Hemin as a Molecular Probe for Nitric Oxide Detection in Physiological Solutions: Experimental and Theoretical Assessment.

Given its pivotal role in modulating various pathological processes, precise measurement of nitric oxide (●NO) levels in physiological solutions is imperative. The key techniques include the ozone-based chemiluminescence (CL) reactions, amperometric ●NO sensing, and Griess assay, each with its advantages and drawbacks. In this study, a hemin/H2O2/luminol CL reaction was employed for accurately detecting ●NO in diverse solutions. We investigated how the luminescence kinetics was influenced by ●NO from two donors, nitrite and peroxynitrite, while also assessing the impact of culture medium components and reactive species quenchers. Furthermore, we experimentally and theoretically explored the mechanism of hemin oxidation responsible for the initiation of light generation. Although both hemin and ●NO enhanced the H2O2/luminol-based luminescence reactions with distinct kinetics, hemin's interference with ●NO/peroxynitrite- modulated their individual effects. Leveraging the propagated signal due to hemin, the ●NO levels in solution were estimated, observing parallel changes to those detected via amperometric detection in response to varying concentrations of the ●NO-donor. The examined reactions aid in comprehending the mechanism of ●NO/hemin/H2O2/luminol interactions and how these can be used for detecting ●NO in solution with minimal sample size demands. Moreover, the selectivity across different solutions can be improved by incorporating certain quenchers for reactive species into the reaction.

Assessment of the mode of action of perchloroethylene-induced mouse liver tumors.

Perchloroethylene (PCE) is used as a solvent and chemical intermediate. Following chronic inhalation exposure, PCE selectively induced liver tumors in mice. Understanding the mode of action (MOA) for PCE carcinogenesis in mice is important in defining its possible human cancer risk. The proposed MOA is based on the extensive examination of the peer-reviewed studies that have assessed the mouse liver effects of PCE and its major oxidative metabolite trichloroacetic acid (TCA). Similar to PCE, TCA has also been demonstrated to liver tumors selectively in mice following chronic exposure. The Key Events (KE) of the proposed PCE MOA involve oxidative metabolism of PCE to TCA [KE 1]; activation of the peroxisome proliferator-activated receptor alpha (PPARα) [KE 2]; alteration in hepatic gene expression including cell growth pathways [KE 3]; increase in cell proliferation [KE 4]; selective clonal expansion of hepatic preneoplastic foci [KE 5]; and formation of hepatic neoplasms [KE 6]. The scientific evidence supporting the PPARα MOA for PCE is strong and satisfies the requirements for a MOA analysis. The PPARα liver tumor MOA in rodents has been demonstrated not to occur in humans; thus, human liver cancer risk to PCE is not likely.

Photo-thermal activation of persulfate for the efficient degradation of synthetic and real industrial wastewaters: System optimization and cost estimation.

The photo-thermal activation of persulfate (PS) was carried out to degrade various pollutants such as reactive blue-222 (RB-222) dye, sulfamethazine, and atrazine. Optimizing the operating parameters showed that using 0.90 g/L of PS at pH 7, temperature of 90 °C, initial dye concentration of 21.60 mg/L, and reaction time of 120 min could attain a removal efficiency of 99.30%. The degradation mechanism was explored indicating that hydroxyl and sulfate radicals were the prevailing reactive species. The degradation percentages of 10 mg/L of sulfamethazine and atrazine were 83.30% and 70.60%, respectively, whereas the mineralization ratio was 63.50% in the case of real textile wastewater under the optimal conditions at a reaction time of 120 min. The treatment cost per 1 m3 of real wastewater was appraised to be 1.13 $/m3 which assured the inexpensiveness of the proposed treatment system. This study presents an effective and low-cost treatment system that can be implemented on an industrial scale.

Bibliometric analysis of Advanced Oxidation Processes studies with a focus on Life Cycle Assessment and Costs.

Advanced oxidation processes (AOPs) are wastewater treatment technologies that stand out for their ability to degrade Contaminants of Emerging Concern (CECs). The literature has extensively investigated these removal processes for different aqueous matrices. Once technically mature, some of these systems have become accredited to be applied on a large scale, and therefore, their systemic performances in the environmental and cost spheres have also become essential requirements. This study proposed corroborating this trend, analyzing the available literature on the subject to verify how experts in the AOP area investigated this integration during 2015-2023. For this purpose, a sample of publications was treated by applying the Systematic Review (SR) methodology. This resulted in an extract of 83 studies that adopted life-cycle logic to estimate environmental impacts and process costs or evaluated them as complementary to the technical dimension of each treatment technology. This analysis found that both dimensions can be used for selecting or sizing AOPs at the design scale. However, the appropriate choice of the impact categories for the environmental assessment and establishing a methodology for cost analysis can make the approach still more effective. In addition, a staggering number of processes would broaden the reality and applicability of the estimates, and adopting multicriteria analysis methodologies could address essential aspects of decision-making processes during the design of the arrangements. By meeting the original purposes, the study broadened the requirements for designing AOPs and disseminating their use in mitigating the discharge of CECs.

Structural Impact Assessment of Cytochrome P450 2A13 Polymorphisms Using Molecular Dynamics Simulations.

One of the members of CYP, a monooxygenase, CYP2A13 is involved in the metabolism of nicotine, coumarin, and tobacco-specific nitrosamine. Genetic polymorphisms have been identified in CYP2A13, with reported loss or reduction in enzymatic activity in CYP2A13 allelic variants. This study aimed to unravel the mechanism underlying the diminished enzymatic activity of CYP2A13 variants by investigating their three-dimensional structures through molecular dynamics (MD) simulations. For each variant, MD simulations of 1000 ns were performed, and the obtained results were compared with those of the wild type. The findings indicated alterations in the interaction with heme in CYP2A13.4, .6, .8, and .9. In the case of CYP2A13.5, observable effects on the helix structure related to the interaction with the redox partner were identified. These conformational changes were sufficient to cause a decrease in enzyme activity in the variants. Our findings provide valuable insights into the molecular mechanisms associated with the diminished activity in the CYP2A13 polymorphisms.

Simultaneous removal of antibiotic resistance genes and improved dewatering ability of waste activated sludge by Fe(II)-activated persulfate oxidation.

Waste activated sludge properties vary widely with different regions due to the difference in living standards and geographical distribution, making a big challenge to developing a universally effective sludge dewatering technique. The Fe(II)-activated persulfate (S2O82-) oxidation process shows excellent ability to disrupt sludge cells and extracellular polymeric substances (EPS), and release bound water from sludge flocs. In this study, the discrepancies in the physicochemical characteristics of sludge samples from seven representative cities in China (e.g., dewaterability, EPS composition, surface charge, microbial community, relative abundance of antibiotic resistance genes (ARGs), etc.) were investigated, and the role of Fe(II)-S2O82- oxidation in enhancing removal of antibiotic resistance genes and dewatering ability were explored. The results showed significant differences between the EPS distribution and chemical composition of sludge samples due to different treatment processes, effluent sources, and regions. The Fe(II)-S2O82- oxidation pretreatment had a good enhancement of sludge dewatering capacity (up to 76 %). Microbial analysis showed that the microbial community in each sludge varied significantly depending on the types of wastewater, the wastewater treatment processes, and the regions, but Fe(II)-S2O82- oxidation was able to attack and rupture the sludge zoogloea indiscriminately. Genetic analysis further showed that a considerable number of ARGs were detected in all of these sludge samples and that Fe(II)-S2O82- oxidation was effective in removing ARGs by higher than 90 %. The highly active radicals (e.g., SO4-·, ·OH) produced in this process caused drastic damage to sludge microbial cells and DNA stability while liberating the EPS/cell-bound water. Co-occurrence network analysis highlighted a positive correlation between population distribution and ARGs abundance, while variations in microbial communities were linked to regional differences in living standards and level of economic development. Despite these variations, the Fe(II)-S2O82- oxidation consistently achieved excellent performance in both ARGs removal and sludge dewatering. The significant modularity of associations between different microbial communities also confirms its ability to reduce horizontal gene transfer (HGT) by scavenging microbes.

Highly efficient heterogeneous electro-Fenton reaction for tetracycline degradation by Fe-Ni LDH@ZIF-67 modified carbon cloth cathode: Mechanism and toxicity assessment.

In this work, a novel and efficient Fe-Ni LDH@ZIF-67 catalyst modified carbon cloth (CC) cathode was developed for tetracycline (TC) degradation in heterogeneous electro-Fenton (Hetero-EF) process. Compared to Fe-Ni LDH/CC (75.7%), TC degradation rate of Fe-Ni LDH@ZIF-67/CC cathode increased to 95.6% within 60 min. The synergistic effect of hetero-EF and anodic oxidation process accelerated electron transfer, the maximum H2O2 production of Fe-Ni LDH@ZIF-67/CC electrode reached 264 mg/L, improving utilization efficiency of H2O2. The cathode possessing a satisfied TC degradation performance over a wide pH (3-9). Free radical capture experiment revealed the collaboration of ·O2-, ·OH, and 1O2 play a significant role in TC degradation. The 5 cycles experiment and metal ion leaching experiment showed that the proposed Fe-Ni LDH@ZIF-67/CC has good recyclability and stability. In addition, the proposed Fe-Ni LDH@ZIF-67/CC cathode achieved satisfying performance in real water (tap water: 97.3%, lake water: 97.7%), demonstrating the possibility for practical application. TC degradation pathways were proposed by theory analysis and experimental results. The toxicity of TC intermediates was reduced by Hetero-EF degradation according to Toxicity Estimation Software Tool and Escherichia coli growth inhibition experiments. This work provides a novel modified cathode to improve removal efficiency of antibiotics in wastewater.

Scientometric analysis of electrocatalysis in wastewater treatment: today and tomorrow.

Electrocatalytic methods are valuable tools for addressing water pollution and scarcity, offering effective pollutant removal and resource recovery. To investigate the current status and future trends of electrocatalysis in wastewater treatment, a detailed analysis of 9417 papers and 4061 patents was conducted using scientometric methods. China emerged as the leading contributor to publications, and collaborations between China and the USA have emerged as the most frequent partnerships. Primary article co-citation clusters focused on oxygen evolution reaction and electrochemical oxidation, transitioning towards advanced oxidation processes ("persulfate activation"), and electrocatalytic reduction processes ("nitrate reduction"). Bifunctional catalysts, theoretical calculations, electrocatalytic combination technologies, and emerging contaminants were identified as current research hotspots. Patent analysis revealed seven types of electrochemical technologies, which were compared using SWOT analysis, highlighting electrochemical oxidation as prominent. The technological evolution presented the pathway of electro-Fenton to combined electrocatalytic technologies with biochemical processes, and finally to coupling with electrocoagulation. Standardized evaluation systems, waste resource utilization, and energy conservation were important directions of innovation in electrocatalytic technologies. Overall, this study provided a reference for researchers to understand the framework of electrocatalysis in wastewater treatment and also shed light on potential avenues for further innovation in the field.

Cheese wastewater treatment through combined coagulation-flocculation and photo-Fenton-like advanced oxidation processes for reuse in irrigation: effect of operational parameters and phytotoxicity assessment.

The present study aims to investigate the efficiency of a combined cheese wastewater treatment approach involving coagulation with ferric chloride coupled with a photo-Fenton-like oxidation process for potential reuse in irrigation. Laboratory-scale tests were conducted, examining the effect of various operational parameters on the treatment process. Specifically, the effects of initial wastewater pH, coagulant dosage, decantation time for the coagulation process, and initial pH, chemical oxygen demand (COD) concentration, and Fe3+ and H2O2 dosages for photo-Fenton-like oxidation were studied. Coagulation was found effective at natural pH of 6 and showed a highest removal efficiency in terms of COD (50.6%), biological oxygen demand BOD5 (42.1%), turbidity (99.3%), and least sludge volume generation (11.8% v/v) for an optimum coagulant dose of 400 mg Fe3+ L-1 and 8 h of decantation time. Thereafter, photo-Fenton-like oxidation (Fe3+/H2O2/UVA-300W) of the pretreated cheese effluent enhanced the removal of COD, BOD5 and TOC to 91.2%, 91.4%, and 97.5%, respectively, using the optimized conditions (pH = 3; [Fe3+] = 5.0 × 10-4 mol L-1; [H2O2] = 0.2 mol L-1 and tirr = 24 h). This study also shows that the proposed combined process allowed a significant phytotoxicity reduction toward lentil seed germination. The obtained outcome was encouraging and supports the possible use of the treated cheese wastewater as an additional water source for agricultural irrigation.

Formation of autotrophic nitrogen removal granular sludge driven by the dual-partition airlift internal circulation: Insights from performance assessment, community succession, and metabolic mechanism.

Granular sludge has been recognized as an effective method for the application and industrialization of the anammox-based process due to its good biomass retention capacity and environmental tolerance. In this study, a one-stage autotrophic nitrogen removal (ANR) dual-partition system with airlift internal circulation was implemented for 320 days. A high nitrogen removal efficiency of 84.6% was obtained, while the nitrogen removal rate reached 1.28 g-N/L/d. ANR granular sludge dominated by Nitrosomonas and Candidatus Brocadia was successfully cultivated. Results showed that activity and abundance of functional flora first increased with granulation process, but eventually declined slightly when particle size exceeded the optimal range. Total anammox activity was observed to be significantly correlated with protein content (R2 = 0.9623) and nitrogen removal performance (R2 = 0.8796). Correlation network revealed that AnAOB had complex interactions with other bacteria, both synergy for nitrogen removal and competition for substrate. Changes in abundances of genes encoding the Carbohydrate Metabolism, Energy Metabolism, and Membrane Transport suggested energy production and material transfer were possibly blocked with further sludge granulation. Formation of ANR granular sludge promoted the interactions and metabolism of functional microorganisms, and the complex nitrogen metabolic pathways improved the performance stability. These results validated the feasibility of granule formation in the airlift dual-partition system and revealed the response of the ANR system to sludge granulation.

Hybrid radical coupling during MnO2-mediated transformation of a mixture of organic UV filters: Chemistry and toxicity assessment.

Manganese oxide (MnO2) is one of the most abundant metal oxides, and it is renowned for its ability to degrade various phenolic micropollutants. However, under MnO2-mediated transformation, BP-3 transforms into 12 different radical-coupled transformation products (TPs) out of 15 identified TPs. These radical-coupled TPs are reported with adverse environmental impacts. This study explored the effects of MnO2 on organic UV filter mixtures and different water constituents (i.e., bicarbonate ion (HCO3-), humic acid (HA) and halide ions) in terms of degradation efficiency and transformation chemistry. When a mixture of benzophenone-3 (BP-3) and avobenzone (AVO) underwent transformation by MnO2, hybrid radical-coupled TPs derived from both organic UV filters were generated. These hybrid radical-coupled TPs were evaluated by an in silico prediction tool and Vibrio fischeri bioluminescence inhibition assay (VFBIA). Results showed that these TPs were potentially toxic to aquatic organisms, even more so than their parent compounds. The higher the concentration of HCO3-, HA, chloride ion (Cl-) and bromide ion (Br-), the greater the reduction in the efficiencies of degrading BP-3 and AVO. Contrastingly, in the presence of iodide ion (I-), degradation efficiencies of BP-3 and AVO were enhanced; however, iodinated TPs and iodinated radical-coupled TPs were formed, with questionable toxicity. This study has revealed the environmental risks of hybrid radical-coupled TPs, iodinated TPs and iodinated radical-coupled TPs when the organic UV filters BP-3 and AVO are transformed by MnO2.

Assessment of the UV/DCCNa and UV/NaClO oxidation process for the removal of diethyl phthalate (DEP) in the aqueous system.

In this work, the removal and transformation process of diethyl phthalate (DEP) in UV/dichloroisocyanurate (UV/DCCNa) and UV/sodium hypochlorite (UV/NaClO) systems were compared to evaluate the application potential of UV/DCCNa technology. Compared with UV/NaClO, UV/DCCNa process has the advantage of DEP removal and caused a higher degradation efficiency (93.8%) within 45 min of oxidation in ultrapure water due to the sustained release of hypochloric acid (HOCl). Fourteen intermediate products were found by high-resolution mass spectrometry, and the transformation patterns including hydroxylation, hydrolysis, chlorination, cross-coupling, and nitrosation were proposed. The oxidation processes were also performed under quasi-realistic environmental conditions, and it was found that DEP could be effectively removed in both systems, with yields of disinfection byproduct meeting the drinking water disinfection standard (<60.0 µg/L). Comparing the single system, the removal of DEP decreased in the mixed system containing five kinds of PAEs, which could be attributed to the regeneration of DEP and the competitive effect of •OH occurred among the Dimethyl phthalate (DMP), DEP, Dipropyl phthalate (DPrP), Diallyl phthalate (DAP) and Diisobutyl phthalate (DiBP). However, a greater removal performance presented in UV/DCCNa system compared with UV/NaClO system (69.4% > 62.1%). Further, assessment of mutagenicity and developmental toxicity by Toxicity Estimation Software Tool (T.E.S.T) software indicated that UV/DCCNa process has fewer adverse effects on the environment and is a more environmentally friendly chlorination method. This study may provide some guidance for selecting the suitable disinfection technology for drinking water treatment.

Ultrasound for the degradation of endocrine disrupting compounds in aqueous solution: A review on mechanisms, influence of operating parameters and cost estimation.

Availability of drinking water is one of the basic humanitarian goals but remains as a grand challenge that the world is facing today. Currently, water bodies are contaminated not only with conventional pollutants but also with numerous recalcitrant pollutants, such as PPCPs, endocrine disrupting compounds, etc. These emerging pollutants require special attention because of their toxicity to living organisms, bio-resistant and can sustain even after primary and secondary treatments of wastewater. Among different treatment technologies, sonolysis is found to be an innovative and promising technique for the treatment of emerging pollutants present in aqueous solution. Sonolysis is the use of ultrasound to enhance or alter chemical reactions by the formation of free radicals and shock waves which ultimately helps in degradation of pollutants. This review summarizes several studies in the sonochemical literature, including mechanisms of sonochemical process, physical and chemical effects of ultrasound, and the influence of several process variables such as ultrasound frequency, power density, temperature and pH of the medium on degradation performance for endocrine disrupting compounds. In addition, this review highlighted techno-economic perspectives focusing on the total cost required for translating the ultrasound-based processes on a large scale. Overall, the objective of this study is to exhibit a critical review of information available in the literature to encourage and promote future research on sonolysis for the degradation of Endocrine Disrupting Compounds (EDCs).

Investigation of seasonality of human spontaneous physical activity and energy expenditure in respiratory chamber in Phoenix, Arizona.

OBJECTIVE: The existence of seasonal changes in energy metabolism is uncertain. We investigated the relationship between the seasons and spontaneous physical activity (SPA), energy expenditure (EE), and other components measured in a respiratory chamber. METHODS: Between 1985-2005, 671 healthy adults (aged 28.8 ± 7.1 years; 403 men) in Phoenix, Arizona had a 24-hour stay in the respiratory chamber equipped with radar sensors; SPA (expressed as a percentage over the time interval), the energy cost of SPA, EE, and respiratory exchange ratio (RER) were measured. RESULTS: In models adjusted for known covariates, SPA (%) was lower during summer (7.2 ± 2.9, p = 0.0002), spring (7.5 ± 2.9, p = 0.025), and fall (7.6 ± 3, p = 0.038) compared to winter (8.3 ± 3.5, reference). Conversely, energy cost of SPA (kcal/h/%) was higher during summer (2.18 ± 0.83, p = 0.0008), spring (2.186 ± 0.83, p = 0.017), and fall (2.146 ± 0.75, p = 0.038) compared to winter (2.006 ± 0.76). Protein (292 ± 117 kcal/day, ß = -21.2, p = 0.08) oxidation rates was lower in the summer compared to winter. Carbohydrate and lipid oxidation rates (kcal/day) did not differ across seasons. RER and 24-h EE did not differ by season. CONCLUSION: SPA, representing fidgeting-like behavior in the chamber, demonstrated a winter peak and summer nadir in humans living in a desert climate. These findings indicate that the physiological propensity for movement may be affected by seasonal factors. CLINICAL TRIAL REGISTRATION: ClinicalTrials.gov identifiers: NCT00340132, NCT00342732.

A comprehensive assessment of redox balance in small for gestational age newborns and their mothers.

OBJECTIVE: The objective of this study was to assess oxidative stress in small for gestational age (SGA) newborns and their mothers by evaluating intra- and extracellular thiol homeostasis and the quantification of major oxidants and antioxidants. METHODS: A total of 75 mothers and their 75 newborns (43 SGA) were enrolled in this study. Thiol-disulfide homeostasis, serum myeloperoxidase, catalase, total oxidant, and antioxidant status were analyzed. Additionally, erythrocytic glutathione (GSH) homeostasis was measured. RESULTS: Although native and total thiol levels were decreased, disulfide levels were increased in SGA groups. Additionally, myeloperoxidase activity and total oxidant status levels were significantly elevated whereas total antioxidant status levels and enzymatic antioxidant systems were diminished in SGA groups. Similarly, intra-erythrocytic GSH homeostasis was shifted in favor of oxidants in SGA groups. CONCLUSION: Our results demonstrate that insufficient antioxidant systems in mothers and a robust source of oxidative stress in SGA might contribute to the pathophysiology of SGA births.

Degradation of Ampicillin with antibiotic activity removal using persulfate and submersible UVC LED: Kinetics, mechanism, electrical energy and cost analysis.

Effective water treatment to remove antibiotics and its activity from contaminated water is urgently needed to prevent antibiotic-resistant bacteria (ARB) emergence. In this study, we investigated degradation of Ampicillin (AMP), an extensively used ß-lactam antibiotic, using submersible Ultraviolet C Light Emitting Diode (λmax = 276 nm) irradiation source, and Persulfate (UVC LED/PS system). Pseudo first order rate constant (kobs) for degradation of AMP (1 ppm) by UVC LED/PS system was determined to be 0.5133 min-1 (PS = 0.2 mM). kobs value at pH 2.5 (0.7259 min-1) was found to be higher than pH 6.5 (0.5133 min-1) and pH 12 (0.1745 min-1). kobs value for degradation of AMP in deionized water spiked with inorganic anions (Cl-=0.5369 min-1,SO42-=0.4545 min-1, NO3-=0.1526 min-1, HCO3-=0.0226 min-1), in real tap water (0.1182 min-1) and simulated ground water (0.0372 min-1) were presented. Radical scavenging experiment reveal involvement of sulfate radical anion and hydroxyl radical in UVC LED/PS system. EPR analysis confirms the generation of sulfate radical anion and hydroxyl radical. Importantly, 74% reduction of total organic carbon (TOC) occurred within 60 min of AMP treatment by UVC LED/PS system. Seven degradation by-products were identified by high resolution mass spectrometry, and degradation pathways were proposed. Antibacterial activity of AMP towards Bacillus subtilis and Staphylococcus aureus was completely removed after UVC LED/PS treatment. ECOSAR model predicted no very toxic degradation by-products generation by UVC LED/PS system. Electrical Energy per order (EEo) and cost of UVC LED/PS system were determined to be 0.9351 kW/m3/order and ₹ 7.91/m3 ($ 0.095/m3 or € 0.087/m3), respectively. Overall, this study highlights, UVC LED/PS system as energy efficient, low-cost, and its potential to emerge as sulfate radical anion based advanced oxidation process (AOP) to treat water with antibiotics.

Multi-target assessment of advanced oxidation processes-based strategies for indirect potable reuse of tertiary wastewater: Fate of compounds of emerging concerns, microbial and ecotoxicological parameters.

Two advanced oxidation processes (AOPs), namely ozone/H2O2 and UV/H2O2, were tested at pilot scale as zero-liquid-discharge alternative treatments for the removal of microbiological (bacteria and viruses), chemical (compounds of emerging concern (CECs)) and genotoxic responses from tertiary municipal wastewater for indirect potable reuse (IPR). The AOP treated effluents were further subjected to granular activated carbon (GAC) adsorption and UV disinfection, following the concept of multiple treatment barriers. As a reference, a consolidated advanced wastewater treatment train consisting of ultrafiltration, UV disinfection, and reverse osmosis (RO) was also employed. The results showed that, for the same electrical energy applied, the ozone/H2O2 treatment was more effective than the UV/H2O2 treatment in removing CECs. Specifically, the ozone/H2O2 treatment, intensified by high pressure and high mixing, achieved an average CECs removal efficiency higher than UV/H2O2 (66.8% with respect to 18.4%). The subsequent GAC adsorption step, applied downstream the AOPs, further improved the removal efficiency of the whole treatment trains, achieving rates of 98.5% and 96.8% for the ozone/H2O2 and UV/H2O2 treatments, respectively. In contrast, the ultrafiltration step of the reference treatment train only achieved a removal percentage of 22.5%, which increased to 99% when reverse osmosis was used as the final step. Microbiological investigations showed that all three wastewater treatment lines displayed good performance in the complete removal of regulated and optional parameters according to both national and the European Directive 2020/2184. Only P. aeruginosa resulted resistant to all treatments with a higher removal by UV/H2O2 when higher UV dose was applied. In addition, E. coli STEC/VTEC and enteric viruses, were found to be completely removed in all tested treatments and no genotoxic activity was detected even after a 1000-fold concentration. The obtained results suggest that the investigated treatments are suitable for groundwater recharge to be used as a potable water source being such a procedure an IPR. The intensified ozone/H2O2 or UV/H2O2 treatments can be conveniently incorporated into a multi-barrier zero-liquid-discharge scheme, thus avoiding the management issues associated with the retentate of the conventional scheme that uses reverse osmosis. By including the chemical cost associated with using 11-12 mg/L of H2O2 in the cost calculations, the overall operational cost (energy plus chemical) required to achieve 50% average CECs removal in tertiary effluent for an hypothetical full-scale plant of 250 m3/h (or 25,000 inhabitants) was 0.183 €/m3 and 0.425 €/m3 for ozone/H2O2 and UV/H2O2 treatment train, respectively.

Kinetic and structural assessment of the reduction of human 2-Cys peroxiredoxins by thioredoxins.

We have studied the reduction reactions of two cytosolic human peroxiredoxins (Prx) in their disulfide form by three thioredoxins (Trx; two human and one bacterial), with the aim of better understanding the rate and mechanism of those reactions, and their relevance in the context of the catalytic cycle of Prx. We have developed a new methodology based on stopped-flow and intrinsic fluorescence to study the bimolecular reactions, and found rate constants in the range of 105 -106 m-1 s-1 in all cases, showing that there is no marked kinetic preference for the expected Trx partner. By combining experimental findings and molecular dynamics studies, we found that the reactivity of the nucleophilic cysteine (CN ) in the Trx is greatly affected by the formation of the Prx-Trx complex. The protein-protein interaction forces the CN thiolate into an unfavorable hydrophobic microenvironment that reduces its hydration and results in a remarkable acceleration of the thiol-disulfide exchange reactions by more than three orders of magnitude and also produces a measurable shift in the pKa of the CN . This mechanism of activation of the thiol disulfide exchange may help understand the reduction of Prx by alternative reductants involved in redox signaling.

Heat and carbon co-activated persulfate to regenerate gentamicin-laden activated carbon: Performance, mechanism, and safety assessment.

Activated carbon enriched with high concentrations of gentamicin (ACG) was generated in the production process of gentamicin. Inappropriate handling methods for ACG not only squanders carbon resource, but also seriously hinders achieving global carbon neutrality and hazardous to human health. In the present work, thermal and carbon co-activated persulfate method (TC-PS) was developed to regenerate ACG with degrading gentamicin. The results showed that ACG was effectively regenerated by TC-PS, restoring the adsorption performance for gentamicin. When the treatment temperature was 80 °C, the persulfate dosage was 20 mM and the initial pH was 3.0, the degradation efficiency of gentamicin reached 100%. The HO• and SO4•- were the major reactive species for gentamicin degradation. The possible degradation routes of gentamicin were proposed and the safety assessment indicated that the produced intermediates during the regeneration process of ACG by TC-PS have insignificant impact on the biological and ecological environment.

Study on the hydrolytic degradation behaviour of bictegravir by LC-PDA-Q/TOF-MS/MS NMR and in silico toxicity assessment.

Forced degradation studies provide rapid access to degradation products (DPs), where structural characterization and assessment of their potential toxicity are vital for pharmaceutical safety and regulatory compliance. As per the International Council for Harmonization of Technical Requirements for Pharmaceuticals for Human Use (ICH) Q1A R(2) guidelines, a forced degradation study of Bictegravir (BIC), a USFDA-approved drug for HIV wild type, in hydrolytic conditions (acid, base, and neutral) revealed the formation of six DPs in RP-HPLC (Reverse Phase- High-Performance Liquid Chromatography) gradient elution program using a C18 (4.6 × 250 mm, 5 µm) column. DP-1, 2, and 3 were characterized using liquid chromatography-tandem mass spectrometry (LC-MS/MS), whereas DP-4, 5, and 6 posed difficulties in characterization due to their isomeric nature. Using characteristic NOEs (Nuclear Overhauser Effect) from 2D ROESY NMR (Nuclear Magnetic Resonance) studies, we have elucidated diastereomeric DP-4/5 and isomeric DP-6/BIC configurational structures. Furthermore, in silico toxicity studies for the six degradation products were predicted for toxicity endpoints by employing DEREK, SARAH, and Pro Tox-II application tools. The DP-1 (methanamine) and DP-3 (carboxylic acid) resulting from acid-catalyzed hydrolysis, were predicted to have potential carcinogenic and mutagenic properties. These findings contribute significantly to our understanding of BIC's stability and safety profile in pharmaceutical development and underscore the rigorous characterization of stereoisomers by NMR that were further utilized for toxicity prediction.