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Bisphenols (BPs) are pervasive environmental contaminants extensively found in indoor environments worldwide. Despite their ubiquitous presence and potential health risks, there remains a notable gap in the comprehensive reviews focusing on BPs in indoor dust. Existing literature often addresses specific aspects such as exposure pathways, transformation products, or biomonitoring techniques, but lacks a consolidated, in-depth review encompassing all these facets. This review provides a comprehensive overview of the global distribution of BPs, emphasizing their prevalence in diverse indoor settings ranging from households and workplaces to public areas. Variations in BP concentrations across these environments are explored, influenced by factors such as industrial activities, consumer product usage patterns, and geographical location. Exposure assessments highlight ingestion, inhalation, and dermal contact as primary pathways for BP exposure, with ingestion being particularly significant for vulnerable groups such as infants and young children. Studies consistently reveal higher concentrations of BPs in urban indoor dust compared to rural settings, reflecting the impact of urbanization and intensive consumer practices. Moreover, BPs from mobile sources like vehicles contribute significantly to overall human exposure, further complicating exposure assessments. The review also delves into the transformation of BPs within indoor environments, emphasizing the diverse roles of physical, chemical, and biological processes in generating various transformation products (TPs). These TPs can exhibit heightened toxicity compared to their parent compounds, necessitating deeper investigations into their environmental fate and potential health implications. Critical examination of biomonitoring techniques for BPs and their metabolites underscores the importance of non-invasive sampling methods, offering ethical advantages and practicality in assessing human exposure levels. The emerging use of bioindicators, encompassing plants, animals, and innovative approaches like spider webs, presents promising avenues for effectively monitoring environmental contamination., 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 © 2024. Published by Elsevier Ltd.)

Indoor environments are particularly vulnerable to microplastics (MPs) and associated copollutants due to limited air circulation and particulate matter accumulation. Continuous monitoring is essential to evaluate exposure levels and health risks. We propose using indoor spider webs as passive monitors for MPs and their copollutants. MPs were found in both web and dust samples with nonuniform distribution ( p < 0.05), indicating contamination hotspots. Web samples had significantly higher MP levels (138-33,570 MPs/g) compared to dust samples (59-9324 MPs/g). A strong positive correlation ( r = 0.93, p < 0.05) between MPs in dust and webs suggests that spider webs are effective bioindicators of indoor MP contamination. The study also revealed the presence of Bisphenol A and various phthalic acid esters (PAEs). Co-pollutant concentrations ranged from 52.02-1971.78 μg/kg in webs and 43.18-518.42 μg/kg in dust. Diethyl phthalate (DEP) was more common in webs, while Dibutyl phthalate (DBP) predominated in dust. These findings highlight spider webs' potential as both effective biomonitoring tools and significant sinks for MPs and their cocontaminants in indoor environments., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

In India, Ceramic Water Filters (CWF) named G-filters are becoming a point-of-use household water treatment solution. The filter's reliability may be primarily characterized by the filtrate turbidity and microbial removal efficiency. The temperature and moisture gradients of the location affect its performance. This paper describes a 19-week laboratory investigation of G-filters simulating field conditions. The basic objective during the study was to ascertain the effective useable life of the filter. The discharge rate and turbidity reduction ability of the filters are studied in depth. The G-filters were prepared using locally available salty clay and sawdust taken in equal volume fractions. A total of 30 filters with a 9-liter capacity each were used for the experiments. The results showed that CWFs can reduce turbidity effectively. The influent water used for the study had a mean turbidity of 7.65 NTU, which reduced in the range of 0.03 NTU to 1.03 NTU. Over the course of four months, the average flow rate decreased from 1.94 Lh -1 to 0.93 Lh -1 . Although a soft brushing of filters improved the filtration rate but that too failed in the long run. Brunauer-Emmett-Teller (BET) nitrogen adsorption-desorption measurements were used to determine the variation in pore size of filters with time. An average pore radius of 2.91 nm was found in the original filter that has not been used for filtration experiments. Moreover, an average pore radius of 1.77 nm, 1.21 nm, and 1.22 nm were reported in G-filters through which 427.5 L, 807.5 L, and 1035.5 L, respectively, of water were passed. This reduction in pore size is attributed to the clogging of pores over a period of time. This study aims to collect performance data to establish a scientific model using statistical analysis for implementing CWF technology in developing nations., Competing Interests: Declaration of competing interest There is not conflict of interest among the authors which penning down the paper titled “Assessment of the physiochemical properties and sustainability of locally produced ceramic G-filter in a long term experiment”., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The natural phototransformation of organic pollutants in the environment depends on several water constituents, including inorganic ions, humic substances, and pH. However, the literature information concerning the influence of various water components on the amount of phototransformation and their impact on the development of various transformation products (TPs) is minimal. This study investigated the phototransformation of ofloxacin (OFL), a fluoroquinolone antibiotic, in the presence of various water components such as cations (K + , Na + , Ca 2+ , NH 4 + , Mg 2+ ), anions (NO 3 - , SO 4 2- , HCO 3 - , CO 3 2- , PO 4 3- ), pH, and humic substances when exposed to natural sunlight. The study reveals that neutral pH levels (0.39374 min⁻ 1 ) enhance the phototransformation of OFL in aquatic environments. Carbonate, among anions, shows the highest rate constant (2.89966 min⁻ 1 ), significantly influencing OFL phototransformation, while all anions exhibit a notable impact. In aquatic environments, indirect phototransformation of OFL, driven by increased reactive oxygen species, expedites light-induced reactions, potentially enhancing OFL phototransformation. A clear difference was visible in the type of transformation products (TPs) formed during direct and indirect photolysis. The impact of indirect photolysis in the product profile was evaluated by examining the unique properties of TPs in direct and indirect photolysis. The primary transformation products were generated by oxidation and cleavage processes directed towards the ofloxacin piperazinyl, oxazine, and carboxyl groups. The toxicity assessment of TPs derived from OFL revealed that among the 26 identified TPs, TP3 (demethylated product), TP7 and TP8 (decarboxylated products), and TP15 (piperazine ring cleaved product) could potentially have some toxicological effects. These findings suggest that the phototransformation of OFL in the presence of various water components is necessary when assessing this antibiotic's environmental fate., 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 © 2024. Published by Elsevier Ltd.)

Meeting societal demand for potable water supply remains one of the prioritized challenges faced in the modern era. The anthropogenic intervention has led to a dire situation threatening ecological balance and human health. There is an inevitable need for the development of new technologies and innovations in existing technologies for water treatment. Photocatalytic Membrane technology, encompassing the merits of membrane filtration and photocatalytic degradation has evolved as a potential and reliable technology for sustainable water treatment. Innovations in photocatalytic materials and membrane fabrication techniques can lead to the goal of commercialization of membrane water treatment technology. Herein, we demonstrate the potential of graphitic carbon nitride (g-C 3 N 4 ) and its functionalized analog as photocatalytic membranes for sustainable water treatment. g-C 3 N 4 and Tetracarboxyphenylporphyrin sensitized g-C 3 N 4 (g-C 3 N 4 /TCPP) was introduced onto commercial nylon membrane surface via a layer-by-layer (LBL) assembly method using chitosan and sodium salt of polystyrene sulphonic acid as polyelectrolytes. The fabricated membranes were characterized to ensure the integration of the photocatalysts. The performance of the membranes for water treatment was assessed by selecting some common dyes as model pollutants. The modified membranes exhibited excellent flux recovery and could afford high rejection rates upon irradiation indicating the prospects for sustainable filtration., 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 © 2024 Elsevier Ltd. All rights reserved.)

Steroid hormones (SHs) are among the important classes of Contaminants of Emerging Concern (CECs) whose detection in aquatic environments is vital due to their potential adverse health impacts. Their detection is challenging because of their lower stability in natural conditions and low concentrations. This study reports the presence of steroid hormones in a major river system, the Periyar River, in Kerala (India). Water samples were collected from thirty different river locations in the case of SHs and five locations within these in the case of other CECs. These were subjected to LC-MS/MS and LC-Q-ToF/MS analyses. Five SHs, estriol, estrone, 17 β estradiol, progesterone, and hydroxy progesterone, were separated and targeted using MS techniques. The studies of the water samples confirmed the presence of the first three estrogens in different sampling sites, with estrone present in all the sampling sites. The concentration of estrone was detected in the range from 2 to 15 ng/L. Estriol and estradiol concentrations ranged from 1.0 to 5 ng/L and 1-6 ng/L, respectively. The hormones at some selected sites were continuously monitored for seven months. The chosen areas include the feed water sites for the drinking water treatment plants across the river. The monthly data revealed that estrone is the only SHs detected in all the samples in the selected months. The highest concentration of SH was found in August. Twelve CECs belonging to pharmaceuticals and personal care products were identified and quantified. In addition, 31 other CECs were also identified using non-target analysis. A detailed study of the hormone mapping reported here is the first from any South Indian River., 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 © 2024 Elsevier Ltd. All rights reserved.)

Polyelectrolyte multilayer (PEM) deposition conditions can favorably or adversely affect the membrane filtration performance of various pollutants. Although pH and ionic strength have been proven to alter the characteristics of PEM, their role in determining the buildup interactions that control filtration efficacy has not yet been conclusively proved. A PEM constructed using electrostatic or non-electrostatic interactions from controlled deposition of a weak polyelectrolyte could retain both charged and uncharged pollutants from water. The fundamental relationship between polyelectrolyte charge density, PEM buildup interaction, and filtration performance was explored using a weak-strong electrolyte pair consisting of branching poly (ethyleneimine) and poly (styrene sulfonate) (PSS) across pH ranges of 4-10 and NaCl concentrations of 0 M-0.5 M. PEI/PSS multilayers at acidic pH were dominated by electrostatic interactions, which favored the selective removal of a charged solute, phosphate over chloride, while at alkaline pH, non-electrostatic interactions dominated, which favored the removal of oxybenzone (OXY), a neutral hydrophobic solute. The key factor determining these interactions was the charge density of PEI, which is controlled by pH and ionic strength of the deposition solutions. These findings indicate that the control of buildup interactions can largely influence the physico-chemical and transport characteristics of PEM membranes., 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 © 2023 Elsevier Ltd. All rights reserved.)

The present study involved monitoring the distribution of two widely consumed parabens (methyl paraben (MeP) and butyl paraben (BuP)) and their transformation products in indoor dust from different categories of settlement (urban, semi-urban, rural, and tribal homes). The results revealed a prevalent occurrence of parabens in all the settlement categories. A non-normal distribution pattern for MeP and BuP levels across the sampling sites was noted. While comparing the residence time of parabens in dust samples, it was found that the half-lives of the analytes were greater in the dust from urban (MeP t1/2 : 47.510 h; BuP t1/2 : 22.354 h) and rural (MeP t1/2 : 27.725 h and BuP t1/2 : 31.500 h) areas. The presence of paraben metabolites, such as hydroxy methylparaben (OH-MeP), para hydroxy benzoic acid (p-HBA), and benzoic acid (BA) in dust samples supports their transformation within indoor spaces. The average daily intake of parabens through dust ingestion and dermal absorption by children was higher than adults. BuP was the prime contributor (>85%) to the total estradiol equivalency quotient (tEEQ) in all the settlement categories., 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 © 2023. Published by Elsevier Inc.)

The degradation of recalcitrant organic pollutants by sulphate radical (SO 4 •- ) represents one of the most recent developments in oxidation-based water treatment. In most cases, persulfate (PS) acts as a precursor of sulphate radicals. This study employed ultrasound-activated PS to generate reactive species, facilitating the degradation of bisphenol S (BPS), a well-known contaminant of emerging concern (CECs). An ultrasound with a frequency of 620 kHz and 80 W power was utilised for the degradation studies. The applied oxidation system successfully resulted in the complete degradation of BPS in both pure and real environmental water samples. Additionally, the Chemical oxygen demand (COD) was reduced to an acceptable limit in both matrices, with a reduction of 85 % in pure water and 73 % in river water. The degradation was monitored by varying chemical parameters such as pH, inorganic ions, and organics concentration. The results indicate that under specific pH conditions, the degradation efficiency followed the order of pH 3 > 4 > 7 > 11. The presence of coexisting matrices suppressed the efficiency by scavenging the reactive species. Utilizing high-resolution mass spectrometry (HRMS) analysis, this study identified seven intermediate products during identified during the degradation of BPS. Furthermore, a comprehensive mechanism has been deduced for the transformation and degradation process. All the results presented in this study underscore the applicability of the US/PS system in the removal of CECs., 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 © 2023. Published by Elsevier B.V.)

The degradation of pollutants by a non-radical pathway involving singlet oxygen ( 1 O 2 ) is highly relevant in advanced oxidation processes. Photosensitizers, modified photocatalysts, and activated persulfates can generate highly selective 1 O 2 in the medium. The selective reaction of 1 O 2 with organic pollutants results in the evolution of different intermediate products. While these products can be identified using mass spectrometry (MS) techniques, predicting a proper degradation mechanism in a 1 O 2 -based process is still challenging. Earlier studies utilized MS techniques in the identification of intermediate products and the mechanism was proposed with the support of theoretical calculations. Although some reviews have been reported on the generation of 1 O 2 and its environmental applications, a proper review of the degradation mechanism by 1 O 2 is not yet available. Hence, we reviewed the possible degradation pathways of organic contaminants in 1 O 2 -mediated oxidation with the support of density functional theory (DFT). The Fukui function (FF, f - , f + , and f 0 ), HOMO-LUMO energies, and Gibbs free energies obtained using DFT were used to identify the active site in the molecule and the degradation mechanism, respectively. Electrophilic addition, outer sphere type single electron transfer (SET), and addition to the hetero atoms are the key mechanisms involved in the degradation of organic contaminants by 1 O 2 . Since environmental matrices contain several contaminants, it is difficult to experiment with all contaminants to identify their intermediate products. Therefore, the DFT studies are useful for predicting the intermediate compounds during the oxidative removal of the contaminants, especially for complex composition wastewater., 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 © 2023 Elsevier Ltd. All rights reserved.)

The molecular basis of protein unfolding on exposure to the widely used herbicide, Glyphosate (GLY), its metabolite aminomethylphosphonic acid (AMPA), and the commercial formulation Roundup have been probed using human and bovine serum albumins (HSA and BSA). Protein solutions were exposed to chemical stress at set experimental conditions. The study proceeds with spectroscopic and imaging tools. Steady-state and time-resolved fluorescence (TRF) measurements indicated polarity changes with the possibility of forming a ground-state complex. Atomic force microscopy imaging results revealed the formation of fibrils from BSA and dimer, trimer, and tetramer forms of oligomers from HSA under the chemical stress of GLY. In the presence of AMPA, serum albumins (SAs) form a compact network of oligomers. The compact network of oligomers was transformed into fibrils for HSA with increasing concentrations of AMPA. In contrast, Roundup triggered the formation of amorphous aggregates from SAs. Analysis of the Raman amide I band of all aggregates showed a significant increase in antiparallel β-sheet fractions at the expense of α-helix. The highest percentage, 24.6%, of antiparallel β-sheet fractions was present in amorphous aggregate formed from HSA under the influence of Roundup. These results demonstrated protein unfolding, which led to the formation of oligomers and fibrils., 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 © 2023 Elsevier B.V. All rights reserved.)

The investigations of protein adsorption and release on interfaces aid in the elucidation of the protein-surface interaction mechanism, which has several applications in the biomedical area. The spectro-kinetic and morphological analysis of the release of lysozyme (Lyz) from chitosan/polystyrene sulphonate (CHI/PSS) multilayer immobilized at pHs 10.6, 8.8 and 5.0 shows that the extent of release strongly depends on the pH of Lyz loading and the ionic strength of the desorbing solution. When compared to pH 8.8, the release for pH 10.6 achieves equilibrium more rapidly. At loading pH 10.6, the release is surface-mediated, at pH 8.8, it is both surface- and bulk-mediated, while at pH 5.0 it is bulk mediated with minimal release. Lyz released for loading pH 10.6 retains its native secondary structure. Kinetic fitting suggests that high loading pH 8.8-10.6 and high release ionic strength (0.5-1.0 M NaCl) lead to burst release of Lyz from CHI/PSS multilayer. Surface morphology changes of multilayer interface upon Lyz loading and release are highlighted by SEM topography and AFM height distribution analysis. The present work indicates that CHI/PSS multilayer system can function as a reservoir for burst as well as controlled release of lysozyme by selecting the loading pH and ionic strength., 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 © 2023 Elsevier B.V. All rights reserved.)

The successful evolution of an effective drug depends on its pharmacokinetics, efficiency and safety and these in turn depend on the drug-target/drug-carrier protein binding. This work, deals with the interaction of a pyridine derivative, 2-hydroxy-5-(4-methoxyphenyl)-6-phenylpyridine 3-carbonitrile (HDN) with serum albumins at physiological conditions utilizing the steady state and time-resolved fluorescence techniques by probing the emission behavior of Trp in BSA and HSA. In-silico studies revealed a combined static and dynamic quenching mechanism for the interactions. The binding studies suggests a spontaneous binding between HDN and the albumins with a moderate binding affinity (Kb ∼ 10 -5  M-1) with a single class of binding site. The FRET mediated emission from HDN indicates preferential binding of HDN in subdomain IIA of the albumins with Trp residue in close proximity. Circular dichroism results indicate HDN induced conformational changes for BSA and HSA, but the α-helical secondary structure was well preserved even up to a concentration of 10 µM HDN. Moderate binding affinity of HDN with BSA and HSA and the unaltered secondary structure of proteins on binding propose the potential application of HDN as an efficient drug. The application of docking method on the affinity of HDN towards the proposed target/receptor is discussed., (Copyright © 2022. Published by Elsevier B.V.)

Graywater reuse is one of the important concepts in attaining water sustainability. A major challenge in this area is to realize various components present in graywater. The present study involves the identification of the chemical components of graywater collected from three different environments and to investigate the efficiency of removal of some of these chemical components using ultrafiltration membranes (polyelectrolyte multilayer (PEM) membranes). The chemical components were analyzed using liquid chromatography connected with quadrupole time-of-flight (UPLC-Q-ToF-MS). A number of micropollutants including surfactants and certain contaminants of emerging concern (CECs) were identified from these samples. Out of 16 compounds identified, 13 were surfactants and the remaining were caffeine, oxybenzone, and benzophenone. These surfactants are mostly the ingredients of various detergents. Low-pressure filtration studies of the collected samples were carried out utilizing chitosan/polyacrylic acid (CHI/PAA) multilayer membranes. A 5.5 bilayer membrane showed more than 95% rejection of the identified compounds in the selected samples and significant improvement in the water quality parameters. This demonstrates that the membrane used in this work is effective in the removal of various chemicals from graywater as well as enhancing the water quality., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Copper is an essential trace element for human biology where its metal dyshomeostasis accounts for an increased level of serum copper, which accelerates protein aggregation. Protein aggregation is a notable feature for many neurodegenerative disorders. Herein, we report an experimental study using two model proteins, bovine serum albumin (BSA) and human serum albumin (HSA), to elucidate the mechanistic pathway by which serum albumins get converted from a fully folded globular protein to a fibril and an amorphous aggregate upon interaction with copper. Steady-state fluorescence, time-resolved fluorescence studies, and Raman spectroscopy were used to monitor the unfolding of serum albumin with increasing copper concentrations. Steady-state fluorescence studies have revealed that the fluorescence quenching of BSA/HSA by Cu(II) has occurred through a static quenching mechanism, and we have evaluated both the quenching constants individually. The binding constants of BSA-Cu(II) and HSA-Cu(II) were found to be 2.42 × 10 4 and 0.05 × 10 4 M -1 , respectively. Further nanoscale morphological changes of BSA mediated by oligomers to fibril and HSA to amorphous aggregate formation were studied using atomic force microscopy. This aggregation process correlates with the Stern-Volmer plots in the absence of discernible lag phase. Raman spectroscopy results obtained are in good agreement with the increase in antiparallel β-sheet structures formed during the aggregation of BSA in the presence of Cu(II) ions. However, an increase in α-helical fractions is observed for the amorphous aggregate formed from HSA., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Indoor dust is an important matrix that exposes humans to a broad spectrum of chemicals. The information on the occurrence of contaminants of emerging concern (CECs), their metabolites, and re-emerging contaminants in indoor dust is rather limited. As the indoor environment is exposed to various chemicals from personal care products, furniture, building materials, machineries and cooking/cleaning products, there is a high chance of the presence of hazardous contaminants in indoor dust. In the present study, dust samples were collected from four different micro indoor environments (photocopying centres, residential houses, classrooms, and ATM cabins) located in an urban environment located in India's southwestern part. The collected samples were subjected to ATR - FTIR and LC-Q-ToF-MS analyses. The ATR - FTIR analysis indicated the presence of aldehydes, anhydrides, carboxylic acids, esters, sulphonic acids, and asbestos - a re-emerging contaminant. A total of 19 compounds were identified from the LC-Q-ToF-MS analysis. These compounds belonged to various classes such as plasticisers, plasticiser metabolites, photoinitiators, personal care products, pharmaceutical intermediates, surfactants, and pesticides. To the best of our knowledge, this is the first report regarding the presence of CECs in indoor environments in Kerala and also the suspected occurrence of pesticides (metaldehyde and ethofumesate) in classroom dust in India. Another important highlight of this work is the demonstration of ATR-FTIR as a complementary technique for LC-Q-ToF-MS in the analysis of indoor pollution while dealing with totally unknown pollutants. These results further highlight the occurrence of probable chemically modified metabolites in the tropical climatic conditions in a microenvironment., 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 © 2021. Published by Elsevier B.V.)

Extensive use of surfactants in numerous fields resulted in their discharge into various environmental compartments including soil, sediment, and water. Alcohol ethoxysulfates (AES) together with alcohol ethoxylates (AE), alkyl sulfates (AS), and linear alkyl benzene sulfonates (LAS) find wide variety of applications in consumer products including both domestic and industrial applications. Consequently, all these surfactants pose several concerns to both aquatic and human health. In the context of environmental impacts, AES has almost equal importance as that of LAS though the literature on this topic is only emerging. This review provides a detailed overview on the various aspects of the anionic surfactant, AES, such as toxicity of AES, its fate in the ecosystem, technical advancements in the area of identification and quantification, its occurrence and distribution in different environmental compartments spanning across the world, and finally a remark of its potential removal strategy from the environment., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Heavy metal based toxicity has a direct relation with the perturbation of protein structure. We have investigated the progressive unfolding of ovalbumin, in the presence of increasing concentration mercury (0-6.25 μM) using different spectroscopic techniques. Formation of amorphous aggregate has been observed at the physiological pH. Initial addition of HgCl 2 resulted in the association of monomers to oligomers that proceeded to non-fibrillar aggregates on further addition. The sigmoidal curve obtained from the Stern-Volmer plot clearly divided into three stage transition. A strong lag phase is observed indicating the time dependence for the association of competent monomers. The second stage was resolved into non-cooperative binding. These results match very well with the data from atomic force microscopy and the free energy change observed in the regions. Raman spectroscopic studies indicated toxic antiparallel β-sheets structure. Time dependent atomic force microscopy study revealed the off-pathway nature of amorphous aggregates. At molten globular state, similar quenching behaviour is observed. The atomic force microscopy images clearly indicate at pH 2.2 the initiation of fibril formation occurs at lower concentration of HgCl 2 itself. Our results revealed the conformation switch of ovalbumin upon the contact of an environmental toxin and its possible way of toxicity., Competing Interests: Declaration of competing interest The authors declare no competing financial interests., (Copyright © 2021 Elsevier B.V. All rights reserved.)

A low saline backwater canal, mainly utilized for domestic and agricultural purposes, has been analyzed for the possible presence of organic micropollutants (OMP) and their potential removal was explored by multilayered microfiltration membranes. The qualitative as well as quantitative analysis were carried out for a span of one year using the technique of liquid chromatography connected with high resolution mass spectrometry (LC-Q-TOF-MS). The identification of the formally unknown compounds was initially done using non-target analysis based on the mass accuracy, isotopic pattern and MS/MS spectral interpretation. Results of the non target screening revealed the presence of 11 OMPs. Five of these OMPs were confirmed using standards; these include chlorophene (CHP), oxybenzone (OXY), N, N-diethyl-meta-toluamide (DEET), N, N-diethyl-benzamide (DEB) and dibutyl phthalate (DBP). Among the confirmed OMPs, the highest concentration was observed for DBP (244.61 ng l -1 ). The most frequently observed OMP in the study area was DBP while the least was DEB which is an insect repellent as well as a degradation product of DEET. The ecological risk associated with the target compounds has also been analyzed by calculating the risk quotient (RQ) and the results revealed that at the detected levels, these compounds are capable of causing low to medium risk. Low pressure (<0.3 bar) filtrations of the compounds were attempted using microfiltration (MF) and, poly(ethyleneimine)/poly(styrene sulfonate) (PEI/PSS) multi-layered MF membrane for spiked ultrapure water and also for natural water from the back-water canal. The batch mode illustrates nearly complete removal of CHP and OXY in spiked solutions and a good removal efficiency from natural water. The effect of coexisting ions and surfactants in feed is also illustrated. The high efficiency of the removal of both CHP and OXY, in such a complex medium highlights the potential application of the present method for the removal of similar OMPs in natural waters., 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. Published by Elsevier B.V.)

Degradation of benzenesulfonic acid (BSA), the simplest aromatic sulfonic acid with extreme industrial importantance, by sonochemically generated hydroxyl radical (OH) have been thoroughly investigated. A reasonable reduction (∼50%) in the total organic carbon (TOC) was achieved only after prolonged irradiation (∼275 min, 350 kHz) of ultrasound, although a short irradiation of less than an hour is enough to degrade significant amount of BSA. The degradation efficiency of ultrasound has been reduced in lower and extremely higher frequencies, and upon increasing the pH. An irregular, but continuous, release of sulfate ions was also observed. Further, the release of protons upon the oxidation of BSA consistently reduces the experimental pH to nearly 2. High resolution mass spectrometric (HRMS) analyses reveals the formation of a number of aromatic intermediates, including three mono (I a-c ) and two di (II a&b ) hydroxylated BSA derivatives as the key products in the initial stages of the reaction. Pulse radiolysis studies revealed the generation of hydroxycyclohexadienyl-type radicals, characterized by absorption bands at 320 nm (k 2  = (7.16 ± 0.04) × 10 9  M -1  s -1 ) and 380 nm, as the immediate intermediates of the reaction. The mechanism(s) leading to the degradation of BSA under sonolytic irradiation conditions along with the effect of various factors, such as the ultrasound frequency and reaction pH, have been explained in detail. The valuable mechanistic aspects obtained from our pulse radiolysis and HRMS studies are essential for the proper implementation of sonochemical techniques into real water purification process and, thus, receives extreme environmental relevance., 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.)

The intriguing resemblances of amyloid fibrils and spider silk in protein aggregation diseases have instigated the exploration of identical structural features if any in their oligomeric pathways. The serpin group protein, ovalbumin, on defolding in HgCl 2 shares commonness to the micellar pathway of spidroins for their aggregation in response to a pH trigger. The structural feature changes from monomer to worm like fibril with a shift in the primary protein pH to slightly acidic pH (4.5), and then proceeds through a secondary nucleation pathway to 'hillock' and 'hydra' like protofibrils rich in β-sheet and random coil conformers upon exposure to mercury. The findings are backed by atomic force microscopy, confocal Raman spectroscopy and fluorescence measurements. Unlocking such structural features can favorably assist in the design of therapeutics., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Layer by layer (LbL) assembly can be regarded as an emerging technology for the separation of organic micro-pollutants from water. Direct assembly of polyelectrolytes (PEs) under LbL mode on natural support material is rare. Here we report the integration of LbL to one of the most resourceful support materials that might have an enduring impact on water treatment in color industry. A low-cost adsorbent is developed from chitosan (CHI) and polyacrylic acid (PAA) through LbL deposition on coir fiber (CF) by alternate exposure to their aqueous solutions. Their layer dependent formation is characterized by spectroscopic and microscopic techniques. CHI/PAA multilayer coated coir fiber or simply, layered coir fiber (LCF) showed high loading of cationic and anionic dyes both at acidic and alkaline loading pH. The loading was between 70% and 99% at the acidic pH 3 which is attributed to the binding between LCF and dye molecules by electrostatic and hydrophobic forces. The performance of LCF in presence of NaCl, Na 2 SO 4 and sodium dodecyl sulfate (SDS) in dye solution is discussed. Textile industrial waste water showed significant reduction in dye (81%) content along with COD (84%) and TDS., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Triphenylmethane (TPM) dyes are an important category of dyes with a variety of industrial applications and consequently, these are found in the aquatic environment at relatively higher concentrations. Here, we report the degradation of two important TPM dyes (para rosaniline (PRA) and ethyl violet (EV)) in an aqueous medium by ultrasound which is one among the Advanced Oxidation Processes (AOPs). The main objective of this work is to study the effect of various inorganic ions on the degradation and the product formation of TPM dyes from the sonochemical reactions. Using a typical concentration of 10 ppm dyes and an ultrasonic frequency of 350 kHz and power of 60 W, a complete degradation of EV and PRA was observed with a pseudo first order rate constant of 0.2339 min -1 and 0.1956 min -1 , respectively. The product analyses using high-resolution mass spectrometry (LC-Q-TOF-MS) revealed the formation of hydroxylated, de-alkylated, and other collapsed conjugated structure destructed products. The evolution of these products in the presence of various inorganic ions (Cl - , SO 4 2- , NO 3 - , and CO 3 - ) showed that only carbonate ions had a significant impact on the product evolution. The carbonate ions facilitated the formation of conjugated structure destructed product for both the dyes. This is attributed to the reactivity of carbonate radical, which facilitated the formation of carbon-centered radicals. This carbon-centered radical further undergoes reaction to cause the destruction of conjugated structures. This is confirmed by the identification of the corresponding product peaks in the mass spectra. The scavenging effect of carbonate ions was also reflected in the product study where there is a reduction in the formation of most of the hydroxylated products. One of the major inorganic species in any wastewater is carbonate ions and therefore the present result is very relevant to the understanding of oxidation based treatment protocol., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The present study describes the monitoring of some of the major classes of surfactants in water. The separation, identification, and the quantitative estimation of the compounds were achieved using LC-Q-ToF-MS. The analyses revealed the presence of variety of surfactants including linear alkylbenzene sulfonate (LAS), alcohol ethoxysulfates (AES), and alcohol ethoxylates (AE). Further, emphasis was given to AES as they are one of the most produced and consumed surfactants in the world. And as far as India is concerned, the present study is one of the most significant attempt regarding the identification and quantification of AES. The data obtained during the analysis revealed that the average concentration of AES C12Ex varied from 0.7 to 13.6 μg L -1 while that of C14Ex ranged between 1.3 and 10.4 μg L -1 . The risk assessment revealed that higher chain AES are capable of posing medium level risk to the aquatic compartment. In addition, the study also included the physicochemical analysis of water from the selected area. Water was found to be acidic in nature and the salinity, TDS, and EC values were found to be high during the pre-monsoon season. The order of the levels of anionic constituents was of Cl - >SO 4 2- SO 4 2- >F - >NO 3 2- ≅ PO 4 2- while that of cations were Na +  > Mg 2+  > K +  > Ca 2+ . Results of correlation analysis showed that statistically negative correlation exists between AES homologs and pH while slight positive correlations were found between AES and other parameters including TDS and EC. The suitability of this water for domestic and agricultural purposes has been examined on the ground of basic quality indices such as the water quality index (WQI) and sodium adsorption ratio (SAR). The WQI measurements also revealed that the water quality of the region falls under the "very poor" category especially during the pre-monsoon season. The study could explore the cumulative share of these canals in the quality impairment of the receiving Vembanad Lake.

The presence of emerging contaminants (ECs) in different aquatic systems may contribute to hazardous effects on aquatic organisms and subsequently on human health. In the present work, liquid chromatography coupled to a quadrupole time of flight mass spectrometer (LC-Q-ToF-MS) was used to identify and quantify a series of ECs in Periyar River in Aluva region, Kerala, India. The water samples were pre concentrated using solid-phase extraction (SPE) prior to analysis. The compounds were probed in both positive and negative ionization mode using electro spray ionization (ESI). Method validations were performed for linearity, limit of detection (LOD), limit of quantification (LOQ), accuracy, and precision (intraday and inter day). The ECs were quantified using standard calibration curve. The identified nine ECs include pharmaceuticals, personal care products, steroids, surfactants, and phthalate. A relatively high concentration was observed in the case of 2-dodecyl benzene sulfonic acid (1012 ng/l) and low concentration was observed for lignocaine (4.3 ng/l; since this is below LOQ, the value is only approximate). In addition, we have identified another 28 organic compounds using the technique of non-target analysis out of which seven compounds fall in the category of surfactants. Being the first report on ECs in Periyar River, the data is very important as this river is one of the biggest and important rivers of Kerala having several purification units for drinking water in the province.

The sonochemical transformation of para-aminosalicylic acid (PAS), a widely used antibiotic and an identified Emerging Pollutant (EP) under the class of Pharmaceuticals and Personal Care Products (PPCPs), have been investigated in aqueous medium. Ultrasound having frequency of 350kHz and power of 80W was utilized for the degradation of PAS. A complete degradation (100%) of PAS after 60min and about 83% of COD removal after 120min of sonication, were obtained. Fourteen intermediate products were identified using LC-Q-TOF-MS. On a comparison with UV/H 2 O 2 method, it is understood that four products out of fourteen were nitro derivatives which are formed only in the sonolysis, and the rest are from hydroxyl radicals. The involvement of nitrite which is formed from the sonolysis of solution containing PAS, in the formation of the other four nitro products has been established from the control studies. Nitrite ion partially scavenge hydroxyl radical in the course of the reaction to form nitrite radical which is the reactive species for the production of nitro compounds. It is, therefore, proposed that in addition to hydroxyl radical, contribution of in-situ generated nitrite also plays an important role in the sonochemical transformation of PAS., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The emergence of issues related to environment from ECs is a topic under serious discussions worldwide in recent years. Indian scenario is not an exception as it is tremendously growing in its rate of production and consumption of compounds belongs to ECs categories. However, a comprehensive documentation on the occurrence of ECs and consequent ARGs as well as their toxic effects on vertebrates on Indian context is still lacking. In the present study, an extensive literature survey was carried out to get an idea on the geographical distribution of ECs in various environmental matrices (water, air, soil, sediment and sludge) and biological samples by dividing the entire subcontinent into six zones based on climatic, geographical and cultural features. A comprehensive assessment of the toxicological effects of ECs and the consequent antibiotic resistant genes has been included. It is found that studies on the screening of ECs are scarce and concentrated in certain geological locations. A total of 166 individual compounds belonging to 36 categories have been reported so far. Pharmaceuticals and drugs occupy the major share in these compounds followed by PFASs, EDCs, PCPs, ASWs and flame retardants. This review throws light on the alarming situation in India where the highest ever reported values of concentrations of some of these compounds are from India. This necessitates a national level monitoring system for ECs in order to assess the magnitude of environmental risks posed by these compounds., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Pollution and fate of pollutants in polar region are important topics of investigation in the last several decades. We have analysed sediment samples from Kongsfjorden and Krossfjorden, two sites from Arctic region, and detected a number of emerging contaminants (ECs) using high-resolution mass spectrometry connected to UPLC (LC-Q-ToF-MS). Out of the seven sampling sites selected, bisphenol S (BPS), an identified pollutant and plasticiser, was detected and quantified in three sediment samples from Kongsfjorden (≈ 0.2 ppm). Four major surfactants (decylbenzenesulphonic acid, undecylbenzenesulphonic acid, 2-dodecylbenzenesulphonic acid and tridecylbenzenesulphonic acid) were also identified. A possible metabolite of BPS (sulphur trioxide derivative of BPS) was identified in one of the samples. It is proposed that the presence of ECs is the result of human activities in the region for a long time. To the best our knowledge, this is the first report on the identification of BPS and surfactants in the Arctic region.

The heterogeneous catalytic degradation of a model azo dye, acid red 1 (AR1), initiated by zero valent iron nanoparticles (ZVINP), and its synergic effect with ultrasound (US) have been investigated in the present study. The treatment of AR1 using ZVINP at pH 3 showed maximum efficiency in terms of colour removal (53.0%) and mineralization (48.5% TOC reduction) after 25 min of reaction. However, the coupling of this system with US showed an enhanced efficiency against the decolourization and mineralization of AR1. More than 95% colour removal was achieved within 5 min in the case of US/ZVINP system. Around 55% TOC reduction suggests the conversion of the parent molecules in to aromatic transformed products, and it is further supported by LC-Q-TOF analysis. The remarkably higher efficiency in the coupled system is attributed to the synergic effect of ZVINPs and ultrasound. The highest degradation rates observed at highly acidic (pH 3) and alkaline pH (pH 9) suggests that different mechanisms are operating at both pH. The products identified gave some insight into the mechanism. The ZVINPs prepared in the present study was easily recoverable (and reusable) and hence may be considered as an effective replacement for the conventional Fenton's reagent.

Ultrasound is known to degrade organic compounds by pyrolysis and by the reaction of free radicals. In this work, sonolytic degradation of an identified water pollutant, coomassie brilliant blue (CBB), has been carried out in pure water as well as in river water. In the case of pure water, 90 % degradation was obtained after 30 min of sonication (350 kHz frequency, 60 W power), whereas in river water, the same efficiency was achieved only after 90 min. The degradation was also performed in the presence of varying concentration of (10-100 mg L -1 ) inorganic ions such as chloride, sulfate, nitrate, bicarbonate, and carbonate ions which were detected in the river water sample. Higher concentration of chloride enhanced the degradation due to the salting out mechanism. The enhancement of degradation in the presence of nitrate is mainly due to the change in the surface potential at the interface of the cavitating bubble. Bicarbonate ion and carbonate ion enhanced the degradation due to the involvement of carbonate radicals. A possible degradation mechanism is proposed based on the product profile determined by LC-Q-ToF-MS. The low efficiency of degradation in river water compared to that in pure water is likely due to the increased rate of bubble dissolution or escape of bubbles (degassing effect), and the scavenging of • OH by the organic content (high chemical oxygen demand (COD)).

The study on the possible pathway of hydroxyl radicals mediated sonolytic degradation of paraben in water is reported. Methylparaben (MPB) which is the most utilized of paraben family is selected as a model emerging pollutant. The influence of common anions and some selected emerging contaminants that may coexist in typical water matrix on the degradation pattern is analyzed alongside. Among the anions, carbonate presents a negative influence which is attributed to the competition for OH radical. Some emerging contaminants also showed negative impact on degradation as was clear from HPLC data. The intermediates, analyzed by LC-Q-TOF-MS include hydroxylated and hydrolytic products. Three major steps (aromatic hydroxylation, hydroxylation at the ester chain and hydrolysis) are proposed to involve in the reaction of OH radical with MPB which ultimately leads to mineralization. The intensity of formation and decay of mono and dihydroxy products of MPB in the presence of additives have also been evaluated. COD analysis indicates a percentage reduction of 98% at 90 min of sonolysis and further increase in the degradation time resulted complete mineralization, which became evident from the mass spectrometric data. MTT assay revealed considerable decrease in the potential cytotoxicity., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Ultrasound is extensively used in medical field for a number of applications including targeted killing of cancer cells. DNA is one of the most susceptible entities in any kind of free radical induced reactions in living systems. In the present work, the transformation of thymidine (dT) induced by ultrasound (US) was investigated using high resolution mass spectrometry (LC-Q-ToF-MS). dT was subjected to sonolysis under four different frequencies (200, 350, 620 and 1000 kHz) and at three power densities (10.5, 24.5 and 42 W/mL) in aerated as well as argon saturated conditions. A total of twenty modified nucleosides including non-fully characterized dT dimeric compounds were detected by LC-Q-ToF-MS. Out of these products, seven were obtained only in the argon atmosphere and two only in the aerated conditions. Among the identified products, there were base modified products and sugar modified products. The products were formed by the reaction of hydroxyl radical and hydrogen atom. Under aerated conditions, the reactions proceed via the formation of hydroperoxides, while in argon atmosphere disproportionation and radical recombinations predominate. The study provides a complete picture of sonochemical transformation pathways of dT which has relevance in DNA damage under ultrasound exposure., (Copyright © 2015 Elsevier B.V. All rights reserved.)

This study reports an energy-resolved mass spectrometric (ERMS) strategy for the characterization of position isomers derived from the reaction of hydroxyl radicals ((●)OH) with diphenhydramine (DPH) that are usually hard to differentiate by other methods. The isomer analogues formed by (●)OH attack on the side chain of DPH are identified with the help of a specific fragment ion peak (m/z 88) in the collision-induced dissociation (CID) spectrum of the protonated molecule. In the negative ion mode, the breakdown curves of the deprotonated molecules show an order of stability (supported by density functional theory (DFT) calculations) ortho > meta > para of the positional isomers formed by the hydroxylation of the aromatic ring. The gas phase stability of the deprotonated molecules [M - H](-) towards the benzylic cleavage depends mainly on the formation of intramolecular hydrogen bonds and of the mesomeric effect of the phenol hydroxyl. The [M - H](-) molecules of ortho and meta isomers result a peak at m/z 183 with notably different intensities because of the presence/absence of an intramolecular hydrogen bonding between the OH group and C9 protons. The ERMS approach discussed in this report might be an effective replacement for the conventional methods that requires very costly and time-consuming separation/purification methods along with the use of multi-spectroscopic methods., (Copyright © 2015 John Wiley & Sons, Ltd.)

An accurate, sensitive, precise, reliable, and quick method for the determination of cholesterol content by high-performance thin layer chromatography is developed. In this method, aluminum-backed precoated silica gel 60 F 254 plates were used as the stationary phase and the samples were sprayed with the help of CAMAG sample applicator Linomat 5. The chromatogram was developed with the mobile phase consisting of chloroform:methanol (9.5:0.5, v/v). The samples were detected using CAMAG Scanner 4 and evaluated using the method developed on winCATS software. Densitometric analysis of cholesterol was performed in absorbance mode at 200 nm. In this solvent system, cholesterol gave a compact spot with an R f value of 0.63 ± 0.03. The linear regression analysis of data for the calibration curve showed good linearity over a concentration range of 2-7 μg/spot with a regression value of 0.99933 and standard deviation of 1.44%. The limit of detection and limit of quantification were found to be 100 ng/spot and 500 ng/spot, respectively. Using the developed method, the concentration of cholesterol in the saponified and unsaponified egg yolk sample was determined. This method was found to be reproducible and can even be used for samples containing complex matrices., (Copyright © 2014. Published by Elsevier B.V.)

The development of a sustainable membrane surface based on chitosan/poly(acrylic acid) (CHI/PAA) multilayers suitable for applications in analytical separations is reported here. Bilayers are constructed on polyamide microfiltration membranes at a pH combination of 3/3 (CHI pH/PAA pH) through a layer by layer approach. A 12.5 bilayer yielded a thickness of 400 nm. Low pressure (10 psi) filtrations through a 5.5 bilayered membrane exhibited high flux (7 m(3) m(-2) day(-1)) and selectivity (NaCl/reactive black 5 (RB5) selectivity >8000). The selectivity and flux observed here are the highest reported to date for low pressure filtrations through membranes. The increase in flux with increasing feed salt concentration is correlated with morphological transformations. Salt content above 7500 ppm causes some perturbation of surface layers. The presence of RB5, a model dye in the feed, restores the surface to maintain sustainability. A skin layer as thin as 50 nm imparts a large separation window. An RB5 feed concentration of 500 ppm results in 98.64% rejection with a flux of 25.79 m(3) m(-2) day(-1). The increase in flux with feed dye concentration supports the plasticizing action of RB5. The transport studies with large feed dye concentrations indicate that at a dye concentration of 500 ppm, the linear growing region (pre-exponential, 5.5 bilayer) itself provides a separation window similar to that of 100 ppm. At the same time, 1000 ppm requires a 9.5 bilayer that falls in the nonlinear growing region. Scanning electron microscopy images show the increase in porosity with respect to feed dye. Interesting morphologies that show the sustainable nature of the membrane surfaces along with the transport data of RB5 are presented.

Coomassie Brilliant Blue (CBB), discharged mainly from textile industries, is an identified water pollutant. Ultrasound initiated degradation of organic pollutants is one among the promising techniques and forms part of the Advanced Oxidation Processes (AOPs). Ultrasonic degradation of CBB under different experimental conditions has been investigated in the present work. The effect of frequency (200 kHz, 350 kHz, 620 kHz and 1 MHz) and power density (3.5 W mL(-1), 9.8 W mL(-1) and 19.6 W mL(-1)) on the degradation profile was evaluated. The optimum performance was obtained at 350 kHz and 19.6 W mL(-1). Similar to other sonolytic degradation of organic pollutants, maximum degradation of CBB was observed under acidic pH. The degradation profile indicated a pseudo-first order kinetics. The addition of ferrous ion (1×10(-4) M), hydrogen peroxide (1×10(-4) M), and peroxodisulphate (1×10(-4) M) had a positive effect on the degradation efficiency. The influence of certain important NOM like SDS and humic acid on the sonolytic degradation of CBB was also investigated. Both the compounds suppress the degradation efficiency. LC-Q-TOF-MS was used to identify the stable intermediate products. Nearly 13 transformed products were identified during 10min of sonication using the optimized operational parameters. This product profile demonstrated that most of the products are formed mainly by the OH radical attack. On the basis of these results, a degradation mechanism is proposed., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Oxidative destruction and mineralization of emerging organic pollutants by hydroxyl radicals (˙OH) is a well established area of research. The possibility of generating hazardous by-products in the case of ˙OH reaction demands extensive investigations on the degradation mechanism. A combination of pulse radiolysis and steady state photolysis (H2O2/UV photolysis) followed by high resolution mass spectrometric (HRMS) analysis have been employed to explicate the kinetic and mechanistic features of the destruction of theophylline, a model pharmaceutical compound and an identified pollutant, by ˙OH in the present study. The oxidative destruction of this molecule, for intermediate product studies, was initially achieved by H2O2/UV photolysis. The transient absorption spectrum corresponding to the reaction of ˙OH with theophylline at pH 6, primarily caused by the generation of (T8-OH)˙, was characterised by an absorption band at 330 nm (k2 = (8.22 ± 0.03) × 10(9) dm(3) mol(-1) s(-1)). A significantly different spectrum (λmax: 340 nm) was observed at highly alkaline pH (10.2) due to the deprotonation of this radical (pKa∼ 10.0). Specific one electron oxidants such as sulphate radical anions (SO4˙(-)) and azide radicals (N3˙) produce the deprotonated form (T(-H)˙) of the radical cation (T˙(+)) of theophylline (pKa 3.1) with k2 values of (7.51 ± 0.04) × 10(9) dm(3) mol(-1) s(-1) and (7.61 ± 0.02) × 10(9) dm(3) mol(-1) s(-1) respectively. Conversely, oxide radicals (O˙(-)) react with theophylline via a hydrogen abstraction protocol with a rather slow k2 value of (1.95 ± 0.02) × 10(9) dm(3) mol(-1) s(-1). The transient spectral studies were complemented by the end product profile acquired by HRMS analysis. Various transformation products of theophylline induced by ˙OH were identified by this technique which include derivatives of uric acids (i, iv & v) and xanthines (ii, iii & vi). Further breakdown of the early formed product due to ˙OH attack leads to ring opened compounds (ix-xiv). The kinetic and mechanistic data furnished in the present study serve as a basic frame work for the construction of ˙OH induced water treatment systems as well as to understand the biological implications of compounds of this kind.

Purpose: The hydroxyl radical ((●)OH)-induced oxidation reactions of isomeric hydroxy naphthoquinones (generally having anti-tumor activities) namely, lawsone and juglone, were carried out and the reaction mechanism was elucidated., Materials and Methods: The degradation products from the reaction of (●)OH (produced by H(2)O(2)/UV) with lawsone and juglone were analyzed using a liquid chromatography quadrupole-time-of-flight mass spectrometer (LC-Q-TOF-MS). The transient intermediate studies were investigated using picosecond pulse radiolysis technique., Results: Mono hydroxylated and dihydroxylated adducts of both lawsone and juglone were identified from the product analysis. The isomeric mono-hydroxylated adducts of lawsone were confirmed using survival yield (SY) analysis. The hydroxylated adducts of lawsone also underwent dimerization reaction. The transient spectral analysis using pulse radiolysis studies revealed the formation of hydroxycyclohexadienyl type radical of both lawsone and juglone as the initially formed intermediate., Conclusions: The (●)OH-induced reactions of both lawsone and juglone result in the mono and di-hydoxylated derivatives. The demonstration of the various isomeric products using mass spectrometry is a clear proof of the addition probability of (●)OH at different positions of lawsone and juglone, which is generally a difficult task using other analytical techniques.

The interaction of bisphenol-S (BPS) with serum albumins using steady-state, synchronous, time-resolved, and circular dichroism spectroscopies has been investigated. The binding interactions have also been investigated in the case of bisphenol A (BPA). The fluorescence quenching pathways are different for both of these endocrine disrupting compounds. Steady-state and time-resolved studies reveal static quenching at lower concentrations of BPS and dynamic quenching at higher concentrations. CD results also maintained the concentration dependent variation with a complete distortion of α-helices at 10(-5) M BPS. Besides this, addition of sodium dodecyl sulfate (SDS) results in the further unfolding of protein in the case of BPS, whereas time-resolved studies indicated refolding for BPA denatured human serum albumin (HSA). The entire study indicates an irreversible binding of BPS with HSA. Hence, these results reveal the possible involvement of BPS in the physiological pathway raising a health threat as already their presences in body fluids are known.

Atenolol is a β-blocker drug and an identified emerging pollutant. Advanced oxidation processes (AOPs) utilise the reaction of a highly oxidising species (hydroxyl radicals, (•)OH) for the mineralisation of emerging pollutants since conventional treatment methodologies generally fail to degrade these compounds. In the present work, degradation of atenolol was carried out using ultrasound with frequencies ranging from 200 kHz to 1 MHz as a source of hydroxyl radical. The degradation was monitored by HPLC, total organic carbon (TOC) and chemical oxygen demand (COD) reduction and ion chromatography (IC). Nearly 90 % of degradation of atenolol was observed with ultrasound having 350 kHz. Both frequency and power of ultrasound affect the efficiency of degradation. Nearly 100 % degradation was obtained at a pH of 4. Presence of various additives such as sodium dodecyl sulphate, chloride, sulphate, nitrate, phosphate and bicarbonate was found to reduce the efficiency of degradation. Although nearly 100 % degradation of atenolol was observed under various experimental conditions, only about 62 % mineralisation (from TOC and COD measurements) was obtained. Nearly eight intermediate products were identified using high-resolution mass spectrometry (LC-Q-TOF). These products were understood as the results of hydroxyl radical addition to atenolol. The degradation studies were also carried out in river water which also showed a similar degradation profile. A mechanism of degradation and mineralisation is presented.

The transients formed during the reactions of oxidizing radicals with 1-naphthol (1) and 2-naphthol (2) in aqueous medium have been investigated by pulse radiolysis with detection by absorption spectroscopy and density functional theory (DFT) calculations. The transient spectra formed on hydroxyl radical ((•)OH) reactions of 1 and 2 exhibited λ(max) at 340 and 350 nm at neutral pH. The rate constants of the (•)OH reactions of 1 (2) were determined from build-up kinetics at λ(max) of the transients as (9.63 ± 0.04) × 10(9) M(-1) s(-1) ((7.31 ± 0.11) × 10(9) M(-1) s(-1)). DFT calculations using the B3LYP/6-31+G(d,p) method have been performed to locate favorable reaction sites in both 1 and 2 and identification of the pertinent transients responsible for experimental results. Calculations demonstrated that (•)OH additions can occur mostly at C1 and C4 positions of 1, and at C1 and C8 positions of 2. Among several isomeric (•)OH adducts possible, the C1 adduct was found to be energetically most stable both in 1 and 2. Time-dependent density functional theory (TDDFT) calculations in the solution phase has shown that the experimental spectrum of 1 was mainly attributed by 1a4 (kinetically driven (•)OH-adduct) formed via the addition of (•)OH at the C4 position which was 0.73 kcal/mol endergonic compared to 1a1 (thermodynamic (•)OH adduct), whereas 2a1 (thermodynamic/kinetic (•)OH-adduct) was mainly responsible for the experimental spectrum of 2. Naphthoxyl radicals of 1 and 2 have been predicted as the transient formed in the reaction of (•)OH at basic pH. In addition, the same transient species resulted from the reactions of oxide radical ion (O(•-)) at pH ≈ 13 and azide radical (N3(•)) at pH 7 with 1 and 2. Further, UV photolysis of aqueous solutions of 1 and 2 containing H2O2 (UV/H2O2) were used for the (•)OH induced oxidation product formations up on 60% degradations of 1 and 2; profiling of the oxidation products were performed by using an ultraperformance liquid chromatography quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS) method. According to the UPLC-Q-TOF-MS analyses, the preliminary oxidation products are limited to dihydroxy naphthalenes and naphthoquinones with N2-saturation, while some additional products (mainly isomeric monohydroxy-naphthoquinones) have been observed in the degradations of 1 and 2 in the presence of O2. We postulate that dihydroxy naphthalenes are derived explicitly from the most favorable (•)OH-adducts speculated (preference is in terms of the kinetic/thermodynamic dominancy of transients) by using theoretical calculations which in turn substantiate the proposed reaction mechanisms. The observations of (•)OH-adducts for an aromatic phenol (herein for both 1 and 2 at pH 7) rather than phenoxyl type radical in the pulse radiolysis experiments is a distinct and unique illustration. The present study provides a meaningful basis for the early stages associated with the (•)OH initiated advanced oxidation processes of 1- and 2-naphthols.

The use of ovalbumin (OVA)-immobilized layer-by-layer-assembled chitosan/polystyrene sulfonate membranes for the detection of hydrogen peroxide (H2O2) at subpicomolar levels is reported. The detection of mercuric chloride (HgCl2) and potassium iodide (KI) was also investigated. While the detection limits of HgCl2 and KI remained in the micromolar concentration range, H2O2 could be sensed to a remarkably lower range (subpicomolar). Analysis of fluorescence quenching data of OVA by H2O2 using Stern-Volmer plots revealed a static quenching mechanism with high Stern-Volmer quenching constant (9.10×10(12) L mol(-1)) and k (5.82×10(21) L mol(-1) s(-1)). The possibility of the conformational transition of OVA in the immobilized state is discussed using steady-state and time-resolved spectroscopic techniques. The resulting increased accessibility of tryptophan residues together with the reversibility of the bilayer for the sensing of H2O2 is also illustrated., (Copyright © 2013 Elsevier Inc. All rights reserved.)

Oxidative degradation of fensulfothion, a model organophosphorus compound, has been investigated by pulse radiolysis and H2O2/UV photolysis. A nearly complete transformation of fensulfothion was observed within 4min of irradiation. Very little Total Organic Carbon (TOC) reduction was obtained at this time scale. When the product studies at this stage were conducted using LC-MS/MS analyses, nearly 20 transformation products were obtained. The entire products were identified as from the reaction of OH with fensulfothion or with some of its initially transformed products. Nearly 80% reduction in TOC was observed when photolysis was conducted using higher concentrations of H2O2 at longer time scale. A reaction rate constant (bimolecular) of 1.10×10(10)dm(3)mol(-1)s(-1) was obtained for the reaction of OH with fensulfothion using pulse radiolysis technique. The transient absorption spectrum obtained from the reaction of OH has a maximum at 280nm and a weak, broad maximum around 500nm along with a small shoulder around 340nm. The intermediate spectrum is assigned to the radical cation of fensulfothion (3) and the hydroxyl radical adducts (1 and 2). This assignment is supported by the intermediate spectrum (λmax at 280nm) from the reaction of sulfate radical anion (SO4(-)) (k2=3.20×10(9)dm(3)mol(-1)s(-1)) which is a one electron oxidant. It is thus demonstrated that the combination of both pulse radiolysis and the product estimation using LC-MS/MS is ideal in probing the complete mechanism which is very important in the mineralization reactions using Advanced Oxidation Processes., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The reactions of (•)OH and O(•-), with thymol, a monoterpene phenol and an antioxidant, were studied by pulse radiolysis technique and DFT calculations at B3LYP/6-31+G(d,p) level of theory. Thymol was found to efficiently scavenge OH radicals (k = 8.1 × 10(9) dm(3) mol(-1) s(-1)) to produce reducing adduct radicals, with an absorption maximum at 330 nm and oxidizing phenoxyl radicals, with absorption maxima at 390 and 410 nm. A major part of these adduct radicals was found to undergo water elimination, leading to phenoxyl radicals, and the process was catalyzed by OH(-) (or Na(2)HPO(4)). The rate of reaction of O(•-) with thymol was found to be comparatively low (k = 1.1 × 10(9) dm(3) mol(-1) s(-1)), producing H abstracted species of thymol as well as phenoxyl radicals. Further, these phenoxyl radicals of thymol were found to be repaired by ascorbate (k = 2.1 × 10(8) dm(3) mol(-1) s(-1)). To support the interpretation of the experimental results, DFT calculations were carried out. The transients (both adducts and H abstracted species) have been optimized in gas phase at B3LYP/6-31+G(d,p) level of calculation. The relative energy values and thermodynamic stability suggests that the ortho adduct (C6&#95;OH adduct) to be most stable in the reaction of thymol with OH radicals, which favors the water elimination. However, theoretical calculations showed that C4 atom in thymol (para position) can also be the reaction center as it is the main contributor of HOMO. The absorption maxima (λ(max)) calculated from time-dependent density functional theory (TDDFT) for these transient species were close to those obtained experimentally. Finally, the redox potential value of thymol(•)/thymol couple (0.98 V vs NHE) obtained by cyclic voltammetry is less than those of physiologically important oxidants, which reveals the antioxidant capacity of thymol, by scavenging these oxidants. The repair of the phenoxyl radicals of thymol with ascorbate together with the redox potential value makes it a potent antioxidant with minimum pro-oxidant effects.

This work illustrates the potential use of PEI/PSS bilayers assembled via layer by layer (lbl) method on a nylon microfiltration membrane for the recovery of phosphate from water in the presence of chloride under ultrafiltration conditions. A total of nine bilayers were used for the selective recovery of phosphate. Bilayers were constructed from polyelectrolyte solutions of varying ionic strength (0-1 M of NaCl). The selected pH for deposition of PEI (5.9) and the presence of supporting salt in the polyelectrolyte solution is expected to provide membranes with high permeability and high charge density. This particular combination of bilayers yielded high flux membranes that allowed selective removal of H(2)PO(4)(-) in the presence of Cl(-) at low pressure (0.28 bar). The magnitude of negative solute rejection of chloride showed increasing trend with the number of bilayer for a particular salt concentration. Whereas the increase in magnitude with ionic strength is so high (-6.18 to -269.17 at 0.5 M NaCl for 9 bl) that gave the best observed Cl(-)/H(2)PO(4)(-) selectivity (310.23, flux 13.53 m(3)/m(2)-day). To the best of our knowledge, this is the first time a multilayer polyelectrolyte system with such a high selectivity and rejection for H(2)PO(4)(-) is reported. The solution flux decreased with the number of bilayers and ionic strength. The rejection of phosphate was dependent on feed pH, concentration of deposited polyelectrolyte solution, and composition of membrane support.

Fabrication of protein adhesive and resistant surfaces based on chitosan/polystyrene sulfonate (CHI/PSS) multilayer membranes is presented. Adsorption behavior of bovine serum albumin (BSA) and lysozyme to CHI/PSS multilayer was studied by simple adsorption method and under pressure driven (ultrafiltration) conditions. The protein incorporated membranes were characterized by FT-IR, UV-vis, SEM and AFM. The loading of proteins to the multilayer was found to be dependent on the nature of protein, pH, number of bilayers, methods of adsorption and time of adsorption. Simple adsorption resulted in BSA adhesive layers with some conformational changes at higher number of bilayers. Ultrafiltration leads to protein repellence at higher number of bilayers which is attributed to the presence of irremovable water. Lysozyme adsorption/sorption varied with pH. Surface coverage dominates at pH close to pI and at pH 5 under ultraflitration condition where as simple adsorption resulted in protein repellence at pI. The secondary structure of adsorbed lysozyme is preserved for a wide pH range (5-11). Desorption study of lysozyme adsorbed membranes at pH 8.8 was carried out to understand the adsorption/sorption of protein. Diffusion of the sorbed lysozyme from the inner layers to the surface is found to take place at lower concentrations of NaCl., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Degradation of cyanuric acid (OOOT), a stable end product of oxidative decomposition of atrazine, is investigated in a combined field of gamma radiolysis and fenton reaction. The reaction of hydroxyl radical (OH) at pH 6 was carried out by irradiating N(2)O saturated aqueous solutions containing OOOT (1 x 10(-3) mol dm(-3)), and this resulted only a marginal degradation (20%). However, when the same reaction was carried out in the presence of varying concentrations of ferrous sulfate ((5-10)x10(-5) mol dm(-3)), the decay of OOOT has been enhanced to more than 80%. This decay followed a first order kinetics. Nearly similar effects were observed with another triazine derivative, 2,4-dioxohexahydro-1,3,5-triazine (DHT). Two major reaction mechanisms are proposed for the enhanced decay of OOOT. The formation of unstable hydroxyl radical adducts from the reaction of .OH which is the result of gamma radiolysis and the Fenton reaction (resulting from the reaction of the added Fe(II) and of the H(2)O(2) from the radiolysis of water), is proposed as the first mechanism. The second mechanism, which is likely the major contributor to degradation, is proposed as the reaction of a nucleophilic adduct, Fe(II)OOH, which could directly react with the electron deficient triazine ring. It is highlighted that such degradation reactions must be explored for the complete degradation of the byproducts of the oxidative decomposition of atrazine.

A study is made of the kinetics and mechanism of the reaction of radiolytically produced hydrated electron (e-(aq)) with some triazine derivatives [1,3,5-triazine (T), 2,4,6-trimethoxy-1,3,5-triazine (TMT), 2,4-dioxohexahydro-1,3,5-triazine (DHT), 6-chloro N-ethyl N-(1-methylethyl)-1,3,5-triazine 2,4-diamine (atrazine, AT), and cyanuric acid (CA)] in aqueous medium using pulse and steady-state radiolysis techniques. The second-order rate constants were determined from the pseudo first-order decay of e(-)(aq) in the presence of triazines at 720 nm, and the values obtained with T, TMT, AT, and CA are in the order of 10(9) dm(3) mol(-1) s(-1) and that of DHT was 10(8) dm(3) mol(-1) s(-1) at pH 6. The transient absorption spectra from the reaction of e(-)(aq) with T and TMT are characterized by their lambda(max) at 310 nm, and those of DHT and CA are around 280 and 290 nm, respectively. However, a very weak and featureless absorption spectrum is obtained from AT. On the basis of the spectral evidence and on the quantitative electron transfer from the transient intermediates to the oxidant, methyl viologen (MV(2+)), the intermediate radicals are assigned to N-protonated electron adducts (with the unpaired spin density at carbon) of triazines. The degradation profiles, monitored as the disappearance of parent triazine concentrations as a function of dose, obtained with AT, TMT, CA, and DHT, highlight the potential use of e-(aq) in the degradation of triazines.

One-electron reduction of S-nitrosothiols (RSNO) has been studied using radiolytically produced reducing entity, the hydrated electron (e(aq)(-)), in aqueous medium. Both kinetics of the reaction and the mechanistic aspects of the decomposition of S-nitroso derivatives of glutathione, L-cysteine, N-acetyl-L-cysteine, N-acetyl-D,L-penicillamine, N-acetylcysteamine, L-cysteine methyl ester, and D,L-penicillamine have been investigated at neutral and acidic pH. The second-order rate constants of the reaction of e(aq)(-) with RSNOs were determined using a pulse radiolysis technique and were found to be diffusion controlled (10(10) dm(3) mol(-1) s(-1)) at neutral pH. The product analysis using HPLC, fluorimetry, and MS revealed the formation of thiol and nitric oxide as the major end products. It is therefore proposed that one-electron reduction of RSNO leads to the liberation of NO. There is no intermediacy of a thiyl radical as in the case of oxidation reactions of RSNOs. The radical anion of RSNO (RSN(*)O(-)) is proposed as a possible intermediate. The overall reaction could be written as RSNO + e(aq)(-) --H+--> RSH + (*)NO.

Hydroxyl radical (OH) production, mediated by UV light, from aqueous ferric perchlorate was investigated at low pH using a deoxyribose-thiobarbituric acid (-TBA) assay. The rate of production of OH was found to be dependent on the irradiation time. Addition of suitable substrates such as substituted benzenes can compete for the reaction of OH with deoxyribose, leading to a decreased yield of TBA chromogen formed from the deoxyribose-TBA assay. The second-order rate constants of the added substrates can be determined from such a simple competition kinetic method. The second-order rate constants for the reaction of OH with a number of substituted benzenes were determined using this method and the values were compared with the reported rate constants using pulse radiolysis technique. The values determined using the present method (1 to 8 x 10(9) dm3/mols) are in good agreement with those reported by use of the pulse radiolysis technique. It is proposed that the photoproduction of OH from aqueous ferric perchlorate coupled with deoxyribose-TBA assay is a simple and efficient method for determination of rate constants for the reaction of OH with a variety of substituted benzenes that are known to be organic water contaminants.