Buprenorphine Affects the Initiation and Severity of Interleukin Induced Acute Pancreatitis in Mice.

Acute pancreatitis (AP) is a common disease with no targeted therapy and has varied outcomes ranging from spontaneous resolution to being lethal. While typically painful, AP can also be painless. Various agents, including opioids are used for pain control in AP; the risks, and benefits of which are often debated. Since experimental AP in mice is used to study the efficacy of potential therapies, we studied the effect of a commonly used opioid buprenorphine on the initiation and progression of AP. For this we administered extended-release buprenorphine subcutaneously prior to inducing the previously established severe AP model that uses Interleukins 12 and 18 (IL12,18) in genetically obese (ob/ob) mice and compared this to mice with AP but without the drug. Mice were monitored over 3 days and parameters of AP induction and progression were compared. Buprenorphine significantly reduced the serum amylase, lipase, pancreatic necrosis, and AP associated fat necrosis which is ubiquitous in obese mice and humans. Buprenorphine delayed the AP associated reduction of carotid artery pulse distention, and development of hypothermia, hastened renal injury, and muted the early increase in respiratory rate vs. IL12,18 alone. The site of buprenorphine injection appeared erythematous, inflamed, and microscopically showed thinning, loss of epidermal layers which had increased apoptosis. In summary, subcutaneous extended-release buprenorphine interfered with the induction of AP by reducing serum amylase, lipase, pancreatic and fat necrosis, the worsening of AP by delaying hypotension, hypothermia, while hastening renal injury, respiratory depression, and causing cutaneous injury at the site of injection.

Effects of interaction of multiple large-scale atmospheric circulations on precipitation dynamics in China.

Different scenarios of precipitation, that lead to such phenomena as droughts and floods are influenced by concurrent multiple teleconnection factors. However, the multivariate relationship between precipitation indices and teleconnection factors, including large-scale atmospheric circulations and sea surface temperature signals in China, is rarely explored. Understanding this relationship is crucial for drought early warning systems and effective response strategies. In this study, we comprehensively investigated the combined effects of multiple large-scale atmospheric circulation patterns on precipitation changes in China. Specifically, Pearson correlation analysis and Partial Wavelet Coherence (PWC) were used to identify the primary teleconnection factors influencing precipitation dynamics. Furthermore, we used the cross-wavelet method to elucidate the temporal lag and periodic relationships between multiple teleconnection factors and their interactions. Finally, the multiple wavelet coherence analysis method was used to identify the dominant two-factor and three-factor combinations shaping precipitation dynamics. This analysis facilitated the quantification and determination of interaction types and influencing pathways of teleconnection factors on precipitation dynamics, respectively. The results showed that: (1) the Atlantic Multidecadal Oscillation (AMO), EI Niño-Southern Oscillation (ENSO), East Asia Summer Monsoon (EASM), and Indian Ocean Dipole (IOD) were dominant teleconnection factors influencing Standardized Precipitation Index (SPI) dynamics; (2) significant correlation and leading or lagging relationships at different timescales generally existed for various teleconnection factors, where AMO was mainly leading the other factors with positive correlation, while ENSO and Southern Oscillation (SO) were mainly lagging behind other factors with prolonged correlations; and (3) the interactions between teleconnection factors were quantified into three types: enhancing, independent and offsetting effects. Specifically, the enhancing effect of two-factor combinations was stronger than the offsetting effect, where AMO + NAO (North Atlantic Oscillation) and AMO + AO (Atlantic Oscillation) had a larger distribution area in southern China. Conversely, the offsetting effect of three-factor combinations was more significant than that of the two-factor combinations, which was mainly distributed in northeast and northwest regions of China. This study sheds new light on the mechanisms of modulation and pathways of influencing various large-scale factors on seasonal precipitation dynamics.

Integration of deep learning and improved multi-objective algorithm to optimize reservoir operation for balancing human and downstream ecological needs.

Dam (reservoir)-induced alterations of flow and water temperature regimes can threaten downstream fish habitats and native aquatic ecosystems. Alleviating the negative environmental impacts of dam-reservoir and balancing the multiple purposes of reservoir operation have attracted wide attention. While previous studies have incorporated ecological flow requirements in reservoir operation strategies, a comprehensive analysis of trade-offs among hydropower benefits, ecological flow, and ecological water temperature demands is lacking. Hence, this study develops a multi-objective ecological scheduling model, considering total power generation, ecological flow guarantee index, and ecological water temperature guarantee index simultaneously. The model is based on an integrated multi-objective simulation-optimization (MOSO) framework which is applied to Three Gorges Reservoir. To that end, first, a hybrid long short-term memory and one-dimensional convolutional neural network (LSTM_1DCNN) model is utilized to simulate the dam discharge temperature. Then, an improved epsilon multi-objective ant colony optimization for continuous domain algorithm (ε-MOACOR) is proposed to investigate the trade-offs among the competing objectives. Results show that LSTM _1DCNN outperforms other competing models in predicting dam discharge temperature. The conflicts among economic and ecological objectives are often prominent. The proposed ε-MOACOR has potential in resolving such conflicts and has high efficiency in solving multi-objective benchmark tests as well as reservoir optimization problem. More realistic and pragmatic Pareto-optimal solutions for typical dry, normal and wet years can be generated by the MOSO framework. The ecological water temperature guarantee index objective, which should be considered in reservoir operation, can be improved as inflow discharge increases or the temporal distribution of dam discharge volume becomes more uneven.

Aminic Organoselenium Compounds as Glutathione Peroxidase Mimics and Inhibitors of Ferroptosis.

The synthesis of diarylamine-based organoselenium compounds via the nucleophilic substitution reactions has been described. Symmetrical monoselenides and diselenides were conveniently synthesized by the reduction of their corresponding selenocyanates using sodium borohydride. Selenocyanates were obtained from 2-chloro acetamides by the nucleophilic displacement with potassium selenocyanate. Selenides were synthesized by treating the 2-chloro acetamides with in situ generated sodium butyl selenolate as nucleophile. Further, the newly synthesized organoselenium compounds were evaluated for their glutathione peroxidase (GPx)-like activity in thiophenol assay. This study revealed that the methoxy-substituted organoselenium compounds showed significant effect on the GPx-like activity. The catalytic parameters for the most efficient catalysts were also determined. The anti-ferroptotic activity for all GPx-mimics evaluated in a 4-OH-tamoxifen (TAM) inducible GPx4 knockout cell line using liproxstatin as standard.

NSAIDs do not reduce severity among post-ERCP pancreatitis patients.

OBJECTIVE: Non-steroidal anti-inflammatory drugs (NSAIDs) are the most studied chemoprophylaxis for post-endoscopic retrograde cholangiopancreatography pancreatitis (PEP). While previous systematic reviews have shown NSAIDs reduce PEP, their impact on moderate to severe PEP (MSPEP) is unclear. We conducted a systematic review and meta-analysis to understand the impact of NSAIDs on MSPEP among patients who developed PEP. We later surveyed physicians' understanding of that impact. DESIGN: A systematic search for randomized trials using NSAIDs for PEP prevention was conducted. Pooled-prevalence and Odds-ratio of PEP, MSPEP were compared between treated vs. control groups. Analysis was performed using R software. Random-effects model was used for all variables. Physicians were surveyed via email before and after reviewing our results. RESULTS: 7688 patients in 25 trials were included. PEP was significantly reduced to 0.598 (95%CI, 0.47-0.76) in the NSAIDs group. Overall burden of MSPEP was reduced among all patients undergoing ERCP: OR 0.59 (95%CI, 0.42-0.83). However, NSAIDs didn't affect the proportion of MSPEP among those who developed PEP (p = 0.658). Rectal Indomethacin and diclofenac reduced PEP but not MSPEP. Efficacy didn't vary by risk, timing of administration, or bias-risk. Survey revealed a change in the impression of the effect of NSAIDs on MSPEP after reviewing our results. CONCLUSIONS: Rectal diclofenac or indomethacin before or after ERCP reduce the overall burden of MSPEP by reducing the pool of PEP from which it can arise. However, the proportion of MSPEP among patients who developed PEP is unaffected. Therefore, NSAIDs prevent initiation of PEP, but do not affect severity among those that develop PEP. Alternative modalities are needed to reduce MSPEP among patients who develop PEP.

A novel partitioning of gross primary production and water use efficiency for sustaining water and food security using Budyko hypothesis.

This study coupled the green water and blue water accounting with the existing standard Budyko framework and Fu's 1-parameter Budyko framework to diagnose the basin hydrological behavior. Both Budyko frameworks were employed to determine green water consumption (ETGreen) and blue water consumption (ETBlue) which, in turn, were used to map the blue water index (BWI) hotspots and green water index (GWI) bright spots. The relative contributions of green water and blue water were quantified for sustaining water and food security. A new methodology is proposed using BWI and GWI for partitioning the Gross Primary Production (GPP) and Water Use Efficiency (WUE) into GPPBlue, GPPGreen and WUEBlue and WUEGreen. The methodology was applied to five sub-basins of the Central Godavari River Basin (CGRB): Purna, Dhalegaon, GR Bridge, Yeli and Delta. Results showed that all five basins exhibited larger deviations from the theoretical Budyko curve of Fu's 1-parameter Budyko framework than did the standard Budyko framework and the Dhalegaon basin showed the largest deviations. The partitioning of GPP and WUE by the proposed methodology showed that the proportion of GPPGreen to the total GPP was much higher than that of the GPPBlue. Similarly, the proportion of WUEGreen to WUE was more than that of WUEBlue. The mapping of GPPBlue and GPPGreen, and WUEBlue and WUEGreen showed that the Delta and Yeli basins had the highest values of both GPPGreen & GPPBlue and WUEBlue and WUEGreen (bright spot basins) and the Dhalegaon and parts of GR Bridge basin had the lowest values (hot spot basins). The proposed partitioning of GPP and WUE will help identify the relative contributions of green water and blue water (for managing agricultural waters) and formulate agronomical and engineering practices for stakeholders and policy makers for increasing the overall WUE and GPP to sustain water and food security.

A review of widely used drought indices and the challenges of drought assessment under climate change.

Under climate change, drought assessment, which can address nonstationarity in drought indicators and anthropogenic implications, is required to mitigate drought impacts. However, the development of drought indices for a reliable drought assessment is a challenging task in the warming climate. Thus, this study discusses factors that should be considered in developing drought indices in changing climate. Inconsistent drought assessment can be obtained, depending on the baseline period defined in developing drought indices. Therefore, the baseline period should represent the contemporary climate but should also correspond to long enough observations for stable parameter estimation. The importance of accurate potential evapotranspiration (PET) for drought indices becomes higher under a warming climate. Although the Penman-Monteith method yields accurate PET values, depending on the climate and vegetation cover, other suitable PET formulas, such as the Hargreaves method, with fewer hydrometeorological data can be used. Since a single drought index is not enough to properly monitor drought evolution, a method that can objectively combine multiple drought indices is required. Besides, quantifying anthropogenic impacts, which can add more uncertainty, on drought assessment is also important to adapt to the changing drought conditions and minimize human-induced drought. Drought is expected to occur more frequently with more severe, longer, and larger areal extent under global warming, since a more arid background, which climate change will provide, intensifies land-atmosphere feedback, leading to the desiccation of land and drying atmosphere. Thus, an accurate drought assessment, based on robust drought indices, is required.

Glutathione Peroxidase-like Antioxidant Activity of 1,3-Benzoselenazoles: Synthesis and In Silico Molecular Docking Studies as Pancreatic Lipase Inhibitors.

The synthesis of 1,3-benzoselenazoles was achieved by the reaction of corresponding bis[3-amino-N-(p-tolyl)benzamide-2-yl] diselenide, bis[3-amino-N-(4-methoxyphenyl)benzamide-2-yl] diselenide, and bis[3-amino-N-(4-(dimethylamino)phenyl) benzamide-2-yl] diselenide with aryl aldehydes. The 1,3-benzoselenazoles continued to exist as planar molecules due to the presence of secondary Se···O interactions as revealed by the single-crystal X-ray analysis. The presence of secondary Se···O interactions in 1,3-benzoselenazoles was confirmed using natural bond orbital (NBO) and atoms in molecules (AIM) calculations. Nucleus-independent chemical shift (NICS) values suggested the presence of aromatic character in a five-membered benzoselenazole heterocyclic ring. The glutathione peroxidase (GPx)-like antioxidant activity of all 1,3-benzoselenazoles was assessed using a thiophenol assay, exhibiting greater antioxidant activity than Ph2Se2 used as a reference. The most active catalyst carrying a strong electron-donating group (-NMe2) at the ortho-position to the benzoselenazole ring was further investigated at different concentrations of thiophenol, H2O2, and 1,3-benzoselenazoles as catalyst for determining their catalytic parameters. Moreover, the potential applications of all 1,3-benzoselenazoles against pancreatic lipase (PL) have been identified using in silico interactions between the active sites of the 1LPB protein as evaluated using a molecular docking study.

A framework for water supply regulation in coastal areas by avoiding saltwater withdrawal considering upstream streamflow distribution.

Freshwater availability in coastal areas depends on the withdrawal from tidal rivers. It is severely threatened by saltwater intrusion, especially in the dry season. Freshwater availability is associated closely with natural factors and human activities. Limited research has investigated how freshwater availability is influenced by saltwater intrusion, streamflow, projects, etc., and how the water supply security downstream is affected by the abovementioned factors. To fill these gaps, this paper presents a new framework, i.e., water supply regulation by avoiding saltwater withdrawal (RASW). The framework is based on data on streamflow, tide, wind, the salinity of withdrawal stations, capacities of withdrawal projects and reservoirs, and water demand, which holistically develops relationships among saltwater intrusion, upstream streamflow, and water supply. The RASW contains three phases, i.e., estuary salinity-exceedance simulation, upstream streamflow distribution design, and local water supply security analysis. The proposed intellectual framework and methodology have been tested on the water supply for Zhuhai-Macao of the Guangdong-Hong Kong-Macao Great Bay Area, South China. Results demonstrated that the meta-Gaussian copula efficiently simulated the six-dimensional monthly streamflow distribution and was appropriate for streamflow distribution scenario design. Water supply security benefited greatly from the joint river-reservoir regulation mode. Nevertheless, the water supply security was threatened in the extreme scenarios when the extremely low streamflow distribution happened in the late period or lasted for an extended period. The proposed framework facilitates integrated decision-making for water supply security in coastal areas. Utilizing the streamflow distribution as a management tool and controlling them to avoid extremely low streamflow and adjust their occurrence time can alleviate water supply pressure. Moreover, the capacities of local regulating facilities should be designed with full consideration.

Enhancing the Fruit Yield and Quality in Pomegranate: Insights into Drip Irrigation and Mulching Strategies.

Pomegranate (Punica granatum L.) is a fruit tree that is globally distributed, especially in warm areas with low annual rainfall and limited water availability. This species exemplifies the critical role of water in agriculture and the need for efficient irrigation practices due to its characteristics, cultivation requirements, and geographic diffusion. In this study, we investigated the effects of drip irrigation and mulching on the vegetative growth, yield, and fruit quality attributes of pomegranate. The experiment involved three irrigation regimes (100% of evapotranspiration, 80%, and 60%) and three mulching treatments (no mulch, plastic mulch, and organic mulch) in a factorial combination. Both irrigation and mulching had significant positive influences on the yield and fruit quality attributes. Specifically, deficit irrigation strategies showed a negative impact on the fruit yield per tree, with a greater effect observed as the severity of the irrigation deficit increased. Mulching, on the other hand, led to a significant increase in the fruit yield, primarily attributed to an increase in fruit size. Furthermore, the analysis indicated that irrigation and mulching treatments had distinct effects on fruit traits such as the fruit length, width, volume, and rind thickness. Interestingly, the study highlighted that the effects of irrigation and mulching on fruit quality attributes were mostly independent of each other, suggesting an additive influence rather than an interaction between the two factors. These findings underscore the importance of considering irrigation and mulching practices for optimizing fruit quality in pomegranate cultivation, particularly in semi-arid regions. The results contribute valuable insights for farmers and researchers seeking to enhance fruit production and quality.

Assessing the long-term impact of cascade hydropower development on the inundation patterns of floodplain wetlands.

The inundation process of floodplain wetlands plays a crucial role in maintaining the balance of river ecosystems, which are highly sensitive to hydrological alteration. Nevertheless, the specific mechanisms through which these hydrological changes affect the inundation patterns of floodplain wetlands are still unclear. This study aimed to investigate the impact mechanism of cascade hydropower development on the inundation process of floodplain wetlands. Multitemporal remote sensing datasets and long-term hydrometeorological data series were utilized in this study. By employing the water appearance frequency (WAF) index, wetland hydrological stability assessment, and wavelet analysis, the inundation changes in floodplain wetlands and the underlying hydrological driving mechanisms were examined. The results revealed significant alterations in the inundation frequency of floodplain wetlands due to the construction of upstream dams. Specifically, the construction of the Danjiangkou and Wangfuzhou dams led to an increase in the total inundated area of Part A (16.09 km2) and Part B (76.93 km2), respectively. Conversely, the moderate frequency inundation zone in Part C decreased (26.7 km2) after the construction of the Cuijiaying Dam. The typical floodplain wetland 7 shifted from high to low (8.94 km2) stability after the construction of the Cuijiaying Dam. Furthermore, the cascade hydropower dam construction resulted in increased fluctuations in downstream water discharge. This study provides an effective approach to understanding the impact of cascade hydropower dams on the inundation process of floodplain wetlands.

Drought prediction: Insights from the fusion of LSTM and multi-source factors.

In the context of current global climate change, accurate drought prediction is crucial for water resources management and agricultural production. Although traditional drought forecasting methods largely rely on historical climatic data, these methods cannot fully consider the long-term effects of factors, such as climate change, and the evaluation of prediction results is limited. Therefore, this study proposed a drought prediction and evaluation framework based on Long Short-Term Memory (LSTM), integrating multi-source factors to significantly enhance the accuracy and reliability of drought prediction models. This framework applied two distinct forecasting schemes. The first scheme utilized ten diverse factors, including precipitation, evaporation, bare soil percentage area coverage, percentage crop cover, leaf area index, runoff, surface runoff, soil moisture, temperature, and total vegetated percentage cover, to predict future precipitation and evaporation, which was then used to calculate the Standardized Precipitation-Evaporation Index (SPEI) to evaluate drought characteristics. The second scheme directly used these ten factors and historical SPEI to predict future SPEI, further assessing future drought characteristics. By comparing the drought prediction results of the two schemes in terms of data statistics, drought characteristics, and spatial patterns, it was found that the LSTM model significantly improved accuracy when handling high-dimensional complex data and predicting key factors such as precipitation, evaporation, temperature, and soil moisture. The first scheme was more accurate when predicting severe and extreme droughts, whereas the second scheme was more sensitive to predicting moderate and mild droughts and exhibited higher stability and regularity in predicting the spatial variability of drought. In summary, LSTM has made significant improvements in the accuracy, stability, and reliability of drought prediction, providing stronger support for practical applications, such as agriculture and water resources management, and offering a new research tool for further climate change research.

Amphipathic Liponecrosis Impairs Bacterial Clearance and Causes Infection During Sterile Inflammation.

BACKGROUND & AIMS: Although transient bacteremia is common during dental and endoscopic procedures, infections developing during sterile diseases like acute pancreatitis (AP) can have grave consequences. We examined how impaired bacterial clearance may cause this transition. METHODS: Blood samples from patients with AP, normal controls, and rodents with pancreatitis or those administered different nonesterified fatty acids (NEFAs) were analyzed for albumin-unbound NEFAs, microbiome, and inflammatory cell injury. Macrophage uptake of unbound NEFAs using a novel coumarin tracer were done and the downstream effects-NEFA-membrane phospholipid (phosphatidylcholine) interactions-were studied on isothermal titration calorimetry. RESULTS: Patients with infected AP had higher circulating unsaturated NEFAs; unbound NEFAs, including linoleic acid (LA) and oleic acid (OA); higher bacterial 16S DNA; mitochondrial DNA; altered ß-diversity; enrichment in Pseudomonadales; and increased annexin V-positive myeloid (CD14) and CD3-positive T cells on admission. These, and increased circulating dead inflammatory cells, were also noted in rodents with unbound, unsaturated NEFAs. Isothermal titration calorimetry showed progressively stronger unbound LA interactions with aqueous media, phosphatidylcholine, cardiolipin, and albumin. Unbound NEFAs were taken into protein-free membranes, cells, and mitochondria, inducing voltage-dependent anion channel oligomerization, reducing ATP, and impairing phagocytosis. These were reversed by albumin. In vivo, unbound LA and OA increased bacterial loads and impaired phagocytosis, causing infection. LA and OA were more potent for these amphipathic interactions than the hydrophobic palmitic acid. CONCLUSIONS: Release of stored LA and OA can increase their circulating unbound levels and cause amphipathic liponecrosis of immune cells via uptake by membrane phospholipids. This impairs bacterial clearance and causes infection during sterile inflammation.

Weather-driven synergistic water-economy-environment regulation of farmland ecosystems.

Farmland ecosystems (FEs) constitute the most important source of food production, and water is one of the most important factors influencing FEs. The amount of water can affect the yield and thus the economic efficiency. Water migration can generate environmental effects through the migration of fertilizers. Interlinkages and constraints exist between the water, economy and environment, which require synergistic regulation. Meteorological elements influence the reference crop uptake amount and thus the water cycle processes and are key drivers of regulation at the water-economy-environment nexus. However, the weather-driven, synergistic water-economy-environment regulation of FEs has not been sufficiently researched. As such, this paper employed a dynamic Bayesian prediction of the reference evapotranspiration (ETo) and a quantitative characterization of the total nitrogen (TN) and total phosphorus (TP) contents in agricultural crops and soils via field monitoring and indoor experimental analysis. Consequently, multiobjective optimization modeling was conducted to weigh the mutual trade-offs and constraints between water, the economy and the environment. The proposed method was verified via an example involving the modern agricultural high-tech demonstration park in Harbin, Heilongjiang Province, China. The results indicated that (1) the effect of meteorological factors gradually decreased over time, but the prediction results were very accurate, and the higher the delay order of the dynamic Bayesian network (DBN) was, the more accurate the predictions; (2) ETo was significantly driven by meteorological elements, and the most important meteorological factor influencing ETo throughout the year was average temperature. When the average temperature was reduced by 10.0 %, ETo was reduced by 1.4 %, the required amount of irrigation water was reduced by 4.9 %, and the economic benefits of a single cube of water increased by 6.3 %; (3) resource-economy-environment multidimensional synergy enabled a 12.8 % reduction in agricultural ecosystem pollutant emissions, while the economic benefits per unit of water increased by 8.2 % and the system synergy increased by 23.2 %.

Oceanic climate changes threaten the sustainability of Asia's water tower.

Water resources sustainability in High Mountain Asia (HMA) surrounding the Tibetan Plateau (TP)-known as Asia's water tower-has triggered widespread concerns because HMA protects millions of people against water stress1,2. However, the mechanisms behind the heterogeneous trends observed in terrestrial water storage (TWS) over the TP remain poorly understood. Here we use a Lagrangian particle dispersion model and satellite observations to attribute about 1 Gt of monthly TWS decline in the southern TP during 2003-2016 to westerlies-carried deficit in precipitation minus evaporation (PME) from the southeast North Atlantic. We further show that HMA blocks the propagation of PME deficit into the central TP, causing a monthly TWS increase by about 0.5 Gt. Furthermore, warming-induced snow and glacial melt as well as drying-induced TWS depletion in HMA weaken the blocking of HMA's mountains, causing persistent northward expansion of the TP's TWS deficit since 2009. Future projections under two emissions scenarios verified by satellite observations during 2020-2021 indicate that, by the end of the twenty-first century, up to 84% (for scenario SSP245) and 97% (for scenario SSP585) of the TP could be afflicted by TWS deficits. Our findings indicate a trajectory towards unsustainable water systems in HMA that could exacerbate downstream water stress.

Introduction of Methyl Group in Substituted Isoselenazolones: Catalytic and Mechanistic Study.

Copper-catalyzed direct selenation of substituted 2-bromo-N-phenylbenzamide substrates with elemental selenium powder provided a series of methoxy-substituted isoselenazolones via the C-Se and Se-N bond formations. Phenolic substituted isoselenazolones have been obtained by O-demethylation of the corresponding methoxy-substituted analogues using boron tribromide. Some isoselenazolones have been structurally characterized by X-ray single-crystal analysis. The glutathione peroxidase (GPx)-like antioxidant activity of isoselenazolones has been evaluated both in thiophenol and coupled-reductase assays. All isoselenazolones showed good GPx-like activities in the coupled-reductase assay. The ferric-reducing antioxidant power of phenolic antioxidants has also been evaluated. The best phenolic antioxidants were found to be good ferric-reducing antioxidant power agents. The single electron transfer, hydrogen atom transfer, and proton-coupled electron transfer mechanisms for the antioxidant properties of all catalysts have been supported by density functional theory calculations. The catalytic cycle was proposed for one of the phenolic isoselenazolones involving diselenide, selenenyl sulfide, selenol, and selenenic acid as intermediates using 77Se{1H} NMR spectroscopy.

Synthesis, Reactions, and Antioxidant Properties of Bis(3-amino-1-hydroxybenzyl)diselenide.

Bis(3-amino-1-hydroxybenzyl)diselenide containing two ortho groups was synthesized from 7-nitro-3H-2,1-benzoxaselenole and in situ generated sodium benzene tellurolate (PhTeNa). One-pot synthesis of 1,3-benzoselenazoles was achieved from bis(3-amino-1-hydroxybenzyl)diselenide and aryl aldehydes using acetic acid as a catalyst. The X-ray crystal structure of chloro-substituted benzoselenazole revealed a planar structure with T-shaped geometry around the Se atom. Both natural bond orbital and atoms in molecules calculations confirmed the presence of secondary Se···H interactions in bis(3-amino-1-hydroxybenzyl)diselenide and Se···O interactions in benzoselenazoles, respectively. The glutathione peroxidase (GPx)-like antioxidant activities of all compounds were evaluated using a thiophenol assay. Bis(3-amino-1-hydroxybenzyl)diselenide and benzoselenazoles showed better GPx-like activity compared to that of the diphenyl diselenide and ebselen, used as references, respectively. Based on 77Se{1H} NMR spectroscopy, a catalytic cycle for bis(3-amino-1-hydroxybenzyl)diselenide using thiophenol and hydrogen peroxide was proposed involving selenol, selenosulfide, and selenenic acid as intermediates. The potency of all GPx mimics was confirmed by their in vitro antibacterial properties against the biofilm formation of Bacillus subtilis and Pseudomonas aeruginosa. Additionally, molecular docking studies were used to evaluate the in silico interactions between the active sites of the TsaA and LasR-based proteins found in Bacillus subtilis and Pseudomonas aeruginosa.

Modulation of the chain-breaking antioxidant activity of phenolic organochalcogens with various co-antioxidants at various pH values.

Phenolic organochalcogen chain-breaking antioxidants, i.e. 6-bromo-8 (hexadecyltellanyl)-3,3-dimethyl-1,5-dihydro-[1,3]dioxepino[5,6-c]pyridin-9-ol and 2-methyl-2,3-dihydrobenzo[b]selenophene-5-ol, have been investigated in a two-phase (chlorobenzene/water) lipid peroxidation model system as potent inhibitors of lipid peroxyl radicals with various co-antioxidants at various pH values. The pH has a significant effect on the chain-breaking antioxidant activities of phenolic organochalcogens. The key chain-breaking mechanism profile was attributed to the first oxygen atom transfer from the lipid peroxyl radicals to the Se/Te atom, followed by hydrogen atom transfer in a solvent cage from the nearby phenolic group to the resulting alkoxyl radical. Finally, regeneration of organochalcogen antioxidants could take place in the presence of aqueous-soluble co-antioxidants. Also, in the presence of aqueous soluble N-acetylcysteine at pH 1-7, both antioxidants behaved as very good inhibitors of lipid peroxyl radicals. The role of aqueous soluble mild co-antioxidants in the regeneration studies of organochalcogen antioxidants has been investigated in a two-phase lipid peroxidation model system. The importance of the phase transfer catalyst has been explored in the inhibition studies of selenium containing antioxidants using an Fe(II) source. The overall pH-dependent antioxidant activities of organochalcogens depend on their hydrogen atom transfer ability, relative stability, and distribution in the aqueous/lipid phase.

Water-Energy-Carbon Nexus: Greenhouse Gas Emissions from Integrated Urban Drainage Systems in China.

Greenhouse gas (GHG) emissions from integrated urban drainage systems (IUDSs), including sewer, wastewater treatment plants (WWTPs), and receiving water systems, have not yet been integrated due to the lack of modeling tools. Here, we updated the computable general equilibrium-based System Dynamics and Water Environmental Model (CGE-SyDWEM), a recently developed model simulating the water-energy-carbon nexus at the watershed level, to calculate the direct and indirect (electricity use and external) GHG emissions from IUDSs considering carbon mitigation strategies and water engineering practices. The updated CGE-SyDWEM was applied to an estuary watershed in Shenzhen, the fourth largest city in China. With increasing socio-economic development and water infrastructure systems upgrading, GHG emissions are projected to increase from 129.2 (95% CI: 95.9-162.5) kt in 2007 to 190.7 (144.8-236.6) kt in 2025, with 89% from WWTPs (direct: 17%; electricity use: 65%; and external: 7%), 10% from the sewer (direct: 1% and electricity use: 9%) and 1% from receiving waters (direct). Carbon mitigation can reduce GHG emissions by 7% and emission intensity by 6% by 2025, with 63% contributed by external emission reduction from chemical uses. The integrated model can aid water, energy, and carbon decision-makers in finding cost-effective solutions for water and energy security in the future.