contrast, in apolar solvents, in particular hexane, KP has the lowest triplet excited state, hence acting as an energy acceptor quenching the AB triplet manifold, thus inhibiting the desired photoreaction.

Water decontamination still remains a major challenge to some developing countries not having centralized wastewater systems. Therefore, this study presents the optimization of photocatalytic degradation of Basic Blue 41 dye in an aqueous medium by an activated carbon (AC)-TiO 2 photocatalyst under UV irradiation. The mesoporous AC-TiO 2 synthesized by a sonication method was characterized by X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy for crystal phase identification and molecular bond structures, respectively. The efficiency of the AC-TiO 2 was evaluated as a function of three input variables viz. catalyst load (2-4 g), reaction time (15-45 min) and pH (6-9) by using Box-Behnken design (BBD) adapted from response surface methodology. Using color and turbidity removal as responses, a 17 run experiment matrix was generated by the BBD to investigate the interaction effects of the three aforementioned input factors. From the results, a reduced quadratic model was generated, which showed good predictability of results agreeable to the experimental data. The analysis of variance (ANOVA), signposted the selected models for color and turbidity, was highly significant ( p < 0.05) with coefficients of determination ( R 2 ) values of 0.972 and 0.988, respectively. The catalyst load was found as the most significant factor with a high antagonistic impact on the process, whereas the interactive effect of reaction time and pH affected the process positively. At optimal conditions of catalyst load (2.6 g), reaction time (45 min), and pH (6); the desirability of 96% was obtained by a numerical optimization approach representing turbidity removal of 93% and color of 96%.

Clinical tissue specimens are often unscreened, and preparation of tissue sections for analysis by mass spectrometry imaging (MSI) can cause aerosolization of particles potentially carrying an infectious load. We here present a decontamination approach based on ultraviolet-C (UV-C) light to inactivate clinically relevant pathogens such as herpesviridae, papovaviridae human immunodeficiency virus, or SARS-CoV-2, which may be present in human tissue samples while preserving the biodistributions of analytes within the tissue. High doses of UV-C required for high-level disinfection were found to cause oxidation and photodegradation of endogenous species. Lower UV-C doses maintaining inactivation of clinically relevant pathogens to a level of increased operator safety were found to be less destructive to the tissue metabolome and xenobiotics. These doses caused less alterations of the tissue metabolome and allowed elucidation of the biodistribution of the endogenous metabolites. Additionally, we were able to determine the spatially integrated abundances of the ATR inhibitor ceralasertib from decontaminated human biopsies using desorption electrospray ionization-MSI (DESI-MSI).

The risk of extensive exposure of the human epidermis to solar ultraviolet radiation is significantly increased nowadays. It not only induces skin aging and solar erythema but also increases the possibility of skin cancer. Therefore, a simply prepared, highly sensitive, and optically readable device for monitoring the solar ultraviolet radiation is highly desired for the skin health management. Because of the photoinitiated polymerization triggered by graphene-carbon nitride (g-C 3 N 4 ) under ultraviolet radiation, g-C 3 N 4 is homogeneously distributed in the hybrid hydrogels containing N -isopropylacrymide (NIPAM), poly(ethylene glycol) methyl ether methacrylate (OEGMA 300 ), and sodium alginate (SA). By further immersing the hybrid hydrogels into calcium chloride solution, hybrid alginate-Ca 2+ /P(NIPAM- co -OEGMA 300 )/g-C 3 N 4 interpenetrating polymeric network (IPN) hydrogels are obtained. Due to the homogeneous distribution of g-C 3 N 4 and the existence of thermoresponsive polymers, the hybrid IPN hydrogels present good adsorption capability and high degradation efficiency for methylene blue (MB) especially at high temperature under ultraviolet radiation. Based on this unique property, the bracelet monitoring skin health is prepared by simply immersing the hybrid IPN hydrogels into the MB solution and then wrapping it with PET foil. Because the immersion time for the top, middle, and bottom parts of the hybrid IPN hydrogels is gradually increased, their colors vary from light to dark blue. A longer time is required for the discoloration of the darker part under solar ultraviolet radiation. Thus, the bracelet can be used to conveniently monitor the dose of solar ultraviolet radiation by simply checking the discoloration in the bracelet under sunshine. Due to the facile preparation and low cost of the bracelet, it is a promising candidate for wearable devices for skin health management.

Gadusols are efficient nature UV sunscreens with antioxidant capacity. The kinetics of the quenching reactions of singlet oxygen O 2 ( 1 ∆ g ) by gadusol species was evaluated in aqueous solution as well as in the presence of direct charged micelles. Time-resolved phosphorescence detection of O 2 ( 1 ∆ g ) indicated that gadusolate, the main species under biological pH, is a more efficient quencher than the enol form with a rate constant of ca. 1.3 × 10 8  L mol -1  s -1 . The deactivation proceeds via a collisional mechanism with clear dominance of chemical pathways, according to the rates of gadusol and oxygen consumptions, and typical photooxidation quantum yields of ca. 7%. The relative contributions of the chemical and physical quenching steps were not affected by the presence of anionic or cationic micelles emulating simple pseudo-biological environments. The products of the photo-oxidative quenching support a type II mechanism initiated by the addition of O 2 ( 1 ∆ g ) to the C-C double bond of gadusolate. These results point to the relevance of considering the role of sacrifice antioxidant along with the UV-screening function for gadusol, particularly in the context of potential biotechnological applications of this natural molecule., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The photodegradation process of seven glucocorticoids (GCs), cortisone (CORT), hydrocortisone (HCORT), betamethasone (BETA), dexamethasone (DEXA), prednisone (PRED), prednisolone (PREDLO) and triamcinolone (TRIAM) was studied in tap and river water at a concentration close to the environmental ones. All drugs underwent sunlight degradation according to a pseudo-first-order decay. The kinetic constants ranged from 0.00082 min -1 for CORT to 0.024 min -1 for PRED and PREDLO. The photo-generated products were identified by high-pressure liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). The main steps of the degradation pathways were the oxidative cleavage of the chain 17 for CORT, HCORT and the rearrangement of the cyclohexadiene moiety for the other GCs. The acute and chronic toxicity of GCs and of their photoproducts was assessed by the V. fischeri and P. subcapitata inhibition assays. The bioassays revealed no significant differences in toxicity between the parent compounds and their photoproducts, but the two organisms showed different responses. All samples produced a moderate acute toxic effect on V. fisheri and no one in the chronic tests. On the contrary, evident hormesis or eutrophic effect was produced on the algae, especially for long-term contact.

The aim of this study was to assess the photostability of quercetin in the presence of anionic and nonionic polymeric gels with varied compositions of an added component-glycerol. The samples were irradiated continuously at constant temperature. The stability of quercetin in solution and incorporated into the gels was evaluated by an UV-Vis spectrophotometer. FTIR spectroscopy (Fourier-transform infrared spectroscopy) was used to detect the changes in the structure of quercetin depending on the polymer used in the gel, and on the exposure time. Photostabilization is an important aspect of quality assurance in photosensitive compounds. The decomposition rate of quercetin in the ionic preparation of polyacrylic acid (PAA) with glycerol was 1.952·10 -3 min -1 , whereas the absence of glycerol resulted in a decay rate of 5.032·10 -4 min -1 . The formulation containing non-ionic methylcellulose resulted in a decomposition rate of quercetin in the range of 1.679·10 -3 min -1 . The decay rate of quercetin under light influence depended on the composition of the gel. It was found that the cross-linked PAA stabilized quercetin and the addition of glycerol accelerated the photodegradation.

Near UV (λ = 320-400 nm) and visible light (λ = 400-800 nm) can lead to the oxidation of pharmaceutical proteins, which can affect efficiency and promote immunogenicity. However, no concise mechanism has been established for the photo-oxidation of pharmaceutical proteins under near UV and visible light. Here, we show that carboxylic acid buffer-Fe 3+ complexes can function as photosensitizers, causing peptide degradation via the formation of various radicals and oxidants. Three pharmaceutical relevant carboxylic acid buffers (citrate, acetate, and succinate) were tested under near UV and visible light. Oxidation reactions were monitored for model peptides containing readily oxidizable amino acids, such as methionine- or leucine-enkephalin and proctolin peptide. Oxidation products were evaluated by RP-HPLC coupled to UV or fluorescent detection and RP-HPLC-MS/MS. Specifically for citrate buffer, the light-induced formation of H 2 O 2 , • OH, • CO 2 - , and formaldehyde was demonstrated. The peptides displayed oxidation of Met, hydroxylation of Tyr and Phe, as well as the formation of novel products from Tyr. Experiments with 18 O 2 resulted in the incorporation of 18 O into various reaction products, consistent with a metal-catalyzed activation of O 2 into reactive oxygen species. The addition of EDTA and DTPA did not prevent the oxidation of the peptides and, in some cases, enhanced the oxidation. Our results demonstrate that pharmaceutical buffer-Fe 3+ complexes, exposed to UV and visible light, can promote various pathways of oxidation reactions in pharmaceutical formulations.

Titanate nanomaterials have been outstanding in the removal of emerging contaminants by the photocatalysis process. These photocatalysts, when modified through techniques such as doping with metals, they have advantages over TiO 2 , especially in the region of visible light. In this work, the photocatalytic performance of four recent reported catalysts, pristine titanate nanowires, cobalt-doped titanate nanowires, iron-doped titanate nanowires and ruthenium-doped titanate nanowires, for the removal of the antidepressant trazodone under visible light radiation was compared. The iron-doped titanate nanowires presented the best catalytic activity by the catalyst surface area. Additionally, thirteen transformation products (TPs) were identified by high-resolution mass spectrometry and, to the best of our knowledge, nine of them have never been described in the literature. It was shown that for each catalyst different TPs were formed with distinct time profiles. Finally, toxicity assessment by computational methods showed that TPs were not readily biodegradable and they presented toxicity to aquatic organisms with mutagenic potential. These findings reinforce the importance of taking into consideration the TPs formed during the removal of pollutants since many of them may be toxic and can be produced during photocatalysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

In the present study, additive-free, pH-driven, hydrothermal crystallization was used to obtain shape-tailored monoclinic BiVO 4 photocatalysts. The as-prepared BiVO 4 products were systematically characterized, uncovering their crystallographic, morphologic and optical properties, while their applicability was verified in the visible light-driven photodegradation of oxalic acid and rhodamine B. Monoclinic clinobisvanite was obtained in most cases, with their band gap values located between 2.1 and 2.4 eV. The morphology varied from large, aggregated crystals, individual microcrystals to hierarchical microstructures. It was found that the degradation efficiency values obtained in the case of oxalic acid were directly related to the presence of (040) crystallographic plane, while the degradation of rhodamine B was partially independent by the presence of this structural feature. The importance of (040) crystallographic plane was also demonstrated via the reduction of Cu 2+ to Cu, by analyzing the Raman spectra of the Cu containing samples, the mean primary crystallite size of Cu and Cu content. Furthermore, the presence of (040) crystallographic plane was directly proportional with the hydrodynamic properties of the powders as well.

Hydrogels for wound management and tissue gluing applications have to adhere to tissues for a given time scale and then disappear, either by removal from the skin or by slow degradation for applications inside the body. Advanced wound management materials also envision the encapsulation of therapeutic drugs or cells to support the natural healing process. The design of hydrogels that can fulfill all of these properties with minimal chemical complexity, a stringent condition to favor transfer into a real medical device, is challenging. Herein, we present a hydrogel design with a moderate structural complexity that fulfills a number of relevant properties for wound dressing: it can form in situ and encapsulate cells, it can adhere to tissues, and it can be degraded on demand by light exposure under cytocompatible conditions. The hydrogels are based on starPEG macromers terminated with catechol groups as cross-linking units and contain intercalated photocleavable nitrobenzyl triazole groups. Hydrogels are formed under mild conditions ( N -(2-hydroxyethyl)piperazine- N '-ethanesulfonic acid (HEPES) buffer with 9-18 mM sodium periodate as the oxidant) and are compatible with encapsulated cells. Upon light irradiation, the cleavage of the nitrobenzyl group mediates depolymerization, which enables the on-demand release of cells and debonding from tissues. The molecular design and obtained properties reported here are interesting for the development of advanced wound dressings and cell therapies and expand the range of functionality of current alternatives.

The interaction between lanthanide diphthalocyanine complexes, LnPc 2 (Ln = Nd, Sm, Eu, Gd, Yb, Lu; Pc = C 32 H 16 N 8 , phthalocyanine ligand) and trifluoroacetic acid (TFA) was investigated in benzene, and the stability of the resulting molecular system was assessed based on spectral (UV-Vis) and kinetic measurements. Structural Density Functional Theory (DFT) calculations provided interesting data regarding the nature of the bonding and allowed estimating the interaction energy between the LnPc 2 and TFA species. Conjugates are created between the LnPc 2 and TFA molecules via hydrogen bonds of moderate strength (>N∙∙H··) at the meso - -bridges of the Pc moieties, which renders the sandwich system to flatten. Attachment of TFA is followed by rearrangement of electronic density within the chromophore system of the macrocycles manifested in considerable changes in their UV-Vis spectra and consequently the color of the studied solutions (from green to orange). The LnPc 2 @TFA conjugates including Nd, Sm, Eu, and Gd appeared evidently less photostable when exposed to UV radiation than the related mother compounds, whereas in the case of Yb and Lu derivatives some TFA-prompted stabilizing effect was noticed. The conjugates displayed the capacity for singlet oxygen generation in contrast to the LnPc 2 s itself. Photon upconversion through sensitized triplet-triplet annihilation was demonstrated by the TFA conjugates of Nd, Sm, Eu, and Gd.

Glycerophospholipids (GPLs), one of the main components of bacterial cell membranes, exhibit high levels of structural complexity that are directly correlated with biophysical membrane properties such as permeability and fluidity. This structural complexity arises from the substantial variability in the individual GPL structural components such as the acyl chain length and headgroup type and is further amplified by the presence of modifications such as double bonds and cyclopropane rings. Here we use liquid chromatography coupled to high-resolution and high-mass-accuracy ultraviolet photodissociation mass spectrometry for the most in-depth study of bacterial GPL modifications to date. In doing so, we unravel a diverse array of unexplored GPL modifications, ranging from acyl chain hydroxyl groups to novel headgroup structures. Along with characterizing these modifications, we elucidate general trends in bacterial GPL unsaturation elements and thus aim to decipher some of the biochemical pathways of unsaturation incorporation in bacterial GPLs. Finally, we discover aminoacyl-PGs not only in Gram-positive bacteria but also in Gram-negative C. jejuni , advancing our knowledge of the methods of surface charge modulation that Gram-negative organisms may adopt for antibiotic resistance.

The development of sustainable methods for the degradation of pollutants in water is an ongoing critical challenge. Anthropogenic organic micropollutants such as pharmaceuticals, present in our water supplies in trace quantities, are currently not remediated by conventional treatment processes. Here, we report an initial demonstration of the oxidative degradation of organic micropollutants using specially designed nanoparticles and visible-wavelength sunlight. Gold "Janus" nanorods (Au JNRs), partially coated with silica to enhance their colloidal stability in aqueous solutions while also maintaining a partially uncoated Au surface to facilitate photocatalysis, were synthesized. Au JNRs were dispersed in an aqueous solution containing peroxydisulfate (PDS), where oxidative degradation of both simulant and actual organic micropollutants was observed. Photothermal heating, light-induced hot electron-driven charge transfer, and direct electron shuttling under dark conditions all contribute to the observed oxidation chemistry. This work not only provides an ideal platform for studying plasmonic photochemistry in aqueous medium but also opens the door for nanoengineered, solar-based methods to remediate recalcitrant micropollutants in water supplies., Competing Interests: The authors declare no competing interest.

In this work, a high-surface-area dual inorganic molecularly imprinted (DIMI) Bi 2 WO 6 /CuO/Ag 2 O photo-catalyst was developed for the selective photocatalytic degradation of methyl green (MG) and auramine O (AO) dyes as target pollutants. The DIMI-Bi 2 WO 6 /CuO/Ag 2 O heterojunction was synthesized by a sono-chemically assisted sol-gel method by coating a layer of molecularly imprinted Ag 2 O/CuO on the surface of Bi 2 WO 6 nanocubes with MG and AO as the templates. This was followed by calcination for the removal of target molecules and annealing for Ag/Cu oxide preparation. This novel photocatalyst was prepared to overcome the challenge of the co-existing non-target molecules, which has limited the photocatalytic degradation performance. The surface DIMI sites could act as surface defects for accelerating the separation of photogenerated holes and electrons, which led to the increased generation of OH radicals. Moreover, the DIMI sites had increased binding affinity toward MG and AO via the formation of multiple H bonds and electrostatic bonds, which were confirmed by FTIR spectroscopy, PL and EIS studies. The surface DIMI sites led to the increased adsorption and improved local concentration of MG and AO on Bi 2 WO 6 /CuO/Ag 2 O. Consequently, the heterojunction properties of the final DIMI product accelerated the transfer and separation of photogenerated carriers. The high binding affinity of the DIMI sites to MG and AO confirmed the selective recognition, which was tested in the presence of coexisting pollutant dyes. The other characterizations confirmed the successful fabrication and high photocatalytic activity of the high-surface-area DIMI-Bi 2 WO 6 /CuO/Ag 2 O heterostructured composite. In general, the superior interfacial electronic interactions, high migration efficiency of photoinduced charge carriers, and strong visible light absorption of the prepared photocatalyst resulted in good photocatalytic performance.

Photolytic cleavage of disulfide bonds in proteins by UV light will influence their structure and functionality. The present study aimed to investigate the efficiency of disulfide cleavage by UV-B light in a system without a protein backbone consisting of combinations of cystine (a disulfide) and tryptophan (Trp) or tyrosine (Tyr) under anaerobic and aerobic conditions and to identify oxidation products formed by UV-B light. Cystine was reduced to cysteine (Cys) almost with a 1:1 stoichiometry by photoexcited Trp for anaerobic equimolar aqueous solutions (each 200 μM; pH 7.0), while photoexcited Tyr provided lower concentrations of Cys. The calculation of apparent quantum yields allowed for a comparison between the efficiency of reactions and showed that formation of Cys from disulfide cleavage of cystine was more efficient by photoexcited Trp than by photoexcited Tyr and of cystine alone and that Trp was more sensitive to photodegradation than Tyr and cystine under both aerobic and anaerobic conditions. Increasing the ratio between cystine and Trp to a 1:2 ratio did not increase the efficiency of free thiol formation but caused a more efficient photodegradation of Trp. The free thiol formed from disulfide cleavage of cystine was further oxidized to other unidentified compounds. Trp oxidation products (3-hydroxykynurenine (3-OH-Kyn) and tryptamine) were only identified in minor concentrations following light exposure of cystine and Trp in 1:1 and 1:2 ratios under both aerobic and anaerobic conditions, indicating further photodegradation to unidentified compounds. 3,4-Dihydroxyphenylalanine (DOPA) was formed from the oxidation of Tyr in the illuminated samples of cystine and Tyr in a 1:1 ratio under both aerobic and anaerobic conditions.

We analyzed the backbone fragmentation behavior of tryptic peptides of a four-protein mixture and of E. coli lysate subjected to ultraviolet photodissociation (UVPD) at 213 nm on a commercially available UVPD-equipped tribrid mass spectrometer. We obtained 15 178 unique high-confidence peptide UVPD spectrum matches by recording a reference beam-type collision-induced dissociation (HCD) spectrum of each precursor, ensuring that our investigation includes a broad selection of peptides, including those that fragmented poorly by UVPD. Type a, b, and y ions were most prominent in UVPD spectra, and median sequence coverage ranged from 5.8% (at 5 ms laser excitation time) to 45.0% (at 100 ms). Overall, the sequence fragment intensity remained relatively low (median: 0.4% (5 ms) to 16.8% (100 ms) of total intensity), and the remaining precursor intensity, high. The sequence coverage and sequence fragment intensity ratio correlated with the precursor charge density, suggesting that UVPD at 213 nm may suffer from newly formed fragments sticking together due to noncovalent interactions. The UVPD fragmentation efficiency therefore might benefit from supplemental activation, as was shown for ETD. Aromatic amino acids, most prominently tryptophan, facilitated UVPD. This points to aromatic tags as possible enhancers of UVPD. Data are available via ProteomeXchange with identifier PXD018176 and on spectrumviewer.org/db/UVPD-213nm-trypPep.

In this paper, a Z-scheme Ag 3 PO 4 /BiVO 4 photocatalyst was successfully prepared by precipitation-deposition method. The Ag 3 PO 4 /BiVO 4 composite exhibited enhanced photocatalytic activity and recyclability for levofloxacin and methylene blue degradation under visible light irradiation. In the Ag 3 PO 4 /BiVO 4 -0.4 system, up to 92.44% of the levofloxacin molecules can be decomposed within 180 min and the photocatalytic degradation efficiency can maintain at 92.02% for methylene blue after recycled for 5 times. The enhanced photocatalytic activity of Ag 3 PO 4 /BiVO 4 heterojunctions could be mainly attributed to the fabrication of hetero-structure between BiVO 4 and Ag 3 PO 4 . The photogenerated electron-hole pair separation was effectively enhanced based on the photocurrent, electro-chemical impedance spectra and photoluminescence data. Furthermore, the electrons transfer from photoinduced BiVO 4 to Ag 3 PO 4 and the visible light harvesting efficiencies were significantly increased due to the BiVO 4 hybridization. The ·OH was the main oxidative species in the Ag 3 PO 4 /BiVO 4 system for the methylene blue decomposition. Finally, a purposed photocatalytic mechanism for methylene blue degradation was discussed in detail on the basis of experimental results., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019. Published by Elsevier B.V.)

The efficacy of photocatalysis strongly depends on the activity of the catalysts and the operational factors, especially factors associated with mass transfer and the possibility of catalyst deactivation. The use of ultrasound has great potential to enhance catalyst activity, during both the synthesis and actual oxidation processes due to the cavitational effects of turbulence and liquid streaming. This article presents an overview of the application aspects of ultrasound, both in the synthesis of the photocatalyst and applications for wastewater treatment. A review of the literature revealed that the use of ultrasound in the synthesis processes can result in a catalyst with a lower mean size and higher surface area as well as uniform size distribution. The application of ultrasound in the actual photocatalytic oxidation facilitates enhancement of the oxidation capacity, leading to higher degradation rates, sometimes synergistic results and definitely lower treatment times. This article also presents guidelines for the selection of the best operating conditions for the use of ultrasound in photocatalytic systems and includes a discussion on the possible reactor configurations suitable for large-scale operations. Overall, a combination of ultrasound with photocatalytic oxidation or the optimized application of ultrasound in catalyst synthesis can yield significant benefits.

In the recent years, copper tungstate (CuWO 4 ) has been widely researched for its photocatalytic properties as it responds in the visible light range to augment the utilization of solar energy. In the present report, CuWO 4 was synthesized through a facile and cost-effective solvothermal method, followed by annealing process at 700 ∘ C. The structural, morphological, compositional and optical property of the synthesized powders were examined by X-ray diffraction, scanning electron microscope, UV-visible, Raman and photoluminescence studies. The photocatalytic activity of the nanostructured CuWO 4 was evaluated by the degradation of methylene blue (MB) and methyl orange (MO) in aqueous solution under one sun light irradiation. The degradation efficiency of MB was found to be about 70% while that of MO was only 57% at 240 min in the same irradiation time. Surprisingly, the degradation process was accelerated by the addition of electron capturing agent H 2 O 2 and thus MB dye was completely degraded within the time interval of 30 min while MO degraded in 75 min. These results prove that CuWO 4 nanoparticles possess significant photocatalytic activity towards MO and MB dyes, thus indicating the feasibility of using CuWO 4 for the active treatment of organic contaminants in the industrial effluents., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Present work compares the green synthesis of iron oxide nanorodes (NRs) using Withania coagulans and reduction precipitation based chemical method. UV/Vis confirmed the sharp peak of Iron oxide NRs synthesized by biologically and chemically on 294 and 278 nm respectively. XRD and SEM showed highly crystalline nature of NRs with average size 16 ± 2 nm using Withania extract and less crystalline with amorphous Nanostructure of 18 ± 2 nm by chemical method. FTIR analysis revealed the involvement of active bioreducing and stabilizing biomolecules in Withania coagulans extract for synthesis of NRs. Moreover, EDX analysis indicates 34.91% of Iron oxide formation in biological synthesis whereas 25.8% of iron oxide synthesis in chemical method. The degradation of safranin dye in the presence of Withania coagulans based NRs showed 30% more effectively than chemically synthesized Nanorods which were verified by the gradual decrease in the peak intensity at 553 nm and 550 nm respectively under solar irradiation. Furthermore, Withania coagulans based NRs showed effective Antibacterial activity against S.aureus and P. aeuroginosa as compared to NRs by chemical method. Finally, we conclude that green synthesized NRs are more effective and functionally more efficient than chemically prepared NRs. Therefore, our work will help the researchers to boost the synthesis of nanoparticles via biological at commercial level., Competing Interests: Declaration of Competing Interest There is no conflict of interest among authors for publication of this work, (Copyright © 2020. Published by Elsevier B.V.)

In this study, the post-treatment of biologically treated acrylonitrile wastewater was investigated during UV/H 2 O 2 process. Five contaminants in the effluent were selected as target compounds, including Furmaronitrile (FMN), 3-Pyridinecarbonitrile (3PCN), 1,3-Dicyanobenzene (1,3-DCB), 5-Methyl-1H-benzotriazole (5MBT), and 7-Azaindole (7AID). Under optimal reaction conditions, the UV/H 2 O 2 post-treatment exhibited good performances in destruction of organic compounds and toxicity. The photo-chemical parameters of the target compounds were measured and it was found that 5MBT and 3PCN had fast degradation rate constants under direct UV photolysis. The second-order rate constants of the target compounds with hydroxyl radicals were determined to be in the range of (1.0-5.0) × 10 9  M -1  s -1 at pH 3.0 and 25 °C. A simplified pseudo-first-order steady state (Sim-PSS) model, which considered direct UV photolysis and radical oxidation simultaneously, agreed well with the experimental data from the post-treatment of a biologically treated effluent. High-performance size exclusion chromatography (HPSEC) coupled with diode-array detector (DAD) and fluorescence detector (FLD) analysis revealed that humic-like sub-peak signals from different molecular weights of fluorescent organic matter decreased consistently during the oxidation process, which made humic-like fluorescence exhibit higher correlation with the target compounds' degradation than the spectral indices of UV absorbance at 254 nm (UVA 254 ) and protein-like fluorescence., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Loss of stability of pharmaceutical APIs (Active Pharmaceutical Ingredient) due to photolytic activity has been a major concern in the pharmaceutical industry as it leads to loss of activity of API and excipients, the formation of toxic by-products, change in color and flavor. Itraconazole (ITZ) bulk drug was exposed to UVC (254 nm) irradiation in an environmental chamber (37 °C, 75 %RH) and its photoprotection by cinnamon, clove, eugenol, and oregano based microemulsion was analyzed. No significant change in the spectra was observed at various time points, confirming the photo-protective activity of microemulsions, unlike the bulk drug. FTIR spectra illustrate the fundamental peaks of the functional groups of ITZ and ITZ loaded MEs. The overlaid spectra showed that there was a minor change in peaks of UV exposed ITZ bulk drug but the ITZ loaded microemulsions were able to protect all the major functional groups. The in vitro anti-microbial assay against C. albicans demonstrated no significant change in the activity of ITZ loaded microemulsion between untreated, 7th day and 15th day while the activity of bulk drug was reduced drastically in the UVC exposed sample. It was concluded that microemulsions can be used as an effective photo-protective drug delivery vehicle for light-sensitive compounds., Competing Interests: Declaration of Competing Interest The authors report no conflicts of interest. The authors alone are responsible for the content and writing of this article., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The graphene oxide (GO)-based materials are appealing channels for water treatment, their separation from water for recycle remains a task. The Cu 3 (btc) 2 (btc = benzene-1,3,5-tricarboxylic acid) metal organic framework (MOF) was covalently immobilized onto chitosan (CS)/graphene oxide (GO) to form a catalyst material, which was subjected to characterization by XRD, FTIR, SEM, TEM, BET, and UV-vis diffusive reflectance spectra. MOFs are permeable crystalline compounds consisting of metal ions and polyfunctional organic ligands. The structural characterization revealed that the Cu 3 (btc) 2 and chitosan were incorporated into the graphene oxide structure. The adsorption of MB by GO-CS@Cu 3 (btc) 2 catalyst was clearly defined by Langmuir isotherm and pseudosecond order kinetic model. GO-CS@Cu 3 (btc) 2 was found to possess an adsorption capacity of ~357.15 mg/g. The findings displayed the probability of reusing the catalyst material for several photocatalytic processes. The GO-CS@Cu 3 (btc) 2 catalyst material exhibited 98% degradation of MB within 60 min under UV irradiation. The obtained MB degradation results were fitted onto a Langmuir-Hinshelwood (L-H) plot. The GO-CS@Cu 3 (btc) 2 catalyst material exhibited high degradation efficiencies at neutral pH conditions. The results have shown that the GO-CS@Cu 3 (btc) 2 catalyst material can be used as a catalyst for adsorption and as a photocatalyst for the efficient degradation of methylene blue from aqueous solutions., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The efficacy of a sunscreen tends to be associated with its sun protection factor (SPF) value, a figure determined in a test that relies on the independence of the SPF value to both UV radiation dose and irradiance. We probe these assumptions when photoinduced product degradation is present, and we estimate that the theoretical limit for their validity is when the sunfilter active molecule relaxation time is faster than ∼10 ns. While such threshold relaxation time should be compatible with the expected ultrafast relaxation mechanisms of sunfilter molecules (picoseconds), recent research on sunfilter photodynamics has identified the existence of much longer-lived molecular states. Such long lifetimes could compromise sunscreen performance and make the SPF value very different in natural sun irradiance conditions than in the solar simulated conditions typically used in SPF determination tests.

Graphyne, a theorized carbon allotrope possessing only sp- and sp 2 -hybridized carbon atoms, holds great potentials in many fields, especially in catalysis and energy-transfer/storage devices. Using a bottom-up strategy, we synthesized a new N-doped graphyne analogue, triazine- and 1,4-diethynylbenzene-based graphyne TA-BGY, in solution in gram-scale. The unique sp/sp 2 carbon-conjugated TA-BGY possesses an extended porous network structure with a BET surface area of approximately 300 m 2  g -1 . Owing to its low optical band gap (1.44 eV), TA-BGY was expected to have many applications, which were exemplified by the photodegradation of methyl orange and photocatalytic bacterial inactivation., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Purpose: Therapeutic proteins are sensitive to photo-degradation by UV A and visible light. As none of the essential amino acids exhibits significant absorption in the UV A and visible light regions, the underlying mechanisms of photo-degradation induced by UV A and visible light are not well understood. This review addresses potential mechanisms, by which protein structure, oxidative modifications or impurities can promote the photo-degradation of therapeutic proteins during the exposure to UV A and visible light.

Linezolid (LIN) and Tedizolid (TED) are representatives of oxazolidinone antibiotics of last resort with a strong efficacy against gram-positive bacteria. This study focused on their solar-mediated degradation to understand better their fate in aquatic environment, for the realistic concentrations in the range of 1 μg/L. Results showed that both antibiotics (ABs) are degradable by simulated sunlight (1 kW/m 2 ), with half-lives of 32 and 93 h in ultrapure water, for LIN and TED, respectively. LIN showed similar photolytic behaviour in pure solution and in surface water, whereas sunlight enhanced the degradation of LIN in pure solutions, but not in surface water. Structure elucidation by liquid chromatography coupled to high resolution mass spectrometry provided information about seven transformation products for LIN and five for TED. The morpholinyl-ring was identified as the target site for most transformation reactions of LIN. TED was prone to oxidation and cleavage of the oxazolidinone ring. Results of a growth inhibition test on Bacillus subtilis exposed to UV light showed antibacterial efficacy of transformation products of LIN and no significant efficacy of degradation products of TED for the concentration range of 100 μg/L-10 mg/L of parent compounds. Photolytically treated solutions of the ABs maintained their inhibitory effect on the bioluminescence of Aliivibrio fischeri., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Folic acid, a synthetic form of folate, is a water-soluble vitamin that is essential during periods of rapid cell division and growth. However, it decomposes upon ultraviolet irradiation to form inactive photoproducts. In this study, the protective effect and mechanisms of antioxidants, including cinnamic acids, flavonoids, catechol and its derivatives, stilbenes, p -benzoquinone and its derivatives, isoprenoids, curcumin, oleic acid, and linoleic acid, against folic acid photodecomposition were investigated by using fluorescence and absorbance spectroscopy, high-performance liquid chromatography, and antioxidant assay. It was found that antioxidants could inhibit or delay the folic acid decomposition in varying degrees, among which caffeic acid was the most effective. The increase in its remarkable antioxidant efficiency and absorbance in the UVA region during irradiation contributed to its effective protection. This finding could be useful for the protection of photolabile components in food and other uses.

In this study, Pd-BiVO 4 bearing highly dispersed Pd nanoparticles was prepared from pure BiVO 4 using an impregnation method. The pure BiVO 4 and Pd-BiVO 4 catalysts were characterized by X-ray diffraction, scanning electron microscopy, UV-visible diffuse reflection, transmission electron microscopy, and X-ray photoelectron spectroscopy. The results showed that the prepared catalysts had a monoclinic scheelite structure and exhibited a flake-like morphology. Pd-BiVO 4 showed a distinct response in the visible light region, with an extended absorption edge at 550 nm. According to the Scherrer formula, the nanocrystal particle sizes of the BiVO 4 and Pd-BiVO 4 catalysts were 35 and 28 nm, respectively. Highly dispersed Pd nanoparticles with sizes of 2.5 ± 0.5 nm were observed on the BiVO 4 surface. Two Pd valence states, Pd(II) and Pd(0), were identified in a 2:1 ratio. Pd-BiVO 4 exhibited excellent activity for paracetamol (PCT) degradation, with 100% removal achieved in 1 h under visible light irradiation. During degradation, the mineralization ratio reached up to 40% total organic carbon removal. Two highly active species, namely, hydroxyl and superoxide radicals, were determined by electron spin resonance (ESR). Furthermore, the potential degradation of PCT in this system was proposed based on intermediate information obtained using HPLC-MS and Gauss analysis. The high dispersion and small size of Pd nanoparticles might favor the removal of emerging contaminants using the Pd-BiVO 4 photocatalytic system., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Contaminants of emerging concern (including pharmaceuticals) are not effectively removed by municipal wastewater treatment plants (WWTPs), so particular concern is related to agricultural wastewater reuse due to their possible uptake in crops irrigated with WWTPs effluents. Advanced oxidation processes (AOPs) and solar AOPs have been demonstrated to effectively remove pharmaceuticals from different aqueous matrices. In this study, an heterogeneous photocatalytic process using powdered nitrogen-doped TiO 2 immobilized on polystyrene spheres (sunlight/N-TiO 2 ) was compared to the benchmark homogenous AOP sunlight/H 2 O 2 in a compound triangular collector reactor, to evaluate the degradation of three pharmaceuticals (carbamazepine (CBZ), diclofenac (DCF), trimethoprim (TMP)) in water. The degradation of the contaminants by sunlight and sunlight-AOPs well fit the pseudo-first order kinetic model (but for TMP under sunlight). High removal efficiency by solar photolysis was observed for DCF (up to 100%, half-life sunlight cumulative energy Q S,1/2  = 2 kJ L -1 , half-life time t 1/2  = 32 min), while CBZ (32%, Q S,1/2  = 28 kJ L -1 , t 1/2  = 385 min) and TMP (5% removal after 300 min) removal was poor. The degradation rate of CBZ, TMP and DCF was found to be slower during sunlight/H 2 O 2 (Q S,1/2  = 5 kJ L -1 , t 1/2  = 77 min; Q S,1/2  = 20 kJ L -1 , t 1/2  = 128 min; Q S,1/2  = 4 kJ L -1 , t 1/2  = 27 min, respectively) compared to sunlight/N-TiO 2 (Q S,1/2  = 4 kJ L -1 , t 1/2  = 55 min; Q S,1/2  = 3 kJ L -1 , t 1/2  = 42 min; Q S,1/2  = 2 kJ L -1 , t 1/2  = 25 min, respectively). These results are promising in terms of solar technology upscale because the faster degradation kinetics observed for sunlight/N-TiO 2 process would result in smaller treatment volume, thus possibly perspective compensating the cost of the photocatalyst., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In this work, a molecular hydrogel made of gelator (S)-4-((3-methyl-1-(nonylamino)-1-oxobutan-2-yl)amino)-4-oxobutanoic acid (SVN) has been employed as soft container to modify the photochemical and photophysical behavior of the antipsychotic drug cyamemazine (CMZ). The interaction of CMZ with the gel network has been evidenced by fluorescence spectroscopy through a hypsochromic shift of the emission band (from λ max  = 521 nm in solution to λ max  = 511 nm in the gel) and an increase of the fluorescence lifetime (5.6 ns in PBS vs. 7.2 ns in the gel). In the laser flash photolysis experiments on CMZ/SVN systems, the CMZ triplet excited state ( 3 CMZ*), monitored at λ = 320 nm, has been more efficiently generated and became much longer-lived than in solution (2.7 μs vs. 0.7 μs); besides, photochemical ionization leading to the radical cation CMZ +• was disfavored. In the steady-state experiments, photooxidation of CMZ to afford the N,S-dioxide derivative CMZ-SONO has been retarded in the gel, which provides a more lipophilic and constrained microenvironment. Both the photophysical properties and the photoreactivity are in agreement with CMZ located in a less polar domain when entrapped in the supramolecular gel, as result of the interaction of the drug with the fibers of the supramolecular SVN gel., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Development of highly robust and solar-light-responsive photocatalysts for the disposal of organic dyes from wastewater is a matter of great significance in order to solve the problems of water pollution. Solar-driven photocatalytic degradation of dyes is considered as a quite efficient, sustainable and cost-effective approach as it involved the inexhaustible and renewable source of energy. In photocatalytic processes, the generation of electron-hole pairs at the surface of the photocatalyst is accomplished by harvesting solar energy. The electron-hole pairs are converted into • OH radicals that are responsible for the degradation of dyes. Herein, we reported the synthesis of nanosized iron (FeNPs) using the aqueous fruit extract of Actinidia chinensis as a reducing as well as the stabilizing agent. The structure and morphology of synthesized nanoparticles were characterized using various advanced techniques. The TEM micrographs showed that the synthesized FeNPs was predominantly cubic and rod-shaped having the size in the range of 91.78-107 nm. The as-prepared FeNPs were acted as effective photocatalysts and their photocatalytic activity evaluated against alizarin yellow R (AYR) dye. The effect of different reaction conditions such as temperature, pH, time and catalyst loading on photocatalytic degradation of AYR dye was investigated under sunlight irradiation. The FeNPs showed promising photocatalytic activity and up to 93.7% of the dye was degraded in 42 h. The kinetics parameter of the reaction was also evaluated which showed that the photocatalytic degradation of AYR dye followed the pseudo-first-order reaction. In terms of better degradation, the role of FeNPs might be extended for the treatment of different organic dyes from wastewater., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Bacterial pathogenicity is becoming a major cause of morbidity and mortality around the globe. Researchers are tirelessly finding solutions to cure or prevent infections caused by bacterial pathogens. Nanotechnology is a fast-growing area of research, effectively influencing and preventing bacterial growth. Nanoparticles (NPs) of silver, copper and gold are being used to kill bacterial pathogens in the past years but the toxicity of NPs at higher concentrations remains a major problem. Therefore, in the present study, Co 3 O 4 @ZrO 2 (CoZ) core/shell NPs were synthesized using a simple sol-gel method. The synthesized NPs were characterized using different analytical techniques revealing the absorption bands at 456 and 277 nm with crystalline size of ~600 nm core/shell. The functional groups and oxidation states were characterized using FTIR analysis. Further bactericidal properties of core/shell of Co 3 O 4 @ZrO 2 NPs were tested against Gram negative (Escherichia coli, Pseudomonas aeruginosa) and Gram positive (Staphylococcus aureus, Bacillus subitilis) pathogens. The core/shell CoZ NPs showed maximum growth inhibitions against S. aureus and P. aeruginosa. At the highest concentration of 200 μg/mL, the maximum zone of inhibition was observed. The synthesized CoZ NPs was also subjected to photocatalytic degradation of rhodamine B in 180 min under visible light irradiation. The present study could be an innovative and efficient research for both biomedical and wastewater treatment applications., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Zeolitic imidazole framework (ZIF) is an emerging class of metal organic frameworks exhibiting unique features such as crystalline nature with tunable pore size, large surface area and biocompatible nature. Exceptional thermal and chemical stabilities of ZIF-L make it a suitable candidate for biomedical applications. The present study has focused on the single step fabrication of catechin encapsulated ZIF-L and evaluation of its antibiofilm efficiency, larvicidal activity and dye degradation ability. The as- prepared CA@ZIF-L nanocomposite was characterized by spectroscopic and microscopic techniques. The results revealed that the CA@ZIF-L showed significant toxicity against mosquito larvae in a dose dependent manner with the IC 50 63.43±1.25 μg/mL. CA@ZIF-L showed dose dependent reduction of biofilm formation in both ATCC and clinical MRSA strains. In addition, CA@ZIF-L exhibited excellent photocatalytic activity with around 92% degradation of methylene blue under direct sunlight. Overall, the present work highlights the possibility of employing the multifunctional CA@ZIF-L nanocomposite as a suitable material for biomedical and photocatalytic applications., (Copyright © 2019. Published by Elsevier B.V.)

The present study reports the biosynthesis of silver nanoparticles (AgNPs) using Bacillus amyloliquefaciens MSR5. The cellfree supernatant of B. amyloliquefaciens acted as a stabilizing agent for the synthesis of AgNPs. The synthesized AgNPs were characterized using UV-vis spectrophotometer, PXRD, FTIR, SEM-EDX, DLS, and TEM. TEM image showed the spherical shape of the biosynthesized AgNPs and it was found to be 20-40 nm in range. In this study, the AgNPs were prepared by ultrasonic irradiation. The stability of the AgNPs was found to be -33.4 mV using zeta potential. The catalytic 4-nitrophenol (4-NP) degradation by AgNPs was examined under solar irradiation and furthermore, the effects of several degradation parameters were studied. The biosynthesized AgNPs exhibited a strong chemocatalytic action with a comprehensive degradation (98%) of 4-NP to 4-aminophenol (4-AP) using NaBH 4 within 15 min. In addition, MTT assay was performed to evaluate the cytotoxicity of the biosynthesized AgNPs (10 - 200 μg). The results have shown that the AgNPs exhibited significant activity on A549 cells, which was dosedependent. The study elucidates the AgNPs synthesized using cellfree culture supernatant can be used for the elimination of hazardous pollutants from wastewater., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The photolysis of thiochrome (THC), an oxidation product of thiamine (vitamin B 1 ) (THE), used for its fluorimetric assay, has been studied in the pH range 7.0-12.0. THC undergoes photooxidation to oxodihydrothiochrome (ODTHC) which is oxidized to a non-fluorescent compound (OP1) on UV irradiation. The kinetics of the consecutive first-order reactions: THC→k 1 ODTHC→k 2 OP1, has been evaluated and the values of first-order rate constants, k 1 (0.58-4.20 × 10 -5 , s -1 ) and k 2 (0.05-2.03 × 10 -5 , s -1 ), at pH 7.0-12.0 have been determined. The rates of degradation of THC and ODTHC are enhanced with pH and the second-order rate constants k 1 ' and k 2 ' for the OH - ion-catalyzed reaction are in the range of 0.002-58.3 M -1  s -1 . The quantum yields of the photolysis of THC and ODTHC in the pH range 7.0-12.0 have been determined. THC, ODTHC and OP1 have been identified by chromatographic, spectrometric and fluorimetric methods. THC and ODTHC have similar fluorescence characteristics and emit at 450 and 445 nm, respectively. THC, ODTHC and OP1 with distinct absorption maxima (370, 344 and 290 nm, respectively) have been determined by a newly developed and validated multicomponent spectrometric method during the photolysis reactions. The on-line formation of THC by the photooxidation of THE may lead to the degradation of THC and give erroneous results in the fluorimetric assay of THE. A scheme for the photolysis reactions of THC in aqueous solution is presented., (Copyright © 2020 Elsevier B.V. All rights reserved.)