Search

Steroids can be used as biomarkers in clinical metabolomics and other fields related to human toxicology. This chemical group is known for its complexity, considering its number of isobaric compounds and the wide variety of phases I and II metabolic pathways that parent compounds can undergo. For a successful analysis of steroids in biological samples, liquid chromatography separation must be finely tuned. It is especially challenging for glucuronidated and sulfated steroids derivatives that bear polar heads and can be affected by non‐specific adsorption. The benefits of a biphenyl stationary phase chemistry for the selectivity of the separation of steroids and their phase II metabolites and the extent to which nonspecific adsorption phenomena could degrade chromatographic performance were investigated. Replacing a conventional hardware by a passivated hardware allowed to considerably reduce peaks width and asymmetry of sulfated species. The addition of weak ion pairing agents in the mobile phase could also help to reduce non‐specific adsorption but are detrimental to mass spectrometry detection. As confirmed by the successful detection of 52 steroids in plasma, the use of a biphenyl stationary phase complemented by a passivated column hardware is of great help for a successful biomedical analysis of steroids and their phase II metabolites. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: It remains an urgent task to develop alternative hole‐transporting layer (HTL) materials beyond commonly used PEDOT:PSS to increase the shelf‐life of organic solar cells (OSCs). Inorganic metal oxide type materials, such as NiOx, CoOx and VOx, with suitable work functions have attracted numerous research attention recently. In this work, more abundant and easily accessible oxygenated salt, vanadyl sulfate (VOSO4) has been demonstrated to be excellent choice as HTL for OSCs. The VOSO4‐based HTL can be readily processed by spin‐coating from the precursor solution with subsequent thermal annealing and UVO treatment. As a consequence, a high power conversion efficiency (PCE) of 18.72% can be achieved for PM8:L8‐BO based OSCs with the VOSO4‐based HTL. High transmittance, smooth film surface, suitable energy level and high conductivity were revealed to contribute to the high OSC performance. More importantly, compared to device with PEDOT:PSS, VOSO4‐based OSCs exhibit improved stability when stored in the N2 filled glove box. After being stored for 600 h, VOSO4‐based device can retain 89% of its initial efficiency. Notably, VOSO4 can be used as general HTL in PM6:BTP‐BO‐4Cl and PM6:IT‐4F based OSCs, yielding high PCEs of 17.87% and 13.85%, respectively. [ABSTRACT FROM AUTHOR]

Nonlinear optical (NLO) crystals that have the capability of achieving tunable lasers through frequency conversion are of great importance in solid‐state lasers. Herein, three new deep‐UV transparent alkali‐scandium sulfates with strong second‐harmonic generation (SHG) response and high thermal stability, A3Sc(SO4)3 (A = K, Rb, Cs), are successfully obtained. It is interesting that the slightly distorted [ScO6] octahedrons are in an ordered/oriented arrangement, which is in favor of the generation of SHG response. Especially, K3Sc(SO4)3 not only exhibits a strong phase‐matching SHG response of 1.6 × KDP, a short deep‐ultraviolet (deep‐UV) cutoff edge of 190 nm, a wide transparent window covering from the deep‐UV region to mid IR, a high laser‐induced damage threshold of 165 MW cm−2 and easy growth of large single crystal, but also behaves thermal stable up to 900 °C under an air atmosphere. Crystal structures and theoretical calculations reveal that their strong SHG responses mainly stem from the slightly distorted [ScO6] octahedron. This study highlights A3Sc(SO4)3 (A = K, Rb, Cs) as promising deep‐UV transparent NLO crystals and offers a new approach for the pursuit of high‐performance NLO crystals. [ABSTRACT FROM AUTHOR]

Bromine chemistry is responsible for the catalytic ozone destruction in the atmosphere. The heterogeneous reactions of sea‐salt aerosols are the main abiotic sources of reactive bromine in the atmosphere. Here, we present a novel mechanism for the activation of bromide ions (Br−) by O2 and H2O in the absence of additional oxidants. The laboratory and theoretical calculation results demonstrated that under dark conditions, Br−, O2 and H3O+ could spontaneously generate Br and HO2 radicals through a proton–electron transfer process at the air–water interface and in the liquid phase. Our results also showed that light and acidity could significantly promote the activation of Br− and the production of Br2. The estimated gaseous Br2 production rate was up to 1.55×1010 molecules cm−2 ⋅ s−1 under light and acidic conditions; these results showed a significant contribution to the atmospheric reactive bromine budget. The reactive oxygen species (ROS) generated during Br− activation could promote the multiphase oxidation of SO2 to produce sulfuric acid, while the increase in acidity had a positive feedback effect on Br− activation. Our findings highlight the crucial role of the proton‐electron transfer process in Br2 production; here, H3O+ facilitates the activation of Br− by O2, serves as a significant source of atmospheric reactive bromine and exerts a profound impact on the atmospheric oxidation capacity. [ABSTRACT FROM AUTHOR]

Fe‐based sulfate materials have attracted much attention in the cathode of sodium‐ion batteries (SIBs) due to their low cost and high operating voltage, as well as possessing application prospects comparable to hard carbon in the anode based on Fe0/Fe2+/Fe3+ redox properties. However, the poor conductivity and the tendency to agglomerate have limited their further application. Herein, the study constructs a dual‐conductive structure that the Na2.31Fe1.72(SO4)3 particles with amorphous carbon in situ‐coated embedded in ketjen black (KB) conducting carbon networks (NFS/KB) via a solid phase ball‐milling strategy, which effectively enhanced inherent conductivity and electron transfer efficiency among particles of the Fe‐based sulphate. The NFS/KB can provide a reversible capacity of 92 mAh g−1 at 0.1 C and stable cycling stability at high current (85% retention after 500 cycles at 20 C) as cathode of SIBs. Surprisingly, as anode of SIBs, the NFS/KB delivers a rate performance (149 mAh g−1 at 10 C) that is superior to that of hard carbon. Notably, further application of the material to symmetric SIBs also achieves favorable results. This work effectively enhances the performance of Fe‐based sulphate materials in SIBs with a low‐cost carbon modification method, providing a new approach for the low‐cost symmetric SIBs. [ABSTRACT FROM AUTHOR]

Mesozoic oceanic anoxic events were characterized by relatively low seawater sulphate concentrations ([SO42−$$ {{\mathrm{SO}}_4}^{2-} $$]), which likely regulated the development and evolution of these major palaeoceanographic phenomena. However, there is little reliable sedimentary evidence for low [SO42−$$ {{\mathrm{SO}}_4}^{2-} $$] in ancient marine waters and understanding of how such a seawater chemistry potentially impacted oceanic anoxic events is limited. This study presents an integrated sedimentological, mineralogical and geochemical investigation of the mineral siderite hosted in dark grey shale and sideritic concretions of Early Aptian (coeval with Oceanic Anoxic Event 1a) from the Tibetan Himalaya. Siderite is present throughout the section and possesses similar morphological characteristics whether in dark grey shale or concretions. Siderite can be present as disseminated and rhombic crystals formed during early diagenesis, or minor spherical crystals formed during late diagenesis. The evidence from redox elements, middle rare‐earth element bulge patterns and extremely low carbon‐isotope values of the sideritic concretions indicates that the iron carbonate was formed in the Fe‐reduction zones by the process of dissimilatory iron reduction. This process would have required conditions of low [SO42−$$ {{\mathrm{SO}}_4}^{2-} $$], reducing environment, abundant iron and high alkalinity. Additionally, the coexistence of siderite and pyrite may indicate that dissimilatory iron reduction occurred close to the microbial sulphate reduction zone, with seawater [SO42−$$ {{\mathrm{SO}}_4}^{2-} $$] hovering around the tipping point at which pyrite could form once seawater sulphate increased. Such an increase during Oceanic Anoxic Event 1a could have resulted from basalt–seawater interaction and associated enhanced continental weathering, and/or hydrothermal activity. This study's observations support the previous hypothesis that low [SO42−$$ {{\mathrm{SO}}_4}^{2-} $$] for Oceanic Anoxic Event 1a was probably caused by massive gypsum burial in the proto‐South Atlantic. Subsequently, enhanced sulphate input could have promoted microbial sulphate reduction and accompanying oxidation of organic matter, which likely further enhanced nutrient recycling, increased primary productivity and organic‐carbon burial, leading to more oxygen consumption and expansion of oxygen minimum zones, as reconstructed for many oceanic anoxic events. [ABSTRACT FROM AUTHOR]

A combination of fixed dose tablet containing 0.5 mg lobeglitazone sulfate (LBZ) and 1 mg glimepiride (GLM) has demonstrated efficacy in enhancing glycemic control in diabetes. The projected work aimed to develop and validate a high‐performance thin‐layer chromatographic (HPTLC) methodology for the precise quantification of both the drugs in tablet formulations. The HPTLC analysis utilized aluminium plates layered with silica gel 60F254, and the solvent system consisted of ethyl acetate, benzene, and hexane (4:3:1 v/v/v) followed by densitometric scanning at 238 nm. The Rf value was found to be 0.68 ± 0.001 for LBZ and 0.48 ± 0.002 for GLM. The methodology exhibited linearity in the range of 100–2000 ng/band for LBZ and 200–4000 ng/band for GLM, with correlation coefficients of 0.9988 and 0.9981, respectively. Exceptional sensitivity was observed, with detection limits of 23.86 ng/band for LBZ and 58.26 ng/band for GLM, along with quantification limits of 72.32 ng/band for LBZ and 176.55 ng/band for GLM. The method demonstrated precision (% relative standard deviation of peak area < 2) and accuracy (recovery between 97% and 102%). The suggested method is suitable for quantifying both the drugs in tablets, making it useful for routine quality control in laboratories. [ABSTRACT FROM AUTHOR]

For the first time, a method for the synthesis of 2,3‐dihydropyrazine 1,4‐dioxide derivatives was devised. The presented approach is based on the reaction of N,N′‐(2,3‐dimethylbutane‐2,3‐diyl)bis(hydroxylamine) with α‐ketoaldehydes. A distinctive feature of the proposed protocol is the application of sulfate of the aforementioned bis‐hydroxylamine in the considered condensation. The advantages of the newly developed route are a one‐step synthetic procedure involving easily available starting materials, atom economy, and simple work‐up of the reaction mixture. The structure of one of the obtained products was confirmed by x‐ray analysis. [ABSTRACT FROM AUTHOR]

Fog processing has a significant impact on sulfur chemistry in the atmosphere. This study analyzed three winter fog events in Hong Kong using single‐particle aerosol mass spectrometry (SPAMS) and a Monitor for AeRosols and GAses in ambient air (MARGA). Black carbon (BC)‐related carbonaceous particles with substantial sulfate amounts comprised the largest particle number fraction (56.7%). Sulfate mass concentration decreased during fog due to the cloud's effective scavenging, but fog processing notably promoted sulfate formation at the single‐particle level (average peak area increases of 31.2%). Hydroxymethanesulfonate (HMS), an important S(IV) compound and fog tracer, was identified accounting for up to 12% by particle number fraction. Although pH showed a positive correlation (r = 0.53–0.69) with HMS particles in each fog scenario, a negative overall correlation (r = −0.51) was observed. Further analysis revealed that the higher aerosol acidity (pH 0.65–3.11), promoted Fe dissolution, leading to 49% of HMS particles being mixed with Fe, which potentially facilitated sulfate formation via the Fenton reaction. Additionally, around 40% of HMS‐Fe particles are mixed with oxalate, thereby warranting further attention for their potential to cause more intricate sulfur oxidation processes. This study reveals the initial identification of a high mixed‐state of HMS‐Fe, which could potentially serve as a crucial avenue for the formation of sulfate on individual particulate matter. Considering the persistent augmentation of aerosol acidity in the Asian region, this phenomenon necessitates further investigation and attention. Plain Language Summary: Cloud and fog processes are crucial for atmospheric chemistry and important pathways in sulfate formation. However, current models often underestimate sulfate production in the atmosphere. While several potential pathways have been proposed, the influence of organic compounds on hydroxymethanesulfonate (HMS) formation and its subsequent sulfate generation is yet to be fully explored. This study, utilizing a single‐particle perspective, reveals that higher aerosol acidity in coastal areas can lead to the dissolution of iron (Fe) in coastal aerosols, thereby promoting the formation of HMS‐Fe. Additionally, as a transition metal, Fe has the potential to catalyze the conversion of HMS to sulfates. This finding challenges the prevailing notion that HMS hinders sulfate production by being less susceptible to oxidation by hydrogen peroxide (H2O2) and other radicals. The significance of this process is particularly pronounced in coastal or remote marine atmospheres, where cloud and fog processes exhibit higher aerosol acidity and limited ammonia sources. Furthermore, considering the current global scenario of increased aerosol acidity, the impact of transition metals on sulfate formation in HMS is likely to be more prominent. Consequently, this phenomenon necessitates further investigation and attention. [ABSTRACT FROM AUTHOR]

Transition metal sulfides (TMS) exhibit significant promise as non‐noble‐metal electrocatalysts for the oxygen evolution reaction (OER) in alkaline environments, notwithstanding their susceptibility to long‐term instability due to the gradual leaching of surface‐reconstructed sulfate ions (SO42−). In this study, a sulfate ion‐assisted strategy is proposed to stabilize the surface‐reconstructed SO42− of FeNiS2. The findings reveal that SO42− experiences considerable loss in KOH due to the infinite concentration gradient of SO42− on the surface. Conversely, in K2SO4/KOH, this strategy mitigates rapid leaching and preserves the predominant surface‐reconstructed SO42−, thereby enhancing stability in both accelerated degradation (5000 cycles) and long‐term (≥120 h) tests, with ≈95% current density retained. Furthermore, the optimal concentration of SO42− proves to be crucial, as supported by both experimental and theoretical results. This approach offers insights into bolstering the long‐term OER stability of TMS and similar compounds, thereby advancing the prospects for widespread application in electrocatalytic water splitting. [ABSTRACT FROM AUTHOR]

The fish‐derived bile salt 5α‐cyprinol sulfate (CPS) has been identified as a kairomone inducing the predator avoidance behavior "diel vertical migration" (DVM) in Daphnia magna in response to fish. However, conclusions about the ecological significance of CPS have been derived from laboratory experiments only. Using a mesocosm approach, we investigate whether the role of CPS as a kairomone can be confirmed in the field. We demonstrate that CPS induces downward migration during daytime in a field‐derived Daphnia community mainly consisting of Daphnia longispina and Daphnia cucullata within the experiment. In the study lake, the actual population of D. longispina shows a similar pattern of DVM, while concomitant quantification of CPS by HPLC‐MS confirms that CPS in situ concentrations are sufficiently high for induction of daytime downward migration of D. longispina in this oligo‐mesotrophic lake. Together, these observations infer that CPS is a significant kairomone‐inducing DVM‐like behavior in Daphnia. [ABSTRACT FROM AUTHOR]

Rhamnan sulphate (RS) is a sulphated polysaccharide found in green algae such as Monostroma nitidum that exhibits various biological functions, including anticoagulant, antitumour, antiviral, and anti‐obesity properties. In our previous clinical trial, we demonstrated that RS intake improves constipation. However, no specific bacteria showed a significant (p <.05) change. Notably, these results were obtained after a short RS inoculation period of only 2 weeks. In the present study, to evaluate the long‐term effects of RS on the gut microbiota, we orally administered RS to BALB/c mice for 11 weeks, analyzed their blood biochemical data, and performed 16s rRNA‐sequencing. Oral administration of RS increased body weight with increased food intake, whereas plasma total cholesterol and fasting plasma glucose levels decreased. RS‐fed mice showed lower fasting insulin levels (p <.1) and decreased homeostatic model assessment for insulin resistance (HOMA‐IR, p <.0001), suggesting that RS improved insulin resistance. In the feces of mice, the amounts of acetic and propionic acids increased. In the gut microbiota, predictive metagenomic profiling using the phylogenetic investigation of communities by reconstruction of unobserved states (PICRUSt2) revealed functional alterations in Kyoto Encyclopaedia of Genes and Genomes (KEGG) pathways in RS‐fed mice. Corresponding to the blood glucose‐lowering effect, the glycolysis and tricarboxylic acid (TCA) cycle pathways were activated. In addition, the Firmicutes/Bacteroides (F/B) ratio, which may be associated with various health outcomes, was also reduced. These results suggest that the blood glucose‐lowering effect, improvement in insulin resistance, and lipid‐lowering effect of RS may be due to changes in the intestinal microbiota. [ABSTRACT FROM AUTHOR]

Objectives: This study aimed to compare the surface roughness and friction of different orthodontic archwires after exposure to salbutamol sulphate inhalation, an anti‐asthmatic medication. Methods: Orthodontic archwires (stainless‐steel [StSt], nickel‐titanium [NiTi], beta‐titanium [β‐Ti], and copper‐NiTi [Cu‐NiTi]) were equally divided into two groups. The exposed groups were subjected to 20 mg salbutamol sulphate for 21 days and kept in artificial saliva. The control groups were only kept in artificial saliva. Surface changes were visualized using scanning electron microscopy (SEM). The average surface roughness (Ra) was evaluated using atomic force microscopy (AFM), and friction resistance forces were assessed using a universal testing machine. Statistical analyses were performed using t‐tests and ANOVA followed by post hoc tests. Results: Salbutamol sulphate did not change the surface roughness of StSt and NiTi archwires (p >.05). However, the change in the surfaces of β‐Ti and Cu‐NiTi archwires was significant (p <.001). The frictional forces of exposed StSt, NiTi, and Cu‐NiTi archwires did not change (p >.05). However, the frictional forces of β‐Ti archwires increased significantly after exposure to salbutamol sulphate (p =.021). Brushing with fluoride after exposure to salbutamol sulphate increased the frictional forces of β‐Ti only (p =.002). Conclusions: Salbutamol sulphate inhalation significantly affected the surface texture of β‐Ti and Cu‐NiTi orthodontic archwires and increased the friction of β‐Ti archwires. These deteriorating effects were not detected on the surface of StSt and NiTi archwires. Therefore, we suggest that β‐Ti and copper titanium archwires should be used cautiously in individuals under salbutamol sulphate inhalation treatment. [ABSTRACT FROM AUTHOR]

Sodium‐ion batteries (SIBs) are crucial energy equipment that sustain low cost and better environmental benefit. Nevertheless, the practical energy density of SIBs is limited by cathode material. Over last decades, the iron‐based sulfate (IBS) has been extensively studied owing to its numerous advantages, including a large theoretical specific energy (over 100 Wh kg−1), high working potential (above 3.4 V), low cost, good structural stability, and environmental friendliness. Nevertheless, the application of IBS in SIBs is limited by its unsuitable electrolyte and low electronic/ionic conductivity. This review summarizes recently developed results on IBS materials for SIBs, ranging from the phase diagram–composition structure–electrochemical performance to modification research. A generalized summary of the future prospects of IBS‐based materials is also provided, with the hope of inspiring further advances in their application in SIBs. [ABSTRACT FROM AUTHOR]

Sulfates with a large bandgap are always promising optical candidates. However, due to insufficient birefringence, their applications are restricted. Here, in terms of this deficiency, two strategies are proposed to rationally modulate the optical anisotropy of sulfates by cations and anions, respectively. For the cation modulation, the [C(NH2)3]Al(SO4)2·6H2O crystal is investigated, which exhibits an unprecedented birefringence (0.098 @ 546 nm) compared with other deep‐ultraviolet transparent sulfates, resulting from the synergy of π‐conjugated [C(NH2)3]+ and non‐π‐conjugated [SO4]2− groups. For the anion modulation, a novel functional group, [S3O6]2−, with a large polarizability anisotropy, is designed. Thus, a new crystal, NaKS3O6, is obtained, which exhibits a large birefringence of 0.130 @ 546 nm with a short ultraviolet absorption cutoff edge of 215 nm. These results confirm the validity of the strategies. Therefore, the strategies play an important role in improving sulfate's birefringence and then promoting their potential applications in advanced optical systems. [ABSTRACT FROM AUTHOR]

Engineered cementitious composites (ECC) are a class of high‐performing fibre‐reinforced cementitious materials recognised for their increased ductility and durability compared to conventional cement‐based materials, owing to their autogenously controlled tight crack widths, even when subjected to high strains. To reduce ECC's environmental impact, this research examines the use of a low‐clinker binder − limestone‐calcined clay cement (LC3) − as an alternative to portland cement (PC), along with fly ash to further reduce the clinker proportion and the embodied CO2 of the formulations. In conventional concrete, LC3 hydrates to a denser microstructure resulting from the synergistic reaction between limestone and calcined clay. At the lower water contents typical of ECC and with the presence of fly ash, the influence of the binder composition on the microstructure is difficult to anticipate. To examine the influence of these compositional variables on microstructure, permeability and durability, the sulphate resistance of LC3‐based ECC is explored. Specifically, the ECC‐LC3 blends are designed with high clinker replacement rate of 75% by mass of binder and contain either conventional fly ash or reclaimed fly ash at 50% by mass of binder. Expansion of ECC‐LC3 samples subjected to standard sodium sulphate test conditions was measured up to 12 months and the depth of penetration of sulphates into the ECC‐LC3 of varying compositions was quantified using micro‐X‐Ray Fluorescence (microXRF) imaging and modelling. The expansion results show that the ECC‐LC3 formulations performed better than the PC samples and can provide adequate resistance to external sulphate attack, even when reclaimed fly ashes are used in place of the conventional ash. In addition, the shallow penetration of sulphate into these cementitious composites demonstrates the low diffusion coefficients values that were determined using the quantitative data from MicroXRF imaging. [ABSTRACT FROM AUTHOR]

Soil fertility diagnosis often omits subsoil measurements, impacting precision. Our objective was to compare the vertical distribution of nitrate and sulfate in agricultural Mollisols. Both anions were measured in 34 Mollisols of the Pampean region (Argentina) sampled to 160‐cm depth at 20 cm intervals. Nitrate exhibited a continuous downward trajectory, with maximum values at 0–20 cm (12.7 mg N kg−1) and minimum values at 140–160 cm (3.3 mg N kg−1). Sulfate displayed a sinuous pattern, with a minimum at 60–80 cm (3 mg S kg−1). The 60–160/0–160 cm concentration ratio was 42% for nitrate and 60% for sulfate, indicating greater topsoil stratification for nitrate. Predicting deep‐layer nitrate concentrations from topsoil data was more accurate than for sulfate. This poses a challenge for assessing soil S bioavailability, as subsoil sulfates go undetected in conventional sampling. Core Ideas: Nitrate content consistently decreased from the shallowest to the deepest soil layer.In contrast, sulfate exhibited a sinuous trajectory, with minimum values at 60–80 cm.Compared to sulfates, the stratification toward the topsoil was 35% higher for nitrates.Sulfates in the upper layers failed to predict sulfate concentrations in deep layers.Nitrate at 20–60 cm was an acceptable predictor of subsoil nitrate (60–160 cm). [ABSTRACT FROM AUTHOR]

Sulfate surfactants in cosmetic products raise concerns due to their skin irritating impact and sustainability. Rhamnolipid, a green and safe biosurfactant, was studied from the perspective of rheology to help develop a formulation with natural and effective ingredients for cosmetics. The viscosity of rhamnolipids was investigated by changing pH, concentration and adding additives like inorganic salts (NaCl, MgCl2) and polymers (Carbopol® Ultrez 20, Carbopol® Aqua SF‐1, Carbopol® 940 and cationic guar gum), showing that the viscosity of rhamnolipid had a positive correlation with the increase of concentration, a negative correlation with the increase of pH, and that polymers instead of inorganic salts were suitable for thickening rhamnolipid. Further rheology tests indicated that Carbopol® Aqua SF‐1 imparted gel properties of rhamnolipid while cationic guar gum determined the liquid properties. In addition, the rhamnolipid‐containing moisturizing cream consisting of stearic acid/squalane ratios all showed shear‐thinning and gel behavior the same as the commercial ones. Visual appearance and particle size analysis indicated that all formulations exhibited high storage stabilities. The knowledge gained from this study may be useful for designing "sulfonate‐free" shampoo and cream with rheological properties that can be tailed for specific commercial cosmetic applications. [ABSTRACT FROM AUTHOR]

In previous studies, CST has been identified as having an immunostimulatory effect on Caenorhabditis elegans and macrophage of rats. Here, we further investigated its immunomodulatory effects on human peripheral blood mononuclear cells (PBMCs). LPS‐stimulated PBMCs inflammatory model was established. Flow cytometry was applied to measure phagocytosis of PBMCs. Cytokine mRNA and protein expression levels of LPS‐stimulated PBMCs with or without CST were measured by qRT‐PCR and ELISA. The transcriptomic profile of CST‐treated PBMCs was investigated by RNA‐sequencing. Gene Ontology (GO) and Kyoto Encylopedia of Genes and Genomes (KEGG) were applied to find potential signalling pathways. PBMCs showed a significant increase in phagocytic activity at 6 h after being incubated with CST at the concentration of 10 μg/mL. In the presence of LPS, CST maintained and promoted the expression of TNF‐α and chemokine CCL24. The content of pro‐inflammatory cytokines, such as IL‐1β, IL‐6 and IFN‐γ, which were released from LPS‐stimulated PBMCs, was reduced by CST at 6 h. Anti‐inflammatory cytokines, such as IL‐4, IL‐13 and TGF‐β1, were significantly increased by CST at 24 h. A total of 277 differentially expressed immune‐related genes (DEIRGs) were detected and cytokine‐cytokine receptor interaction was highly enriched. CST presented obvious anti‐inflammatory and immunoregulatory effects in LPS‐induced PBMCs inflammatory model not only by improving the ability of PBMCs to clear pathogens but also by decreasing pro‐inflammatory cytokines and increasing anti‐inflammatory cytokines. And the mechanism may be related to cytokine‐cytokine receptor interaction. [ABSTRACT FROM AUTHOR]

Sonopiezoelectric therapy (SPT) has gained ever‐increasing prominence in tumor therapy as a combination of ultrasound (US) and piezoelectric nanomaterials to generate cytotoxic reactive oxygen species (ROS) for tumor suppression. In this study, the facile hydrothermal method is used to construct the distinct 2D piezocatalyst Bi2Fe4O9 nanosheets (BFO NSs). The engineered BFO NSs can create a piezoelectric field when exposed to US irradiation, facilitating the separation of electron–hole (e−–h+) pairs to play a crucial role in Fe3+/Fe2+ circulation, which catalyzes the activation of peroxymonosulfate (PMS), resulting in an amplified production of cytotoxic sulfate radical (SO4•−). The produced SO4•− combines with ROS generated by SPT including hydroxyl radicals (•OH), and singlet oxygen (1O2), leading to the augmented oxidative tumor suppression. The BFO NSs and PMS are further integrated into a thermal hydrogel (BFO/PMS‐Gel) for in vitro and in vivo investigations on their catalytic antitumor effects. In both in vitro and in vivo studies, it is validated that BFO/PMS‐Gel, under US irradiation, significantly enhances radicals generation efficiency, which achieves superior antitumor performance while maintaining high therapeutic biocompatibility and biosafety, providing a representative paradigm of US‐activated multiple radicals production as enabled by piezoelectric nanomedicine for antitumor treatment. [ABSTRACT FROM AUTHOR]

Balantioides coli (=Balantidium coli), a large ciliated protozoan, is reported in multiple free‐ranging and captive primate species, often in association with a clinical presentation that requires medical intervention. This report describes the clinical effectiveness of paromomycin sulfate against B.coli in zoo‐kept mandrill monkeys (Mandrillus sphinx, at orally doses of 8–31 mg/kg, once daily (SID) for 7 days) and gorillas (Gorilla gorilla gorilla, at orally doses of 1.4–3.1 mg/kg, SID for 5 days). [ABSTRACT FROM AUTHOR]

Objective: An experiment was conducted to evaluate the effects of repeated copper sulfate (CuSO4) treatments on the growth and survival of juvenile Walleye Sander vitreus. Methods: Culture tanks were treated with 0 or 0.76 mg/L CuSO4 every other day for five exposures, then were not treated for 14 consecutive days; this regimen was repeated for a total of 10 exposures over the course of 50 days. Copper sulfate treatments had a half‐life of about 60 min. The study was conducted in flow‐through well water at ≈1.5 L/m and 23.8°C. Result: The resulting survival data for CuSO4 treated and nontreated fish was 96% and 85% survival, respectively, and not statically different. There was no difference in weight, with treated weighing 25.3 g compared to 25.2 g for nontreated control fish. Both groups had weight increases of over 400% during the study. Neither group differed in length, with treated fish reaching a mean length of 14.6 cm and nontreated reaching a mean length of 14.5 cm. Conclusion: The results indicate that repeated CuSO4 treatments had no effect on Walleye growth or survival. Impact statementCopper sulfate has a long history of use in aquaculture. While it is no secret that copper toxicity or other deleterious effects can happen, if used appropriately copper sulfate can be one of the most useful chemicals in aquaculture. [ABSTRACT FROM AUTHOR]

Crystalline ferric sulfates (e.g., ferricopiapite and Fe(OH)SO4) have been proposed at multiple locations on Mars by the orbiter. While at Meridiani Planum and Gale Crater by rover missions, amorphous ferric sulfates were also suggested to exist in soils and sedimentary rocks. Ferric sulfates with different hydration degrees may play a key role in the water cycle on Mars. In order to understand the role of the hydrated ferric sulfates in the water cycle and their exact hydration states on Mars, five crystalline ferric sulfates and seven amorphous ferric sulfates with different hydration states were synthesized in the laboratory. The water content (number of H2O molecules per ferric sulfate molecule) was quantified by Raman spectroscopy and Laser‐induced breakdown spectroscopy (LIBS), respectively. It was found that the amorphous ferric sulfates water content has a good relationship with the SO4 tetrahedron main Raman feature position around 1,000 cm−1, shown as the intensity and area of water feature around 3,500 cm−1 over SO4 tetrahedron main Raman feature around 1,000 cm−1, respectively. Twelve ferric sulfates' Hα emission line area at 656.7 nm was normalized by the O emission line area at 778 nm in LIBS spectra. The crystalline and amorphous ferric sulfates all showed a good relationship between the values of normalized results and the water content. These results will aid us in precisely constraining the exact phases of hydrated ferric sulfates, provide a better reference for ChemCam, SuperCam, and Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals data interpretation and their use to quantify the water content in detected targets. Plain Language Summary: Hydrated ferric sulfates have been suggested to occur on Mars at different sites (e.g., Meridiani Planum and Gale Crater) during orbital and rover missions. The hydration states of crystalline or amorphous ferric sulfates are greatly affected by environmental conditions, and the amorphous ferric sulfates are metastable phases, which are considered to be produced by rapid dehydration and rehydration processes. The presence of ferric sulfates indicates the occurrence of water‐related processes, while the water content within these compounds can provide valuable insights into Mars' water history. However, the exact phases of ferric sulfates cannot be precisely constrained except for the jarosite that limited our knowledge about the water‐related geochemical process on Mars. In the present study, 12 hydrated ferric sulfates were synthesized in the laboratory and measured by Raman and Laser‐induced breakdown spectroscopy (LIBS) spectroscopy. The unique Raman features of those ferric sulfates will help to identify them on Mars by Raman spectroscopy. Besides, the methods of water content quantification were developed based on their Raman and LIBS spectra, respectively. It will help us to better understand the water cycle and provide a better reference for payloads such as ChemCam, SuperCam, and SHERLOC to determine the ferric sulfates on Mars. Key Points: Seven amorphous ferric sulfates with specific hydration degrees (6w–12w) were synthesizedWater quantification of amorphous and crystalline ferric sulfates is achieved using Raman and Laser‐induced breakdown spectroscopy spectroscopic methodsA new pathway of amorphous ferric sulfates formed by unsaturated solution is suggested to occur on Mars [ABSTRACT FROM AUTHOR]

Objective: The purpose of this in vitro study was to evaluate the effect of potassium aluminum sulfate (alum) application on the stainability and translucency of computer‐aided design and computer‐aided manufacturing (CAD‐CAM) materials after coffee thermocycling (CTC). Materials and Methods: Disk‐shaped specimens (Ø10 × 1 mm; N = 200) were fabricated by using additively (Crowntec [CT] and Varseo Smile Crown Plus [VS]) and subtractively manufactured (Brilliant Crios [RCR], CEREC Block [FC], and Vita Enamic [VE]) CAD‐CAM materials and polished. All specimens were randomly divided into two groups as alum applied and control (n = 10). All specimens were then subjected to CTC (10,000 cycles at 5–55°C) and color coordinates were measured at each time interval. Color differences (ΔE00) and relative translucency parameters (RTPs) were calculated and the data were statistically analyzed (a = 0.05). Results: Among tested time intervals, alum applied specimens had their lowest ΔE00 after alum application (p ≤ 0.006), except for FC (p = 0.177). In addition, alum applied RCR had lower ΔE00 values than its control specimens (p = 0.029). Alum applied specimens had their lowest RTP after CTC (p < 0.001) and alum application decreased the RTP of CT (p = 0.010). CTC reduced the RTP of all materials in control groups (p < 0.001). Alum applied CT had higher RTP than its control specimens (p = 0.049). Conclusions: Alum application's effect on color change varied depending on the material and alum mostly resulted in clinically acceptable changes in translucency. CTC led to unacceptable color and translucency changes based on previously reported threshold values. Clinical Significance: Optical properties of CAD‐CAM materials and the sustainability of these properties over time is critical for longevity. Alum may improve the color stability of reinforced composite resin when subjected to long‐term coffee consumption. [ABSTRACT FROM AUTHOR]

Degradation of organic coatings is essential for recycling valuable substrates. Despite the development of strategies for this purpose, the resulting degradations are typically constrained by the composition of the coating. This paper presents a simple strategy utilizing radicals induced by UV for the degradation of diverse organic coatings. The sulfate radicals, generated from UV‐exposed ammonium persulfates, induce the degradation of various organic coatings, including layer‐by‐layer assembled coating composed of alginate and chitosan polymers as well as polydopamine coating. This strategy also facilitates the separation of two adhered substrates by degrading the adhesive polymer layer positioned between them. This novel approach enables the complete degradation of various organic coatings in aqueous conditions without imposing restrictions on their composition, leading to the recovery of the original surface properties of the substrate. [ABSTRACT FROM AUTHOR]

The sulfur (S) mass fraction of carbonate minerals can be used to reconstruct the environmental conditions and S sources at the time of precipitation. As S is present in a wide range of host materials, there is an urgent need to develop a method to extract S from a single mineral phase. We have developed a method to extract structurally substituted sulfate, termed carbonate‐associated sulfate (CAS), from geological and biogenic carbonate minerals using weakly acidic cation exchange resins. Two types of weakly acidic cation exchange resin (methacrylic acid and acrylic acid types) were tested to minimise the blank S contents and decompose carbonate. After repeated cleaning of the resins with high‐purity water or HCl, the blank S contents were reduced to < 0.1 μg, which is < 0.1% of the CAS in the samples. The cleaned resin was used to dissolve 10 and 25 mg of the JCp‐1 carbonate certified reference material (CRM; Japanese National Institute of Advanced Industrial Science and Technology, AIST). Samples and resin were added to 8 ml of high‐purity water at resin/sample ratios of 2, 5, 10 and 20, set on a shaking table, and reacted. The supernatant solutions were sampled sequentially from 0.5 h to 87 h after the start of experiments. The results show that the optimal conditions for decomposing 10 mg of carbonate is a resin/sample ratio of ≥ 10 with a reaction time of ≥ 40 h. Carbonate‐associated S mass fractions were measured for six geological and biogenic carbonate CRMs. The coefficient of variation in carbonate‐associated S mass fractions was ≤ 7%, regardless of the type of resins used. The mass fractions determined with this method recover 74–94% of the total S mass fractions reported in previous studies, suggesting that this method dissolved carbonate, and did not leach other S‐bearing fractions that are not resistant to weak acids. Another benefit of this method is that the decomposed solution can be introduced directly into the ion chromatograph, allowing for more sensitive analyses. We emphasise that this method can also be used for S isotopic measurements, as S contamination from other S‐bearing mineral phases is low. [ABSTRACT FROM AUTHOR]

Secondary ion mass spectrometry was used to test the δ18O and δ34S nanogram‐scale homogeneity of a suite of candidate sulfate minerals, ultimately selecting three barite, two anhydrite, and two gypsum samples from the Royal Ontario Museum that have repeatabilities for their SIMS measurements of better than ±0.39‰ and ±0.37‰ (1s) for oxygen and sulfur isotope ratios, respectively. Metrological splits of each of the seven materials were sent to multiple gas source isotope ratio mass spectrometry laboratories in order to establish their absolute 18O/16O and 34S/32S ratios. The inter‐laboratory results of GS‐IRMS analyses yielded reasonably narrow ranges in δ18OVSMOW, whereas larger variations in δ34SVCDT values were found between the results from the gas source laboratories. All samples have good reproducibility within laboratories of GS‐IRMS 103δ18O values of between ±0.24‰ and ±0.44‰ (1s). The reproducibility within laboratories of GS‐IRMS 103δ34S values range from ±0.07‰ to ±0.99‰ (1s). Here we also discuss some of the current analytical limitations affecting these isotope‐mineral systems. A total of 256 metrological splits have been prepared from each of these seven materials; these aliquots will be made available to the global geochemical community. [ABSTRACT FROM AUTHOR]

Understanding the interaction between molybdenum (Mo) and organic matter during microbial sulfate reduction is critical for the use of Mo to reconstruct marine redox conditions throughout Earth's history. However, little is known about Mo isotope fractionation and how it relates to organic matter remineralization during microbial sulfate reduction. Here, we report Mo abundances and isotopic (δ98Mo) compositions for bulk‐rock, non‐lithogenic and sequentially extracted fractions, including carbonate (carb), pyrite, and organic matter (OM), of seep carbonate rocks. Our data indicate that the difference between δ98Mocarb and δ98MoOM (Δ98Mocarb‐OM) displays significant variability in the studied samples, ranging between 0.72 and 1.01‰. Remarkably, the obtained Δ98Mocarb‐OM values indicate correlative trends with stable carbon isotope ratios and bulk abundances of (a) total organic carbon, (b) Mo, and (c) pyrite in seep carbonates, which we interpret as reflecting sustained adsorption of isotopically light Mo onto organic matter during enhanced sulfate reduction. On this basis, we put forward the concept that Δ98Mocarb‐OM of authigenic carbonate rocks can be used as a measure of the intensity of sulfate reduction and for reconstructing past interactions between Mo and organic matter in marine sediments. Plain Language Summary: Molybdenum (Mo) is a useful element for reconstructing marine redox conditions throughout the Earth's history. The sequestration of Mo through sulfate‐reducing bacterial activity acts as a significant pathway for Mo burial in the ocean. However, the impact of microbial sulfate reduction in Mo isotope fractionation remains unclear, preventing the understanding of the interaction between Mo and organic matter. We report Mo abundances and isotopic (δ98Mo) compositions for different phases extracted from seep carbonate rock fractions, including carbonate (carb), pyrite, and organic matter (OM). Our findings indicate that organic matter tends to preferentially adsorb isotopically light Mo. The observed δ98Mo difference between carbonate and organic matter fractions (Δ98Mocarb‐OM from 0.72 to 1.01‰) represents the first report of the extent of Mo isotope fractionation during Mo adsorption to organic matter in marine environments. We attribute greater Δ98Mocarb‐OM offsets to the preferential adsorption of isotopically light Mo onto organic matter during enhanced sulfate reduction, and in turn put forward the idea that such offsets can be possibly used in the sedimentary record to trace the intensity of sulfate reduction and to reconstruct the past interaction between Mo and organic matter in marine sediments. Key Points: Organic matter tends to adsorb isotopically light Mo, resulting in low δ98Mo values of organic matter in marine environmentsIsotopically light Mo is inferred to be preferentially adsorbed onto organic matter during enhanced sulfate reductionδ98Mo offset between carbonate and organic phases in authigenic carbonates is promising to trace the past intensity of sulfate reduction [ABSTRACT FROM AUTHOR]

The widely discussed single‐atom catalysts (SACs) are regarded as a kind of attractive material for sulfate radical‐based advanced oxidation processes (SR‐AOPs) owing to their maximum atomic utilization efficiency and outstanding stability. Currently, metal–organic frameworks (MOFs) have appeared as prospective precursors for building SACs due to extensive chelating sites, functional adjustability, and structural tunability. However, there are few critical and systematic reviews about the application of MOF‐derived SACs in SR‐AOPs, especially in‐depth analysis of the mechanisms. Therefore, this review seeks to offer a thorough summary of the development of MOF‐derived SACs in SR‐AOPs. First, the unique advantages of MOFs as derivative precursors for SACs are discussed thoroughly. Afterward, the current synthesis strategies are elaborated categorically to unveil the formation process of single atoms and their coordination environments. Notably, the roles of different reaction sites including the generation of reactive species and mediating electron transfer are further analyzed to explain mechanisms comprehensively. Thereafter, the characterization techniques and theoretical calculations for mechanisms studies are also highlighted. Eventually, critical insights into present challenges and future developments are proposed, which are expected to enhance the catalytic efficiency of MOF‐derived SACs in SR‐AOPs. [ABSTRACT FROM AUTHOR]

The Mars 2020 Perseverance rover has examined and sampled sulfate‐rich clastic rocks from the Hogwallow Flats member at Hawksbill Gap and the Yori Pass member at Cape Nukshak. Both strata are located on the Jezero crater western fan front, are lithologically and stratigraphically similar, and have been assigned to the Shenandoah formation. In situ analyses demonstrate that these are fine‐grained sandstones composed of phyllosilicates, hematite, Ca‐sulfates, Fe‐Mg‐sulfates, ferric sulfates, and possibly chloride salts. Sulfate minerals are found both as depositional grains and diagenetic features, including intergranular cement and vein‐ and vug‐cements. Here, we describe the possibility of various sulfate phases to preserve potential biosignatures and the record of paleoenvironmental conditions in fluid and solid inclusions, based on findings from analog sulfate‐rich rocks on Earth. The samples collected from these outcrops, Hazeltop and Bearwallow from Hogwallow Flats, and Kukaklek from Yori Pass, should be examined for such potential biosignatures and environmental indicators upon return to Earth. Plain Language Summary: Images and compositional data of Mars rocks taken by the Mars 2020 Perseverance Rover at Hogwallow Flats and Yori Pass in Jezero crater show an abundance of sulfate minerals. The goal of this study was to describe the characteristics of these rocks with close‐up views of places where these rocks were abraded to expose fresh rock surface, and to make preliminary interpretations of any preservation potential of any possible environmental and biosignature data. We found sand and silt grains with a variety of colors, some of which are sulfate minerals. We also found sulfate mineral crystals between and cross‐cutting the grains. The sulfate sand and silt grains may have originally grown as chemical sediments in past salty lakes, and the sulfate crystals found between and cross‐cutting the grains formed from past salty groundwater. Sulfate mineral grains and crystals on Earth contain fluid and solid inclusions, which are remnant water, air and other gases, other minerals, and microorganisms and organic compounds. From this knowledge of terrestrial sulfate minerals, we suggest that samples of Hogwallow Flats and Yori Pass, if returned to Earth, should be investigated for fluid and solid inclusions to be evaluated for any enclosed past Martian water, gas, minerals, and possible biosignatures. Key Points: We describe sub‐mm scale observations for abrasion patches Berry Hollow and Uganik Island at Hogwallow Flats and Yori Pass on the western fan front in Jezero craterThese are sulfate‐rich clastic rocks with various diagenetic features that suggest sulfate‐rich surface waters and groundwaterEnvironmental data, such as parent water temperatures and compositions, and any potential biosignatures, may have been preserved [ABSTRACT FROM AUTHOR]

Sulfate crystals typically exhibit minimal optical anisotropy due to the near‐zero polarizability anisotropy (δ) of [SO4]2− tetrahedra, arising from highly symmetrical electron clouds. Recent research sought to enhance δ via chemical modifications, such as fluorination. However, the resultant crystals often maintain subpar optical anisotropy, frequently with birefringence values below 0.1. In this study, we have uncovered that δ can be significantly strengthened by chemically tailoring the tetrahedral [SO4]2− with anisotropic π‐conjugated modules. This has been demonstrated by several newly proposed S−O‐Org (Org: π‐conjugated organic species) moieties, which show a sharp increase in δ based on theoretical computations. To further validate this experimentally, we synthesized and characterized six new 3‐pyridinesulfonate crystals with the formula A(3‐C5H4NSO3) ⋅ xH2O (A=Li, Ag, K, Rb, Cs, and NH4; x=0 and 1). Notably, these materials exhibit strong optical anisotropy, with birefringence values ranging from 0.240 to 0.312 at 546 nm. These values are approximately 23 to 145.5 times greater than those of corresponding sulfates, and they outperform a vast number of sulfate‐related optical materials, thus verifying the effectiveness of the proposed strategy. Furthermore, the title compounds exhibit diverse microstructure peculiarities influenced by the size and binding natures of the counter cations. [ABSTRACT FROM AUTHOR]

Objective: The aim of this study is to use machine learning models to predict drinking water quality from a public health nursing approach. Design: Machine learning study. Sample: "Water Quality Dataset" was used in the study. The dataset contains physical and chemical measurements of water quality for 2400 different water bodies. The process consists of four stages: Data processing with Synthetic Minority Oversampling Technique, hyperparameter tuning with 10‐fold cross‐validation, modeling and comparative analysis. 80% of the dataset is allocated as training data and 20% as test data. ML models logistic regression, K‐nearest neighbor, support vector machine, random forest, XGBoost, AdaBoost Classifier, Decision Tree algorithms were used for water quality prediction. Accuracy, precision, recall, F1 score and AUC performance metrics of ML models were compared. To evaluate the performance of the models, 10‐fold cross‐validation was used and a comparative analysis was performed. The p‐values of the models were also compared. Results: N this study, where drinking water quality was predicted with seven different ML algorithms, it can be said that XGBoost and Random Forest are the best classification models in all performance metrics. There is a significant difference in all ML algorithms according to the p‐value. The H0 hypothesis is accepted for these algorithms. According to the H0 hypothesis, there is no difference between actual values and predicted values. Conclusion: In conclusion, the use of ML models in the prediction of drinking water quality can help nurses greatly improve access to clean water, a human right, be more knowledgeable about water quality, and protect the health of individuals. [ABSTRACT FROM AUTHOR]

Volatile sulfur compounds (VSCs) contribute to acid rain, cloud formation, and albedo, and thus influence the climate. Their global emissions are quite uncertain, especially contributions from freshwater wetlands. We investigated the processes leading to hydrogen sulfide (H2S), methanethiol (MeSH), and dimethyl sulfide (Me2S) emissions in a slightly acidic peatland and found multiple indications that organic matter degradation rather than sulfate reduction is the main driver for Me2S emissions in this system. Evidence includes: the lack of labeled Me234S production after addition of Na234SO4 despite high emissions of Me34SH and H234S, and increased emission rates when soils were amended with organic substrates containing thiol groups (H2S emissions), methylthiols (MeSH), and dimethyl sulfonio groups (Me2S). VSC precursors were identified from an Untargeted Metabolomics data set from the same soil. The abundance of sulfur cycling microbes like Acidobacteria SD 1 and Desulfosporosinus correlated with VSC emissions. We conclude that organic matter degradation is more important than sulfate reduction as a source of Me2S in our peatland system, and potentially also in other organic and wetland soils. Plain Language Summary: Sulfur gases influence acid rain and the way clouds form. In peats and swamps, there are two mechanisms to form sulfur gases. First, when the soils are flooded soil microbes use sulfate for respiration as an alternative to oxygen for the degradation of organic matter. During this process, microbes can convert sulfate to the sulfur gases hydrogen sulfide and methanethiol. In some wetland soils, methanethiol can then be converted to dimethyl sulfide, but we found that this only happens very slowly in our peatland soil. Second, soil microbes degrade organic sulfur compounds and produce sulfur gases as waste even in conditions where O2 is present. Which sulfur gas is produced depends on the structure of the organic sulfur compound that serves as a substrate. Compounds with a free ‐S‐H group form hydrogen sulfide (H‐S‐H), compounds with a ‐S‐CH3 group form methanethiol (CH3‐S‐H), compounds with a ‐S(‐CH3)2 group form dimethyl sulfide (H3C‐S‐CH3), while compounds without those groups do not produce sulfur gases. We also found microbes that could be feeding on these VSC precursors. This means that emissions of sulfur gases from wetlands are caused not just by the reduction of sulfate under anoxic conditions, but directly from the degradation of organic matter, even in oxic soils outside of wetlands. Key Points: Organic matter decomposition is a main source of volatile sulfur compound (VSC) emitted from organic soils and wetlandsSulfate reduction is also an important source of methanethiol and hydrogen sulfide but not dimethyl sulfideInterconversion of volatile sulfur compounds is slower than formation and emission [ABSTRACT FROM AUTHOR]

Sulfate is a potential pollutant and important nutrient linked with the nitrogen, carbon, and phosphorus cycles. The importance of different anthropogenic sulfate sources in suburban streams (septic systems, fertilizer, road salt, and infrastructure) is uncertain, and the temporal dynamics of stream export sparsely documented. We study sources and export dynamics of sulfate in suburban and forested headwater catchments. Stream baseflow discharge and sulfate concentrations were strongly positively correlated in both watersheds with the highest values in spring. Suburban concentrations and fluxes (2.48–7.5 mg/L or 25.8–78.1 μM, 16.6 kg/ha/yr) were consistently higher than forested (0.56–2.78 mg/L or 5.8–28.9 μM, 5 kg/ha/yr). Following precipitation, sulfate concentrations in both forested and suburban streams increased to concentrations above pre‐storm values and remained high after peak discharge. These dynamics suggest that both catchments have a large pool of sulfate that can be mobilized under wet conditions. Ridge‐top forest soil samples contained 210 kg/ha stored, extractable sulfate. Current atmospheric sulfate deposition rates (5–7 kg/ha/yr) are approximately in balance with sulfate export in the forested stream. In the suburban watershed, we estimated septic fields contribute up to 11 kg/ha/yr (about half from surfactants) and lawn care up to 4.3 kg/ha/yr and are the most likely sources of elevated stream sulfate. Sulfate sulfur (4.9–5.8‰ forested; 6.1–7.0‰ suburban) and oxygen isotope values (0.7–2.0‰ forested; −0.1–4.1‰ suburban) are consistent with this interpretation, but do not provide strong corroboration due to large variation and overlap in estimated source values. Plain Language Summary: Sulfate can be a nutrient or pollutant that alters stream biogeochemistry depending on dissolved concentrations. For decades, atmospheric sulfur deposition was elevated due to regional anthropogenic emissions. Regulation in the 1990s resulted in decreasing deposition and increasing importance of other sulfur sources, for example, associated with land use. We studied suburban sulfate sources, including infrastructure and activities not widely recognized as sources of stream sulfate. We measured dissolved sulfate concentrations and sulfate tracer isotopes in neighboring forested and suburban watersheds. Sulfate inputs and exports are compared with budgets of possible sulfate contributions to the stream from septic systems, lawn care, road salt, building materials, and historic agriculture. The suburban stream exports about 3x more sulfate a year from the watershed than the forested stream. Extra suburban stream sulfate appears to be largely caused by human waste and cleaning products flowing to septic fields and lawn care. More sulfate is transported to the stream during the wetter spring and after rain. This elevated transport may be because the groundwater table moves upwards during wetter times and transports sulfate that was stored in soil to the stream. Identifying suburban sources of sulfate pollution is important to protecting stream health. Key Points: The suburban stream has elevated sulfate concentrations and fluxes, likely due to contributions from septic systems and lawn careSulfate mobilized in seasonal‐ and event‐scale wet conditions in both forested and suburban streamsSulfate in the suburban stream is associated with soil storage mobilized in wet conditions, not runoff from impervious surfaces [ABSTRACT FROM AUTHOR]

Rationale: Preparation of BaSO4 from samples of atmospheric rain, snow, and aerosols has been used for δ18O and δ34S analyses. In the present study, we investigated the effect of various sample pretreatments on δ18O and δ34S values determined from a Na2SO4 reagent solution and samples of atmospheric precipitation to improve assay time and cost efficiency. Methods: BaSO4 was prepared from a Na2SO4 solution by (a) evaporative concentration, (b) evaporation to dryness, (c) evaporation to dryness after adding HCl, and (d) evaporation to concentration after adding HCl, followed by cooling and then precipitation using a BaCl2 solution. To analyze the atmospheric precipitation samples for δ18O, BaSO4 prepared from the samples was treated with diethylenetriaminepentaacetic acid (DTPA) and SO42− and separated chromatographically. The values of δ18O and δ34S were measured using a continuous‐flow elemental analyzer coupled to an isotope‐ratio mass spectrometer. Results: The δ34S values in BaSO4 precipitated from Na2SO4 solution determined by methods (a)–(c) were consistent within precisions of ±0.5‰. The δ18O values of methods (a) and (b) were consistent within ±0.2‰, whereas the δ18O values of methods (c) and (d) increased with increasing HCl concentrations. Similar results were obtained from samples of atmospheric precipitations. The δ18O values from DTPA‐treated BaSO4 were consistent with those obtained by chromatographic separation within ±0.5‰. Conclusions: We found no significant differences in the effects of various pretreatments (acidification, heating, concentration, and drying) on δ18O and δ34S values in sulfate from samples of atmospheric precipitation and aerosols extracted as BaSO4 if HCl was not added to the sample before heating and BaSO4 was treated with DTPA for the δ18O analysis. [ABSTRACT FROM AUTHOR]

Two neodymium sulfate based purely inorganic networks, [NH4][Nd(SO4)2(H2O)3] ⋅ H2O (1) and [Nd2(SO4)3(H2O)4] ⋅ H2O (2) have been synthesized at different reaction temperatures and pH values. The structure of 1 features a two‐dimensional (2D) anionic corrugated sheet with an sql topological net built up by linking NdO8 units and μ2‐SO42− anions, in which the NH4+ charge‐compensating/templating cations occupy the intersheet layers. While 2 possesses a 3D neutral framework with an unprecedented (3,42,7‐c) net constructed by NdO9 units and μ4‐ and μ6‐SO42− linkers. They exhibit thermally induced irreversible structural transformation associated with the dehydration and the changes in coordination geometry and dimensionality. Both compound 1 and 2 display typical antiferromagnetic interactions between the Nd3+ centres. In addition, the CO2 adsorption isotherms of the desolvated samples 1 and 2 were also investigated. [ABSTRACT FROM AUTHOR]

Aims: Indoxyl sulfate and parathyroid hormone (PTH), which accumulate in chronic kidney disease (CKD), have been reported to reduce cytochrome P450(CYP)3A activity. Homozygotes of the CYP3A5*3 allele have reduced CYP3A5 activity compared to carriers of at least one CYP3A5*1 allele. 4β‐Hydroxycholesterol (4β‐OHC) has been established as an endogenous substrate reflecting CYP3A activity. 4β‐OHC is produced through hydroxylation by CYP3A4 and CYP3A5 and by autoxidation of cholesterol, whereas 4α‐hydroxycholesterol (4α‐OHC) is produced solely by autoxidation of cholesterol. This study focused on CKD patients and evaluated the effects of plasma indoxyl sulfate and intact‐PTH concentrations on plasma 4β‐OHC concentration, 4β‐OHC/total cholesterol ratio and 4β‐OHC–4α‐OHC, with consideration of the influence of CYP3A5 polymorphism. Methods: Sixty‐three CKD patients were analysed and divided into CYP3A5 carrier group (n = 26) and non‐carrier group (n = 37). Results: Plasma indoxyl sulfate significantly correlated inversely with 4β‐OHC concentration and with 4β‐OHC–4α‐OHC in both the CYP3A5*1 carrier group (r = −0.42, P =.034; r = −0.39, P =.050, respectively) and the non‐carrier group (r = −0.45, P =.0054; r = −0.39, P =.019, respectively). However, multiple regression analysis did not identify plasma indoxyl sulfate concentration as a significant independent factor associated with any of the CYP3A activity indices. There was no significant correlation between plasma intact‐PTH concentration and any of the CYP3A activity indices. Conclusions: The present results suggest that plasma indoxyl sulfate and intact‐PTH concentrations do not have clinically significant effects on CYP3A activity in patients with CKD. [ABSTRACT FROM AUTHOR]

Introduction: Indoxyl sulfate (IS) is a protein‐bound uremic toxin that causes uremic sarcopenia. IS has poor dialysis clearance; however, the addition of a binding competitor improves its removal efficiency. Methods: Dialysis experiments were performed using N‐acetyl‐l‐tryptophan (L‐NAT) instead of l‐tryptophan (Trp) using pooled sera obtained from dialysis patients. The molecular structures of L‐NAT and Trp were similar to that of IS. Therefore, we examined whether Trp and L‐NAT were involved in muscle atrophy in the same manner as IS by performing culture experiments using a human myotube cell line. Results: The removal efficiency of L‐NAT was the same as that of Trp. However, L‐NAT concentrations in the pooled sera increased at the end of the experiment. Trp (1 mM) decreased the area of human myocytes, similar to IS, whereas L‐NAT did not. Conclusion: L‐NAT is a binding competitor with the ability to remove protein‐bound IS while preventing sarcopenia. [ABSTRACT FROM AUTHOR]

SCMs with a large specific surface area, such as calcined clays or fine limestone powder, can significantly accelerate the occurrence of the aluminate heat flow peak during the early hydration of blended cements. These systems therefore require a higher amount of sulfate. While this effect has been drawn back to the sulfate incorporation into C‐S‐H, which is formed more rapidly due to the filler effect, it has been recently shown that in systems with high amounts of metakaolin, the sulfate balance is influenced by further mechanisms. This study provides new results on the influence of aluminum‐rich and aluminum‐free SCMs on the early hydration of alite in presence of calcium sulfate. A synthesized alite was blended with 5 wt% of anhydrite and its hydration was investigated by isothermal calorimetry and in‐situ XRD at a w/b ratio of 0.5. It was shown that the formed C‐S‐H is able to take up the calcium and sulfate ions, indicated by a depletion of the solid anhydrite after approximately 20 hours. This process is significantly accelerated by incorporating 30 wt% of a fine limestone filler. The addition of metakaolin leads to an acceleration of the alite hydration compared to the reference as well, but to a significantly lower extend compared to the limestone. However, this system requires a lower degree of alite reaction to reach sulfate depletion. This indicates that in metakaolin‐rich systems, the sulfate demand is influenced by further effects. The results from in‐situ‐XRD reveal that significant ettringite formation is taking place in the metakaolin‐blended system already during the first hours of hydration. Correlations between the degree of alite hydration and the rate of sulfate depletion provide new insights into the mechanisms affecting the sulfate balance and early hydration of blended cements. [ABSTRACT FROM AUTHOR]

The sulfur biogeochemical cycle controls the sulfur dynamics in the soil. In contrast to almost all deposited sulfur leaching out in temperate catchments, approximately 80% of the deposited S is retained in the catchments in subtropical regions. However, the mechanisms for sulfur retention were unclear, hindering the understanding of potential threats of legacy sulfur with environmental changes. Here, we demonstrated that sulfate reduction (as sulfide fixed in soil) was a prominent yet overlooked mechanism for sulfur retention in addition to the widely recognized sulfate adsorption in soil, based on a study on soil sulfur storage and stable isotope signatures within entire soil profiles in a typical subtropical catchment in China. Using a dual‐isotopic model, the sulfate reduction flux was further determined to be 30% of the S deposition. Due to a lot of deposited sulfur fixed via sulfate reduction, the release of soil legacy sulfur would be less in response to decreasing sulfur deposition compared to the projections only considering adsorption. However, the remobilization of large amounts of reduced S should be regarded as a threat to the environment under climate change in the future. Plain Language Summary: Sulfur budget in catchments reveals substantial retention of around 80% of deposited sulfur in subtropical soils, mitigating acidification arising from heightened sulfur deposition. The substantial sulfur retention was previously ascribed to sulfate adsorption. However, our study unveils sulfate reduction as a prominent yet overlooked retention mechanism, evidenced by soil sulfur storage estimates and stable isotope signatures across complete soil profiles in a typical subtropical Chinese catchment. Sulfate adsorption displays reversibility with declining atmospheric deposition. However, sulfate reduction exhibits relatively stable except during periods of frequent drought attributed to climate change or the soil excavation induced by land‐use change. Key Points: A dual isotopic mass balance model was built to quantify the transformations of S in the ecosystemsSulfur retention accounted for approximately 80% of deposition based on the sulfur input–output budgets for 17 sites in subtropical ChinaSulfate reduction was a prominent mechanism for sulfur retention in addition to widely recognized sulfate adsorption [ABSTRACT FROM AUTHOR]

Wide bandgap and large birefringence, as well as strong second harmonic effect, are important but often mutually restraint prerequisites for deep‐ultraviolet (DUV) nonlinear optical (NLO) crystals, a type of photoelectronic materials that play an indispensable role in the DUV laser generation. For the long term, the search for new DUV NLO crystals has focused on the alkali‐metal inorganic acid salts where the variations of anionic groups are considered. Herein, another design strategy is reported, in which the alkali‐metal cations are substituted by the asymmetrical non‐π‐conjugated cations to harmonize the above mutual restrictions. Accordingly, LiN2H5SO4 (LNHSO) crystal is obtained by the substitution of [N2H5]+ for alkali‐metal ions in LiMSO4 (M = Na, K, and Rb). Compared with LiMSO4 (M = Na, K, and Rb), LNHSO exhibits a moderate phase‐matching second‐harmonic generation response (0.6 × KH2PO4), increased birefringence (two to three times that of other sulfates), and the widest bandgap (7.69 eV) among all the reported NLO sulfates. The structural analysis and theoretical calculation reveal that the structural anisotropy, arrangement, and packing configuration of the novel NLO‐active [N2H5]+ cation in LNHSO effectively promotes the optical properties and enlarges the bandgap. This work provides an innovative perspective for the rational design and synthesis of DUV NLO materials with excellent performance. [ABSTRACT FROM AUTHOR]

Adequate distribution of mineral sulphur (S) nutrition to nodules mediated by sulphate transporters is crucial for nitrogen fixation in symbiosis establishment process. However, the molecular mechanisms underlying this process remain largely unknown. In this study, we characterized the function of Early Senescent Nodule 2 (MtESN2), a gene crucial to nitrogen fixation in Medicago truncatula. Mutations in MtESN2 resulted in severe developmental and functional defects including dwarf shoots, early senescent nodules, and lower nitrogenase activity under symbiotic conditions compared to wild‐type plants. MtESN2 encodes an M. truncatula sulphate transporter that is expressed only in roots and nodules, with the highest expression levels in the transition zone and nitrogen‐fixing zone of nodules. MtESN2 exhibited sulphate transport activity when expressed in yeast. Immunolocalization analysis showed that MtESN2‐yellow fluorescent protein fusion protein was localized to the plasma membranes of both uninfected and infected cells of nodules, where it might transport sulphate into both rhizobia‐infected and uninfected cells within the nodules. Our results reveal an unreported sulphate transporter that contributes to effective symbiosis and prevents nodule early senescence in M. truncatula. Summary statement: In the present study, we performed detailed phenotypic studies of loss‐of‐function mutants and functional characterization of MtESN2 and found that MtESN2 is a sulphate transporter localized on the plasma membrane of infected and uninfected nodule cells with an important role in nitrogen fixation. Our findings have expanded knowledge of an indispensable role of the subgroup II sulphate transporter MtESN2 in legume‐rhizobial symbiosis and nodule senescence. [ABSTRACT FROM AUTHOR]

Sulfated metabolites have shown to have potential as long‐term markers (LTMs) of anabolic–androgenic steroid (AAS) abuse. The compatibility of gas chromatography–mass spectrometry (GC–MS) with trimethylsilyl (TMS)‐derivatives of non‐hydrolysed sulfated steroids has been demonstrated, where, after derivatisation, generally, two closely eluting isomers are formed that both have the same molecular ion [M‐H2SO4]•+. Sulfated reference standards are in limited commercial availability, and therefore, the current knowledge of the GC–MS behaviour of these compounds is mainly based on sulfating and analysing the available standard reference material. This procedure can unfortunately not cover all of the current known LTMs as these are often not available as pure substance. Therefore, in theory, some metabolites could be missed as they exhibit alternative behaviour. To investigate the matter, in‐house sulfated reference materials that bear resemblance to known sulfated LTMs were analysed on GC–MS in their TMS‐derivatised non‐hydrolysed state. The (alternative) gas chromatographic and mass spectrometric behaviour was mapped, evaluated and linked to the corresponding steroid structures. Afterwards, using fraction collection, known sulfated LTMs were isolated from excretion urine to confirm the observed findings. The categories that were selected were mono‐hydroxy‐diones, 17‐methyl‐3,17‐diols and 17‐keto‐3,16‐diols as these are commonly encountered AAS conformations. The ability to predict the GC–MS behaviour of non‐hydrolysed sulfated AAS metabolites is the corner stone of finding new metabolites. This knowledge is also essential, for example, for understanding AAS detection analyses, for the mass spectrometric characterization of metabolites of new designer steroids or when one needs to characterize an unknown steroid structure. [ABSTRACT FROM AUTHOR]

Because of the current water crisis worldwide, it is of great importance to find alternative sources of drinking water, such as sulfur water. This review analyses laboratory, pilot and industrial‐scale technologies available for sulfate removal from water produced for human consumption, from naturally occurring sulfur water and that resulting from human activities. Most of them exceed 90% removal efficiencies. However, the concentrations treated in each study were different; some technologies evaluate concentrations below recommended limits (250 mg L−1), while others evaluate much higher concentrations but require previous treatments. The technologies with higher energy requirements such as reverse osmosis and ion exchange have better removal efficiencies but require larger initial investments and have higher operational costs. Biological treatments, on the other hand, with lower energy and material requirements, are less expensive but require long retention times and depend on the season of the year and/or environmental conditions. Lastly, adsorption removal technologies fall in the middle, especially for energy requirements and operational costs and retention times. This review shows that although there are a variety of sulfate removal technologies suitable for use, there is still room for a novel methodology that removes sulfates from a wider range of concentrations more economically, more effectively and in less time than what is currently available. [ABSTRACT FROM AUTHOR]

To date, bipolar membrane electrodialysis (BMED) is being developed as a competitive technology for waste lithium‐ion battery recovery. However, the purity and concentration of lithium hydroxide generated from a BMED plant could not meet the product criteria for ternary lithium batteries, thus requiring additional condensation, purification, evaporation, and crystallization procedures. Herein, bipolar membrane crystallization (BMC) was proposed for the one‐step conversion of sulfate lithium into high‐purity lithium hydroxide monohydrate crystals. By mediating a continuous saturated feedstock in the salt compartment, it is possible to convert Li2SO4 into 5+ mol/L LiOH at a current density higher than 500 A/m2. Therefore, this unique design allows the production of 99.9% LiOH∙H2O by taking the principle of water dissociation in the bipolar membrane and the simultaneous crystallization procedure. This proof‐of‐concept study proves the feasibility and competitiveness of the BMC for waste lithium recovery by abandoning the condensation and evaporation procedures. [ABSTRACT FROM AUTHOR]

Metal halide perovskite light‐emitting diodes (PeLEDs) are promising high‐definition display candidates due to their narrow emission bandwidth and wide color gamut. However, efficient and stable pure‐red PeLEDs have rarely been achieved. Herein, a robust and strongly‐coordinated sulfate anion passivation strategy is reported to achieve a spectrally stable and efficient pure‐red PeLED with an electroluminescent peak at 630 nm and full width at half maximum of 27 nm. Octylammonium sulfate is employed to construct a PbSO4 layer on the surface of CsPbI3−xBrx nanocrystals, which can effectively inhibit phase separation under UV light, humidity, or heat treatment. Using sulfate passivated CsPbI3−xBrx NC film, pure red PeLEDs with high external quantum efficiency of 12.6%, excellent spectral stability, and an operational half‐life time of over 300 min (T50@100 cd cm−2) are fabricated. This work provides a new avenue to improve performance of pure red PeLEDs via strong‐coordinated sulfate passivation. [ABSTRACT FROM AUTHOR]

The accumulation of authigenic carbonate in marine sediments has been regarded as a significant contributor to the carbon cycle over Earth's history. However, accurate quantification of the extent of authigenic carbonate formation in both modern and ancient oceans has been challenging due to limited approaches. Here, we analyzed calcium, magnesium, dissolved inorganic carbon, and alkalinity pore‐water profiles of 153 sites influenced by methane diffusion from the northern South China Sea. By combining these data with published data of diffusive sulfate flux, we found a significant positive correlation between carbonate precipitation rate and sulfate flux in the subseafloor. This correlation can be used to quantify the regional extent of authigenic carbonate formation, representing an advantage over a spatial interpolation approach. We therefore propose that the observed correlation can serve as a new approach for quantifying authigenic carbonate formation in shallow sediments along continental margins for both modern and ancient oceans. Plain Language Summary: Carbonate mineral precipitation through removing seawater dissolved inorganic carbon—the marine carbonate factory—plays a critical role in shaping marine carbon cycling and global climate. The formation of authigenic carbonate from pore‐water of marine sediments represents a variable share of the marine carbonate factory throughout geological history. However, it is challenging to quantify the extent of such authigenic carbonate formation. By analyzing pore‐water parameters from 153 sites influenced by methane diffusion of the northern South China Sea, we found a significant positive correlation between the rate of carbonate precipitation and the diffusive flux of sulfate into shallow sediments. Given the existence of estimates on the sizes of the seawater sulfate pool and diffusive fluxes of sulfate into sediments over Earth's history, we propose that the observed correlation can be used for quantifying authigenic carbonate formation in shallow sediments along continental margins through time, which will greatly advance our understanding for past carbon cycling and its relation to climate. Key Points: Porewater parameters from 153 sites of the northern South China Sea were evaluated to quantify the extent of authigenic carbonate formationRate of carbonate formation strongly correlates with diffusive flux of sulfate into sediments affected by methane diffusionA correlation of carbonate formation rate with sulfate flux is used to quantify most of authigenic carbonate formation in shallow sediments [ABSTRACT FROM AUTHOR]

A regioselective fluoromethylation by ring‐opening of cyclic sulfamidates and sulfates with α‐fluorocarbanions and subsequent reductive desulfonylation is developed. Fluorobis(phenylsulfonyl)methane (FBSM) was explored as fluoromethide equivalent and the reaction was extended to the α‐fluorocarbanion of ethyl 2‐fluoroacetoacetate. This approach allows access to γ‐ and δ‐fluoroamines as well as γ‐ and δ‐fluoroalcohols in high yields. [ABSTRACT FROM AUTHOR]

Four salts, namely, 2,4,6‐triaminopyrimidinium 6‐chloronicotinate dihydrate, C4H8N5+·C6H3ClNO2−·2H2O, (I), 2,4,6‐triaminopyrimidinediium pyridine‐2,6‐dicarboxylate dihydrate, C4H9N52+·C7H3NO42−·2H2O, (II), 2,4,6‐triaminopyrimidinediium sulfate monohydrate, C4H9N52+·SO42−·H2O, (III), and 2,4,6‐triaminopyrimidinium 3,5‐dinitrobenzoate dihydrate, C4H8N5+·C7H3N2O6−·2H2O, (IV), were synthesized and characterized by X‐ray diffraction techniques. Proton transfer from the corresponding acid to the pyrimidine base has occurred in all four crystal structures. Of the four salts, two [(I) and (IV)] exist as monoprotonated bases and two [(II) and (III)] exist as diprotonated bases. In all four crystal structures, the acid interacts with the pyrimidine base through N—H...O hydrogen bonds, generating an R22(8) ring motif. The sulfate group mimics the role of the carboxylate anions. The water molecules present in compounds (I)–(IV) form water‐mediated large ring motifs. The formation of water‐mediated interactions in these crystal structures can be used as a model in the study of the hydration of nucleobases. Water molecules play an important role in building supramolecular structures. In addition to these strong hydrogen‐bonding interactions, some of the crystal structures are further enriched by aromatic π–π stacking interactions [(I) and (II)]. [ABSTRACT FROM AUTHOR]

The possibility of using heterogeneous construction waste such as masonry rubble as a raw material for the production of lightweight aggregates similar to expanded clays or even pumice has already been reported earlier. This approach has been consistently pursued. As a current aspect, the extent to which gypsum‐containing masonry rubble is also suitable as a raw material was investigated. This not only avoids (expensive) landfilling of this material, but at the same time makes a contribution to at least partially filling the "gypsum gap" created by the elimination of flue gas desulfurization gypsum. The first part of this publication reports on laboratory‐scale tests. The second part focuses on testing the process in the pilot plant. [ABSTRACT FROM AUTHOR]