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Sulfur (S) is an essential macronutrient for plants and its availability in soils is an important determinant for growth and development. Current regulatory policies aimed at reducing industrial S emissions together with changes in agronomical practices have led to a decline in S contents in soils worldwide. Deficiency of sulfate—the primary form of S accessible to plants in soil—has adverse effects on both crop yield and nutritional quality. Hence, recent research has increasingly focused on unraveling the molecular mechanisms through which plants detect and adapt to a limiting supply of sulfate. A significant part of these studies involves the use of omics technologies and has generated comprehensive catalogs of sulfate deficiency-responsive genes and processes, principally in Arabidopsis together with a few studies centering on crop species such as wheat, rice, or members of the Brassica genus. Although we know that sulfate deficiency elicits an important reprogramming of the transcriptome, the transcriptional regulators orchestrating this response are not yet well understood. In this review, we summarize our current knowledge of gene expression responses to sulfate deficiency and recent efforts towards the identification of the transcription factors that are involved in controlling these responses. We further compare the transcriptional response and putative regulators between Arabidopsis and two important crop species, rice and tomato, to gain insights into common mechanisms of the response to sulfate deficiency. [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]

Due to vincristine sulfate's (VCR sulfate) toxicity and non-specific targeting, which might adversely damage healthy cells, its clinical application is restricted. In this study, we loaded VCR sulfate on exosomes generated from mesenchymal stem cells (MSCs) to enhance its targeted distribution. Exosomes are able to deliver molecules to specific cells and tissues and have therapeutic potential. In this study, we isolated exosomes from MSCs, and using probe-sonication approach loaded them with VCR sulfate. Using SRB assay, the cytotoxicity of VCR sulfate-Exo was assessed in T47D breast cancer cells, and the results were contrasted with those of free VCR sulfate. Then We labeled markers (CD44+/CD24−) in the cell line to assess the targeting effectiveness of VCR sulfate-Exo using flow cytometry. Our results showed that the cytotoxicity of VCR sulfate-Exo was nearly the same as that of VCR sulfate. Flow cytometry analysis revealed that VRC sulfate-Exo was more effectively targeted to MSCs than free VCR sulfate. Our study shows that loading VCR sulfate to MSCs-derived exosomes can improve their targeted delivery and lessen their side effects. Additional research is required to determine VCR sulfate-Exo's in vivo effectiveness and safety and improve the loading and delivery strategies. [ABSTRACT FROM AUTHOR]

Sulfate is a critical component of schwertmannite. However, the sulfate content of schwertmannite decreases with the increase in AMD-polluted river pH value, and its impact on the surface properties and Cr(VI) adsorption of schwertmannite remains unclear. To address this issue, different methods, including batch adsorption, N 2 physisorption, scanning electron microscopy (SEM), potentiometric titration, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance–Fourier transform infrared spectroscopy (ATR-FTIR) in combination with two-dimensional correlation spectroscopy (2D-COS) analysis, and surface complexation modeling (SCM) were employed. Our results showed that sulfate existed as both non-protonated bidentate-binuclear complexes and non-protonated outer-sphere complexes in schwertmannite. The surface morphology and particle size of schwertmannite were unaffected by the sulfate content. However, a decrease in sulfate content resulted in a drop in the negative charge on the surface of schwertmannite, which is conducive to particle aggregation. An increase in pH, on the other hand, raised the negative charge and encouraged the dispersion of the particles. And then, reducing the sulfate content of schwertmannite led to a decrease in acid-base buffer and Cr(VI) adsorption capacity of schwertmannite. The adsorption process of Cr(VI) by schwertmannite can be divided into two stages. In the first stage, Cr(VI) was adsorbed primarily through anion exchange reactions with the sulfate; however, the contribution of surface complexation gradually increased as the initial sulfate content decreased because of a reduced likelihood of anion exchange and an increase in the specific surface area of schwertmannite. Additionally, the behavior of sulfate and Cr(VI) in this stage could be predicted based on the initial sulfate content of schwertmannite. In the second stage, surface complexation with hydroxyl sites became the predominant mechanism of adsorption, which still exhibited great potential at higher Cr(VI) concentrations. Finally, the aforementioned hypothesis was used to establish a CD-MUSIC model, and the fitting results demonstrated that the density and Cr(VI) adsorption capacity of the sulfate site dropped as the sulfate content decreased, while the hydroxyl site was less impacted. The findings have provided insights into further understanding the properties of schwertmannite and its adsorption of Cr(VI). [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]

The surface of Venus is in contact with a hot (~470 °C), high pressure (92 bars), and caustic (CO2 with S, but little H2O) atmosphere, which should cause progressive alteration of the crust in the form of sulfate and iron-oxide coatings; however, the exact rate of alteration and mineral species are not well constrained. Different experimental approaches, each with its own limitations, are currently being used to constrain mineralogy and alteration rates. One note is that no experimental approach has been able to fully replicate the necessary conditions and sustain them for a significant length of time. Furthermore, geochemical modeling studies can also constrain surface alteration mineralogy, again with different assumptions and limitations. Here, we review recent geochemical modeling and experimental studies to constrain the state of the art for alteration mineralogy, rate of alteration, open questions about the surface mineralogy of Venus, and what can be constrained before the fleet of missions arrives later this decade. Combining the new results confirms that basalt on the surface of Venus should react quickly and form coatings of sulfates and iron-oxides; however, the mineralogy and rate of alteration are dependent on physical properties of the protolith (including bulk composition, mineralogy, and crystallinity), as well as atmospheric composition, and surface temperature. Importantly, the geochemical modeling results show that the mineralogy is largely controlled by atmospheric oxygen fugacity, which is not well constrained for the near-surface environment on Venus. Therefore, alteration experiments run over a range of oxygen and sulfur fugacities are needed across a wide range of Venus analog materials with varying mineralogy and crystallinity. [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]

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]

Hybrid water electrolysis (HyWES) with iodide oxidation as non-OER for energy-saving H2 production is demonstrated using self-supported sulfate ion modified Ni,Fe(oxy)hydroxide as the anode. The sulfate ions adsorbed on the catalyst show a promoting effect in achieving high electrochemical activity. The HyWES requires a voltage as low as 1.36 V to achieve the bechmark current density of 10 mA cm−2. [ABSTRACT FROM AUTHOR]

Rates of microbial processes are fundamental to understanding the significance of microbial impacts on environmental chemical cycling. However, it is often difficult to quantify rates or to link processes to specific taxa or individual cells, especially in environments where there are few cultured representatives with known physiology. Here, we describe the use of the redox-enzyme-sensitive molecular probe RedoxSensor™ Green to measure rates of anaerobic electron transfer physiology (i.e., sulfate reduction and methanogenesis) in individual cells and link those measurements to genomic sequencing of the same single cells. We used this method to investigate microbial activity in hot, anoxic, low-biomass (~10³ cells mL-1) groundwater of the Death Valley Regional Flow System, California. Combining this method with electron donor amendment experiments and metatranscriptomics confirmed that the abundant spore formers including Candidatus Desulforudis audaxviator were actively reducing sulfate in this environment, most likely with acetate and hydrogen as electron donors. Using this approach, we measured environmental sulfate reduction rates at 0.14 to 26.9 fmol cell-1 h-1. Scaled to volume, this equates to a bulk environmental rate of ~103 pmol sulfate L-1 d-1, similar to potential rates determined with radiotracer methods. Despite methane in the system, there was no evidence for active microbial methanogenesis at the time of sampling. Overall, this method is a powerful tool for estimating species-resolved, single-cell rates of anaerobic metabolism in low-biomass environments while simultaneously linking genomes to phenomes at the single-cell level. We reveal active elemental cycling conducted by several species, with a large portion attributable to Ca. Desulforudis audaxviator. [ABSTRACT FROM AUTHOR]

Through microscopic analyses (e.g., organic macerals, thin section observation, scanning electron microscope (SEM) imaging of fresh bedding planes via argon ion milling, and energy spectrum tests) combined with Rock-Eval analyses, this study systematically investigated the organic matter and pyrites in the continental shales in the 3rd submember of the Chang 7 Member (Chang 7³ submember) in the Yanchang Formation, Ordos Basin and determined their types and the formation and evolutionary characteristics. The results are as follows. The organic matter of the continental shales in the Chang 7³ submember is dominated by amorphous bituminites and migrabitumens, which have come into being since the early diagenetic stage and middle diagenetic stage A, respectively. The formation and transformation of organic matter is a prerequisite for the formation of pyrites. The Ordos Basin was a continental freshwater lacustrine basin and lacked sulphates in waters during the deposition of the Chang 7 Member. Therefore, the syndiagenetic stage did not witness the formation of large quantities of pyrites. Since the basin entered early diagenetic stage A, large quantities of sulfur ions were released as the primary organic matter got converted into bituminites and, accordingly, pyrites started to form. However, this stage featured poorer fluid and spatial conditions compared with the syndepositional stage due to withdraw of water, the partial formation of bituminites, and a certain degree of compaction. As a result, large quantities of pyrrhotite failed to transition into typical spherical framboidal pyrites but grew into euhedral monocrystal aggregates. In addition, pyrites are still visible in the migrabitumens in both microfractures and inorganic pores of mudstones and shales, indicating that the pyrite formation period can extend until the middle diagenetic stage A. [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]

The Beckmann rearrangement of ketoximes to their corresponding amides, using a Brønsted acid-mediated fragmentation and migration sequence, has found wide-spread industrial application. We postulated that the development of a methodology to access ylideneamino sulfates using tributylsulfoammonium betaine (TBSAB) would afford isolable Beckmann-type intermediates and competent partners for subsequent rearrangement cascades. The ylideneamino sulfates generated, isolated as their tributylammonium salts, are sufficiently activated to undergo Beckmann rearrangement without additional reagent activation. The generation of sulfuric acid in situ from the ylideneamino sulfate giving rise to a routine Beckmann rearrangement and additional amide bond cleavage to the corresponding aniline was detrimental to reaction success. The screening of bases revealed inexpensive sodium bicarbonate to be an effective additive to prevent classic Brønsted acid-mediated fragmentation and achieve optimal conversions of up to 99%. [ABSTRACT FROM AUTHOR]

The C(sp2)-aryl sulfonate functional group is found in bioactive molecules, but their synthesis can involve extreme temperatures (>190 °C or flash vacuum pyrolysis) and strongly acidic reaction conditions. Inspired by the 1917 Tyrer industrial process for a sulfa dye that involved an aniline N(sp2)-SO3 intermediate en route to a C(sp2)-SO3 rearranged product, we investigated tributylsulfoammonium betaine (TBSAB) as a milder N-sulfamation to C-sulfonate relay reagent. Initial investigations of a stepwise route involving TBSAB on selected anilines at room temperature enabled the isolation of N(sp2)-sulfamate. Subsequent thermal rearrangement demonstrated the intermediary of a sulfamate en route to the sulfonate; however, it was low-yielding. Investigation of the N-sulfamate to C--sulfonate mechanism through control experiments with variation at the heteroatom positions and kinetic isotope experiments (KIEH/D) confirmed the formation of a key N(sp2)-SO3 intermediate and further confirmed an intermolecular mechanism. Furthermore, compounds without an accessible nitrogen (or oxygen) lone pair did not undergo sulfamation- (or sulfation) -to-sulfonation under these conditions. A one-pot sulfamation and thermal sulfonation reaction was ultimately developed and explored on a range of aniline and heterocyclic scaffolds with high conversions, including N(sp2)-sulfamates (O(sp2)-sulfates) and C(sp2)-sulfonates, in up to 99 and 80% (and 88% for a phenolic example) isolated yield, respectively. Encouragingly, the ability to modulate the ortho-para selectivity of the products obtained was observed under thermal control. A sulfonated analog of the intravenous anesthetic propofol was isolated (88% yield), demonstrating a proof-of-concept modification of a licensed drug alongside a range of nitrogen- and sulfur-containing heterocyclic fragments used in drug discovery. [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]

Since 2006, with the development of an optimized methodology for silicon purification based on alkaline fusion followed by cation-exchange chromatography, silicon isotopes have been widely measured across diverse sample types. Nevertheless, this technique does not remove anions and dissolved organic carbon (DOC), leading to potential matrix effects. Notably, under dry plasma conditions, several studies have reported offset in the δ30Si value up to +1.4‰ when [S]/[Si] > 0.02 (wt/wt) and +0.65‰ when [DOC]/[Si] > 1.75. Here, we examine the matrix effects induced by chloride, sulfate and dissolved organic carbon under wet plasma conditions. To achieve this, we doped the NBS-28 (NIST® RM 8546) solution, with varying amounts of sulfate and chloride and measured the δ30Si value in the doped solutions. To investigate the DOC matrix effect, we used the UV photolysis method to decompose the DOC within natural samples and then compared the resulting δ30Si values with those of untreated samples. Importantly, we did not observe any significant δ30Si offset outside the range of our long-term analytical precision (±0.11‰, 2SD) attributed to chloride, sulfate, or DOC across a range of [Cl−]/[Si] = 0.09 to 5.65, [SO42−]/[Si] = 0.09 to 5.65 and [DOC]/[Si] = 0.08 to 6.38. Even though no offset in δ30Si value is observed for DOC-contaminated samples, we recommend removal of DOC. We suggest that the matrix effect observed under dry plasma conditions can be primarily attributed to the use of introduction systems with desolvating membranes, followed by differences in the operating parameters and the absolute quantity of anions introduced into the plasma. Our study indicates that precise and accurate measurements (<0.11‰, 2SD) can be reached for stable Si isotope ratios by MC-ICP-MS in wet plasma, with a larger tolerance to sample based-matrix effect induced by anion contamination compared to dry plasma. [ABSTRACT FROM AUTHOR]

[Display omitted] • Novel sulfates supported binary RuIrO x be synthesized. • A strong catalyst-support interaction between RuIrO x and BaSrSO 4. • The RuIrO x /BSS exhibits a high OER mass activity of only 324 mV overpotential at 1000 A/g Ru + Ir. • It shows outstanding CER activity and stability. Electrolysis for producing hydrogen powered by renewable electricity can be dramatically expanded by adapting different electrolytes (brine, seawater or pure water), which means the anode materials must stand up to complex electrolyte conditions. Here, a novel catalyst/support hybrid of binary Ru 3.5 Ir 1 O x supported by barium strontium sulfate (BaSrSO 4) was synthesized (RuIrO x /BSS) by exchanging the anion ligands of support. The as-synthesized RuIrO x /BSS exhibits compelling oxygen evolution (OER) and chlorine evolution (CER) performances, which affords to 10 mA cm−2 with only overpotential of 244 mV and 38 mV, respectively. The performed X-ray adsorption spectra clearly indicate the presence of an interface charge transfer effect, which results in the assignment of more electrons to the d orbitals of the Ru and Ir sites. The theoretical calculations demonstrated that the electronic structures of the catalytic active sites were modulated to give a lower overpotential, confirming the intrinsically high OER and CER catalytic activity. [ABSTRACT FROM AUTHOR]

Multiple-step nucleation pathways have been observed during mineral formation in both inorganic and biomineral systems. These pathways can involve precursor aqueous species, amorphous intermediates, or metastable phases. Despite the widespread occurrence of these processes, elucidating the precise nucleation steps and the transformation mechanisms between each step remains a challenging task. Using a suite of potentiometric, microscopic, and spectroscopic tools, we studied the nucleation pathway of SrSO4 as a function of the physico-chemical solution parameters. Our observations reveal that below a threshold supersaturation, nucleation is driven by bound species, akin to the prenucleation cluster model, which directly leads to the formation of the stable phase celestine, SrSO4. At higher supersaturations, this situation is altered, with nucleation dominated by the consumption of free ions. Importantly, this change in nucleation mechanism is coupled to the formation of a hemihydrate metastable phase, SrSO4 · 1/2H2O, which eventually transforms into celestine, adhering to Ostwald's rule of stages. This transformation is a solution-mediated process, also occurring in the presence of a fluid film and is controlled by the physico-chemical parameters of the surrounding environment. It proceeds through the dissolution of the metastable phase and the de novo crystallization of the final phase. Overall, our results reveal that ion association taking place during the prenucleation stage dictates whether the nucleation pathway goes through an intermediate phase or not. This also underlines that although Ostwald's rule of stages is a common process, it is not a prerequisite for mineral formation—even in systems where it can occur. [ABSTRACT FROM AUTHOR]

This paper investigates the tensile behaviors and self-healing of engineered cementitious composite (ECC) under sulfate wet–dry cycles to reflect the durability. Four pretensile strain levels of 0%, 1%, 1.5%, and 2% were designed. The uniaxial tensile test, three-point bending test, and single-crack tensile test were performed, along with the microscopic characterizations of scanning electron microscope (SEM) and X-ray diffraction (XRD). The results indicated that the sulfate wet–dry cycle exposure had a positive effect on the tensile strength and initial cracking strength of the uncracked ECC, while that was negative on the tensile strain capacity. The insufficient margin of the σoc/σcr and Jb′/Jtip indices explained the lower tensile strain. The tensile strength and initial cracking strength of the cracked ECC with 1% pretensile strain surpassed those of the uncracked ECC after undergoing 80 sulfate wet–dry cycles (80 C), while that did not hold for the other cracked ECCs. All the cracked ECCs showed a similar tensile strain after undergoing 80 C. The crack with a width of less than 100 μm achieved complete self-healing. The self-healing products of ECC under sulfate wet–dry cycle exposure may comprise of calcium (alumino) silicate hydrate [C-(A)-S-H] gel, calcite, ettringite, and gypsum. The current findings could offer reference points for applying ECC use in coastal regions. [ABSTRACT FROM AUTHOR]

A rapid and efficient analytical method was established to quantify indoxyl sulfate (IS) in plasma through extraction technique with a deep eutectic solvent (DES) and spectrofluorimetric method. DES (choline chloride: urea) was mixed with plasma samples for the extraction of IS, followed by the addition of dipotassium hydrogen phosphate (K2HPO4) solution to form an aqueous two-phase system. The fluorescence intensity of IS which was first extracted to the DES-rich-phase and then back-extracted into the salt-rich-phase, was measured by spectrofluorimetric method. Some key factors such as pH, centrifugation speed and time, the volume ratio of DES/salt, and salt concentration were optimized. Under the optimized conditions, the suggested method had a dynamic range between 20 and 160 µg/mL with a coefficient of determination (R2) of 0.99. Precision (relative standard deviation) was less than 15% and accuracy (% relative recovery) was ± 15% at the nominal concentration level. In addition, results showed that IS levels in real samples were higher than 40 µg/mL which was compatible with reported IS levels in end-stage renal disease (ESRD) patients. Overall, all the results reflect the fact that the presented analytical method can potentially be used for the determination of IS in real plasma samples. [ABSTRACT FROM AUTHOR]

Salt crystallization is one of the most important factors causing weathering in grottoes. Cumulative crystallization of salts causes damage such as flaking and peeling of the rocks and accelerates the weathering processes of the grottoes. The accumulated crystalline salts cause spalling, skinning and other damage and accelerate the weathering process of the grotto rock body. It is necessary to study the existing glutenite rock grottoes. This paper took the glutenite rock of the Maijishan Grottoes as a case study, and Na2SO4 or MgSO4 solutions were applied to glutenite rock specimens subjected to different deterioration cycles. The crystallization patterns of the two different salts and their damage to the glutenite rock were analyzed and studied, the mechanism for salt crystallization damage to the glutenite rock was explored, and the crystallization pressures of the two salts in the glutenite rock were derived with theoretical calculations. The results showed that both Na2SO4 and MgSO4 crystallization damaged the glutenite rock, and the former different sulfate solutions changed at different rates, and the changes in the wave caused faster damage than the latter. The physical indices of the rock samples in the velocities and tensile strengths were consistent. Na2SO4 was mainly accumulated on the surface of the specimen and damaged the glutenite rock centripetally via pulverization and exfoliation. MgSO4 mainly crystallized inside the glutenite rock, which created internal fissures and reduced the strength of the rock. The theoretical maximum crystallization pressures of Na2SO4 and MgSO4 in the glutenite rock specimens reached 33.00 MPa and 9.94 MPa, respectively. This study provides a theoretical basis for studies of salt crystallization in glutenite rock grottoes and provides a method for protecting the stones in cultural heritage sites against weathering. [ABSTRACT FROM AUTHOR]

Na0.4MnO2 microrods were synthesized to adsorb 100 ppm of SO2 and NO2 at room temperature with the maximum uptake capacity of 78.7 and 42.3 mg g−1, respectively. While SO2 was oxidized to sulphate and bisulphate ions, NO2 was converted to nitrite and nitrate ions via hydroxyl groups and Mnn+ redox cycles. [ABSTRACT FROM AUTHOR]

This paper investigates comprehensively the operational dynamics of a thermochemical heat storage (TCHS) reactor for low-temperature applications using polyaluminum sulfate and takes into consideration a developed simulation model with an experimentation validation. Significant concordances were found between the developed simulation model and the experimental results. Results reveal optimized conditions for the charging process using an electrical heater, with a heating temperature of 120°C at 10 K/min over 500 minutes. This achieves full material charging, with stabilized pressure drops at an equilibrium of 80 mbar, corresponding to a temperature of approximately 108°C, and yielding a thermal power of 950 W. An inlet vapor pressure of 18 mbar at 10°C for 5 hours is sufficient to completely discharge the bed, with pressure drops reaching around 30 mbar and a thermal power of 300 after reaction completion. Insights into conversion extents during both processes are provided, along with a remarkable thermal efficiency of 90% and a coefficient of performance (COP) of 97%, surpassing recommended theoretical values (50%). The study suggests further enhancing system performance through the design and implementation of a dedicated heat exchanger. The achievement of 75% of the targeted thermal power specification represents a significant milestone, offering valuable contributions towards the realization of sustainable technological advancements of both the reactor technology of TCHS and state-of-the-art thermal energy storage solutions. From the research, it is possible to infer further suggestions for enhancing this performance by designing and implementing a dedicated heat exchanger for both heat supply and retrieval mechanisms. [ABSTRACT FROM AUTHOR]

In this study, a sulfonation approach using chlorosulfonic acid (CSA) to prepare cellulose sulfate nanofibers (CSNFs) from raw jute fibers is demonstrated. Both elemental sulfur content and zeta potential in the CSNFs are found to increase with increasing CSA content used. However, the corresponding crystallinity in the CSNFs decreases with the increasing amount of CSA used due to degradation of cellulose chains under harsh acidic conditions. The ammonium adsorption results from the CSNFs with varying degrees of sulfonation were analyzed using the Langmuir isotherm model, and the analysis showed a very high maximum ammonium adsorption capacity (41.1 mg/g) under neutral pH, comparable to the best value from a synthetic hydrogel in the literature. The high ammonium adsorption capacity of the CSNFs was found to be maintained in a broad acidic range (pH = 2.5 to 6.5). [ABSTRACT FROM AUTHOR]

In this study, Afşin Elbistan C-type fly ash (FA) was used, which protects against the sulphate reaction that damages concrete. The detrimental effects of post-reaction decrease with increasing fly ash fineness. The study used 10%, 30%, and 50% weight substitutes of cement. The fly ash was ground in a ball mill for 0, 10, 20, 30, 45, and 60 min, and Blaine fineness values of 1555, 1632, 2347, 2589, 2766, and 3433 cm2/g were obtained, respectively. The effect of the samples on the sulphate resistance was investigated by exposing the samples to 5% or 10% added sulphate solutions, and the compressive strength and ultrasonic pulse velocity of the concrete were tested. The compressive strength values obtained decreased with the increase in sulphate content, and the increase in the grinding time and the amount of substituted FA increased the compressive strength values. It was observed that weight loss increased with increasing sulphate content and decreased with the addition of FA with a high Blaine fineness. It was determined that as the Blaine fineness value increased, the sulphate content, FA substitution amount, and ultrasonic pulse speed decreased. This study was carried out to determine the effects of fly ash used at different fineness and replacement ratios on the performance and strength of concrete after exposure to external influences such as sulphate. The use of fly ash instead of cement will reduce the use of waste materials and natural resources and prevent environmental pollution. The cost of cement and concrete will be reduced. [ABSTRACT FROM AUTHOR]

The α-calcium sulfate hemihydrate whiskers (α-CSHWs) were first prepared using phosphogypsum (PG) and electrolytic manganese residue (EMR) as raw materials for coating urea, demonstrating excellent controlled-release properties. The effects of different reaction conditions on α-CSHWs, achieved by optimizing the reaction time, the concentrations of NH4+, Mn2+, and other factors, were discussed. Results showed that when the EMR content was 25 wt%, the reaction temperature was 100 °C, and the reaction time was 3 h, α-CSHWs with a length-to-diameter ratio of 39 were obtained. Through experiments and density functional theory (DFT), the mechanism of α-CSHWs preparation was elucidated. The results show that the addition of EMR reduces the content of impurity ions PO43− and F− in PG while introducing NH4+ and Mn2+. Interestingly, both NH4+ and Mn2+ can reduce the nucleation time of α-CSHWs, while PO43−, Mn2+, and F− are more likely to adsorb on the (0 0 6) crystal plane of α-CSHWs, NH4+ readily adsorbs on the (4 0 0) crystal plane. The controlled-release performance of modified α-CSHWs incorporated into polyurethane-coated urea (PCU) was investigated, and it was found that the addition of Mα significantly prolonged the nutrient release period, with the period extending up to 116 days for coatings of 5wt% and above. This work not only enhances the efficiency of PG and EMR utilization but also serves as a reference for the straightforward synthesis and application of α-CSHWs. [ABSTRACT FROM AUTHOR]

Na2EDTA is an effective morphology regulator in preparing α-calcium sulfate hemihydrate (α-HH) with high mechanical strength, but its simultaneous effect on the phase transformation process and morphology evolution of α-HH is still unclear. This study finds that the addition of Na2EDTA from 0.00 to 1.40 mM dramatically prolongs the induction time and phase transformation time from 2 to 240 min and 118 to 480 min respectively, due to the complexation of Ca2+ and EDTA2− in solution while further increase to 2.20 mM doesn't continuously increase the induction time and phase transformation time. Meanwhile, the addition of Na2EDTA generates the morphology evolution of α-HH from fibrous to short columnar with an average aspect ratio from 31.5 to 1.7, resulting from the selective adsorption of EDTA2− on both the top and side faces of α-HH crystals where Ca2+ ions are distributed at different densities. This selective adsorption provides more details compared with the conventional understanding of EDTA2− adsorption focusing on the top faces. Altogether, this work gives a clear view of the relationship between Na2EDTA concentration and phase transformation and morphology evolution of α-HH, which contributes to providing theoretical guidance on preparing α-HH crystals with an appropriate phase transformation rate and ideal morphology. [ABSTRACT FROM AUTHOR]

Background Bowel cleansing is an important factor for the quality of colonoscopy. We aimed to evaluate the efficacy of split-dose oral sulfate salts on bowel preparation and to determine parameters influencing the quality of bowel cleaning. Method Consecutive adults who completed their preparation for colonoscopy with a regimen of sulfate salts were enrolled. Results Of the 446 patients, 11 were excluded from the analysis. Among the 435 patients, 257 (59.1%) were female, mean age was 62.0±11.6 years and median body mass index (BMI) 26.1 kg/m2 (interquartile range [IQR] 23.8-29.4). Indications for colonoscopy were screening 155 (35.6%), surveillance 102 (23.5%), or other 178 (40.9%). The median time between the end of second dose of the preparation regimen and colonoscopy initiation was 5:15 h (IQR 4:30-6:00, min: 2:20, max: 12:20). Minor adverse events were reported in 62 (14.3%) patients. BBPS=9 was observed in 279 (64.14%) patients. Segmental BBPS=3 was achieved in 387 (88.97%), 346 (79.54%) and 289 (66.44%) patients (P<0.001) in the descending, transverse and ascending colon, respectively. Multivariate analysis revealed that BMI (odds ratio [OR] 1.05, 95% confidence interval [CI] 1-1.1) and time between the end of the second laxative dose and colonoscopy initiation (OR 1.25, 95%CI 1.08-1.45) were associated with poorer bowel preparation. Conclusions A split dose of oral sulfate salts is an efficacious and well tolerated regimen. Obesity and a longer time interval between the end of the second dose and colonoscopy initiation negatively influence bowel cleanliness. [ABSTRACT FROM AUTHOR]

The roles of keratan sulfate (KS) as a proton detection glycosaminoglycan in neurosensory processes in the central and peripheral nervous systems is reviewed. The functional properties of the KS-proteoglycans aggrecan, phosphacan, podocalyxcin as components of perineuronal nets in neurosensory processes in neuronal plasticity, cognitive learning and memory are also discussed. KS-glycoconjugate neurosensory gels used in electrolocation in elasmobranch fish species and KS substituted mucin like conjugates in some tissue contexts in mammals need to be considered in sensory signalling. Parallels are drawn between KS's roles in elasmobranch fish neurosensory processes and its roles in mammalian electro mechanical transduction of acoustic liquid displacement signals in the cochlea by the tectorial membrane and stereocilia of sensory inner and outer hair cells into neural signals for sound interpretation. The sophisticated structural and functional proteins which maintain the unique high precision physical properties of stereocilia in the detection, transmittance and interpretation of acoustic signals in the hearing process are important. The maintenance of the material properties of stereocilia are essential in sound transmission processes. Specific, emerging roles for low sulfation KS in sensory bioregulation are contrasted with the properties of high charge density KS isoforms. Some speculations are made on how the molecular and electrical properties of KS may be of potential application in futuristic nanoelectronic, memristor technology in advanced ultrafast computing devices with low energy requirements in nanomachines, nanobots or molecular switches which could be potentially useful in artificial synapse development. Application of KS in such innovative areas in bioregulation are eagerly awaited. [ABSTRACT FROM AUTHOR]

The Sample Analysis at Mars-Evolved Gas Analyzer (SAM-EGA) on the Curiosity rover detected hydrogen chloride (HCl) and sulfur dioxide (SO2) gas evolutions above 600 °C and 700 °C, respectively, from several drilled rock and soil samples collected in Gale crater, which have been attributed to NaCl and Mg sulfates. Although NaCl and Mg sulfates do not evolve HCl or SO2 within the SAM temperature range (<~870 °C) when analyzed individually, they may evolve these gases at <870 °C and become detectable by SAM-EGA when mixed. This work aims to determine how Mg sulfate and NaCl interact during heating and how that affects evolved HCl and SO2 detection temperatures in SAM-EGA. Solid mixtures of NaCl and kieserite were analyzed using a thermogravimeter/differential scanning calorimeter furnace connected to a quadrupole mass spectrometer, configured to operate under similar conditions as SAM, and using X-ray diffraction of heated powders. NaCl analyzed individually did not evolve HCl; however, NaCl/kieserite mixtures evolved HCl releases with peaks above 600 °C. The results suggested that kieserite influenced HCl production from NaCl via two mechanisms: (1) kieserite depressed the melting point of NaCl, making it more reactive with evolved water; and (2) SO2 from kieserite decomposition reacted with NaCl and water (i.e., Hargreaves reaction). Additionally, NaCl catalyzed the thermal decomposition of kieserite, such that the evolved SO2 was within the SAM-EGA temperature range. The results demonstrated that SAM-EGA can detect chlorides and Mg sulfates when mixed due to interactions during heating. These phases can provide information on past climate and mineral formation conditions. [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]

Thermal behavior of vergasovaite, ideally Cu3O(SO4)(MoO4), and its synthetic analog has been studied by high-temperature single-crystal X-ray diffraction in the temperature range of 300–1100 K. According to EMPA results, the empirical formulas are (Cu2.36Zn0.61)Σ2.97O[(Mo0.91S0.08V0.04)Σ1.03O4](SO4) for vergasovaite and Cu2.97O[(Mo0.92S0.09)Σ1.01O4](SO4) for its synthetic analog. The mineral is stable up to 950 ± 15 K; at 975 K, the unit-cell parameters and volume increase abruptly due to topotactic transformation of vergasovaite to cupromolybdite, Cu3O(MoO4)2. The transformation is accompanied by loss of sulfur (and excess copper) without destruction of the crystal. The thermal expansion of the vergasovaite structure is strongly anisotropic, being minimal along the [O2Cu6]8+ chains comprised of vertex-sharing OCu4 tetrahedra. This peculiar thermal behavior can be explained by the anisotropy of bond-length evolution in the Cu1O6 and Cu3O6 octahedra and the flexibility of the S-O-Cu and Mo-O-Cu bond angles. Synthetic Zn- and V-free analogs demonstrate negative thermal expansion at 425–625 K and melt at as low temperature as 700 K with no indication of transformation or recrystallization at least below 1200 K. The topotactic transformation observed in vergasovaite may have important implications for the design of novel materials and for understanding the alteration processes of copper minerals. [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]

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]

[Display omitted] • Landfill has extremely strong MPs release capacity in the early stage. • The sedimentary phase of leachate is the main sink of MPs. • Leachate circulation accelerates MPs release and fragmentation. • Sulfate reduction process promotes the release of MPs. • MPs release behavior can be attenuated in advance by leachate circulation. Landfills are essential facilities for treating and disposing municipal solid waste. They emit sulfur-containing odors and serve as an important sink for a new type of pollutant called microplastics (MPs). This study focused on the initial stage of anaerobic degradation to establish the relationship between the release of MPs and odor generation. Our findings show the rapid release of MPs into the leachate in the early stage of landfill and their predominant accumulation in the leachate sediment. The circulating leachate contained 1.45 times higher concentrations of MPs than the noncirculating leachate, with a peak concentration of 39 items·L−1. In addition, fragmentation of MPs occurred. The percentage of MPs with particle sizes of 2.5–5 mm decreased from 66.70 % to 22.32 %, while those measuring 0.1–0.5 mm increased by 33.12 %. A positive correlation was observed between MP release and sulfate reduction. Although leachate circulation increased the release of MPs, it also reduced the overall release time and total amount of MPs exported from the landfill. Compared with the initial landfill waste, the leachate operation mode, regardless of circulation, resulted in a 6.15–8.93-fold increase in MP release. These findings provide a valuable foundation for the simultaneous regulation of traditional pollutant odor and new pollutants (MPs) in landfills. [ABSTRACT FROM AUTHOR]

• Fe/Mg phyllosilicates and mono- and polyhydrated Mg sulfates are detected in Mikumi crater. • Possible desiccation/hydraulic fracturing on crater floor. • Phyllosilicates are on top of the sulfate units, meaning that they formed later than sulfates. • Mikumi crater is a key area in Meridiani Planum to investigate Mars' ancient climate. The region of Meridiani Planum on Mars retains the evidence of multiple surface and near-surface aqueous processes that span from the Noachian to the Hesperian. This makes it an interesting spot for better understanding the characteristics and the evolution of Mars' aqueous environment between these two fundamental epochs. Here we investigate the mineralogy, stratigraphy, and morphology of the Noachian–Hesperian sedimentary materials that fill a 16-km-wide crater named Mikumi, located in the northern part of Meridiani Planum. The analysis was carried out combining observations from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM), the High Resolution Imaging Science Experiment (HiRISE), and the Context Imager (CTX). About 20–30 meters, on average, of Fe/Mg phyllosilicate-rich rocks and a thick sequence (75 m) of both mono- and polyhydrated Mg sulfates are detected on the crater floor. Both layers postdate the impact event. Most of the hydrated terrains are extensively polygonally fractured, suggesting the possible action of water-related processes such as desiccation and hydro fracturing on the sediments. Stratigraphic analysis clearly shows that Fe/Mg phyllosilicates were deposited on top of the sulfate sequence, meaning that they are younger than sulfates. This can have interesting implications on paleoclimatic studies of Mars as it shows that a simple timeline going from a clay-rich Noachian to a sulfate-rich Hesperian oversimplifies the evolution of Mars' mineralogy and related aqueous environment at the Noachian–Hesperian boundary. [ABSTRACT FROM AUTHOR]

• Stable isotopes of riverine sulfate in arid environment were investigated. • Contributions of riverine sulfate sources were identified by an inverse model. • Evaporites dissolution dominates riverine sulfate source with spatial variations. • Lithology, precipitation and temperature dominate sulfur behaviors in river basins. The fate of riverine sulfate ion (SO 4 2-) and its environmental effects in arid environment are difficult to evaluate due to its complicated sources and strongly coupled behaviors with water cycle which is significantly modified by humans. To understand the sulfur cycle in aquatic systems in arid environment, the chemical and sulfur and oxygen isotopic compositions (δ34S SO4 and δ18O SO4) of major rivers around the Badain Jaran Desert, northwestern China, were investigated. These rivers had averaged SO 4 2- content at 1336 µmol/L, over 10 times higher than the global average. The δ34S SO4 and δ18O SO4 values ranged from -5.3‰ to +11.8‰ and +1.6‰ to +12.8‰, respectively. The end-member analysis and the inverse model showed that riverine sulfate was mainly derived from evaporites dissolution (0-87%), sulfide oxidation (13%-100%) and precipitation (0-33%), indicating heterogeneity in sulfur sources and behaviors along the river drainage with the lithology variations and climate gradients. Multiple isotopic tools combining with hydro-chemistry compositions could be applied to reveal sulfur cycle in arid environment. Based on the calculation, sulfide oxidation plays the primary role in the headwater and upstream in the Qilian-Mountains area, where sulfide is widely exposed. While the proportion of evaporites dissolution contributing to riverine sulfate is much higher in downstream in a drier environment. Besides, less precipitation and higher temperature can lead to more intensive evaporation, affecting the process of sulfide oxidation and enhancing the rates of evaporites dissolution and sulfate precipitation in the basin. [Display omitted] [ABSTRACT FROM AUTHOR]

We recently showed that 6-sulfo sialyl N-acetyllactosamine (LacNAc) in O-linked glycans recognized by the CL40 antibody is abundant in the pleural mesothelium under physiological conditions and that these glycans undergo complementary synthesis by GlcNAc6ST2 (encoded by Chst4) and GlcNAc6ST3 (encoded by Chst5) in mice. GlcNAc6ST3 is essential for the synthesis of R-10G-positive keratan sulfate (KS) in the brain. The predicted minimum epitope of the R-10G antibody is a dimeric asialo 6-sulfo LacNAc. Whether R-10G-reactive KS/sulfated LacNAc oligosaccharides are also present in the pleural mesothelium was unknown. The question of which GlcNAc6STs are responsible for R-10G-reactive glycans was an additional issue to be clarified. Here, we show that R-10G-reactive glycans are as abundant in the pulmonary pleura as CL40-reactive glycans and that GlcNAc6ST3 is only partially involved in the synthesis of these pleural R-10G glycans, unlike in the adult brain. Unexpectedly, GlcNAc6ST2 is essential for the synthesis of R-10G-positive KS/sulfated LacNAc oligosaccharides in the lung pleura. The type of GlcNAc6ST and the magnitude of its contribution to KS glycan synthesis varied among tissues in vivo. We show that GlcNAc6ST2 is required and sufficient for R-10G-reactive KS synthesis in the lung pleura. Interestingly, R-10G immunoreactivity in KSGal6ST (encoded by Chst1) and C6ST1 (encoded by Chst3) double-deficient mouse lungs was markedly increased. MUC16, a mucin molecule, was shown to be a candidate carrier protein for pleural R-10G-reactive glycans. These results suggest that R-10G-reactive KS/sulfated LacNAc oligosaccharides may play a role in mesothelial cell proliferation and differentiation. Further elucidation of the functions of sulfated glycans synthesized by GlcNAc6ST2 and GlcNAc6ST3, such as R-10G and CL40 glycans, in pathological conditions may lead to a better understanding of the underlying mechanisms of the physiopathology of the lung mesothelium. [ABSTRACT FROM AUTHOR]

We successfully synthesized a one-dimensional cobalt sulfate coordinating polymer, whose simple hydrogen bond web structure facilitated the analysis of the proton transfer process. At 175 °C, without humidity, the conductivity is 0.0311 S cm−1, which exceeds those of most of the organic inorganic hybrid materials under anhydrous conditions (world record rank 8). Based on its crystal structure and theoretical calculations, the subversive proton conduction pathway was inferred clearly. We, for the first time, found that the proton smartly chose the path with a lower energy barrier but not the one with short distance to transport avoiding short circuit. [ABSTRACT FROM AUTHOR]

Microbial dissimilatory sulfate reduction (DSR) is a key process in the Earth biogeochemical sulfur cycle. In spite of its importance to the sulfur and carbon cycles, industrial processes, and human health, it is still not clear how reduction of sulfate to sulfide is coupled to energy conservation. A central step in the pathway is the reduction of sulfite by the DsrAB dissimilatory sulfite reductase, which leads to the production of a DsrC-trisulfide. A membrane-bound complex, DsrMKJOP, is present in most organisms that have DsrAB and DsrC, and its involvement in energy conservation has been inferred from sequence analysis, but its precise function was so far not determined. Here, we present studies revealing that the DsrMKJOP complex of the sulfate reducer Archaeoglobus fulgidus works as a menadiol:DsrC-trisulfide oxidoreductase. Our results reveal a close interaction between the DsrC-trisulfide and the DsrMKJOP complex and show that electrons from the quinone pool reduce consecutively the DsrM hemes b, the DsrK noncubane [4Fe-4S]3+/2+ catalytic center, and finally the DsrC-trisulfide with concomitant release of sulfide. These results clarify the role of this widespread respiratory membrane complex and support the suggestion that DsrMKJOP contributes to energy conservation upon reduction of the DsrC-trisulfide in the last step of DSR. [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 common approach to creating antimicrobial polymer materials is the distribution of a bactericidal additive in a material by mixing the additive with a solution or a melt of the polymer. This work proposes the method introducing of copper(II) sulfate, which has antimicrobial properties, into a poly(lactic acid) film by forced impregnation of a salt solution via the crazing mechanism. CuSO4 has been found to be uniformly distributed in the bulk of the polymer in the form of particles with sizes of about 100 nm. In the course of the structural modification, the surface of the polymer film becomes rougher and more hydrophobic. The water contact angle increases from 40° to 60°–65°. The incorporation of CuSO4 does not affect the surface properties but has a reinforcing effect on the polymer matrix as is evident from tensile tests (strength and elongation at break increase by 2.5 and 1.4 times, respectively). [ABSTRACT FROM AUTHOR]

New biamphiphilic surfactants (BSs) have been synthesized based on alkylmethylmorpholinium cation and dodecyl sulfate anion (Mor-n(DS), n = 4, 6, 8, 10). The structure of the biamphiphiles has been characterized by IR spectroscopy, 1H NMR spectroscopy, mass spectrometry, and elemental analysis. The aggregation behavior of the biamphiphiles in aqueous solutions has been assessed by tensiometry, conductometry, fluorescence spectroscopy (using a pyrene probe) and dynamic and electrophoretic light scattering. It has been shown that an increase in the hydrophobic tail length by two carbon atoms in an amphiphilic cation leads to an increase in the surface activity of the surfactant by ~5 units and a decrease in the aggregation threshold of the systems by 1.5–2 times. It has been established that the formation of aggregates with hydrodynamic diameters of 20–120 nm depending on the alkyl chain length of the alkylmethylmorpholinium cation and BS concentration. The zeta potential of the systems ranges from –25 to –100 mV and decreases with increasing biamphiphile concentration. Spectrophotometry has been employed to show a significant solubilization capacity of the biamphiphiles with respect to a hydrophobic dye Orange OT. The compounds obtained may be of interest for biomedical applications and other high-tech areas. [ABSTRACT FROM AUTHOR]

• Fucoidan ameliorated dextran sulfate sodium-induced ulcerative colitis through promoting autophagy. • Fucoidan-induced autophagy improved colon barrier and reshaped gut microbiota. • The present study supported the therapeutic potential of fucoidan for the adjuvant treatment of other autophagy-related diseases. Although previous research has unveiled the remedial effects of fucoidan, an extract from marine algae, on ulcerative colitis (UC), the precise mechanisms remain elusive. Animal studies have suggested a connection between autophagy and the beneficial influences of fucoidan intervention. We hypothesized that fucoidan's alleviative effects on dextran sulfate sodium (DSS)-induced UC could be ascribed to autophagy. For our study, we chose 36 male C57BL/6 mice and administered 100 or 400 mg/(kg/body weight/day) of fucoidan via gavage for 5 consecutive weeks. During the last week, the mice were given 3% DSS in drinking water to induce UC. In contrast to the DSS-induced UC model, fucoidan intervention prevented DSS-induced body weight loss, mitigated colon shortening, improved colon mucosa damage, enhanced the intestinal barrier, and reduced serum inflammatory factor concentrations. Furthermore, fucoidan intervention reshaped the gut microbiota compositions, increased the relative abundance of Bacteroidota, Muribaculaceae_unclassified, Clostridiales_unclassified , and Lachnospiraceae_NK4A136_group , and decreased the relative abundance of Firmicutes, Proteobacteria, and Escherichia-Shigella , which led to a lower Firmicutes/Bacteroidota ratio. Additionally, fucoidan treatment enhanced autophagy, as evidenced by upregulated protein expressions of BECLIN1, ATG5, ATG7, and an increased microtubule-associated-proteinlight-chain-3-II/microtubule-associated-proteinlight-chain-3-I ratio. Our findings corroborated the ameliorating effects of fucoidan intervention on DSS-induced UC through autophagy activation, reorganization of gut microbiota, and fortification of the intestinal barrier. This lends support to the therapeutic potential of fucoidan as a natural bioactive ingredient for future UC treatments in humans. Rapidly increasing incidence of UC imposed an enormous burden on health care. The aim of this study was to investigate the potential mechanisms of fucoidan to ameliorate DSS-induced UC. Fucoidan treatments improved the intestinal barrier, regulated gut microbiota composition, decreased serum inflammatory factors concentrations, and promoted autophagy by inhibiting PI3K/AKT/mTOR signaling pathway, thereby ameliorating DSS-induced UC. Abbreviations: AKT, protein kinase B; ATG5, autophagy-related gene 5; ATG7, autophagy-related gene 7; ATG16L1, autophagy-related protein 16-like 1; DSS, dextran sulfate sodium; IL-1β, interleukin-1β; LC3, microtubule-associated-proteinlight-chain-3; mTOR, mammalian target of rapamycin; MUC-2, mucin-2; PI3K, phosphoinositide-3 kinase; TNF-α, tumor necrosis factor-alpha; UC, ulcerative colitis; ULK1, serine/threonine kinase Unc-51-like kinase 1; ZO-1, zonula occludens-1. [Display omitted] [ABSTRACT FROM AUTHOR]

Galvanic interactions present alternative strategies to achieve a more efficient Cu dissolution from CuFeS2. The present work studied the interaction between chalcopyrite–magnetite (CuFeS2-Fe3O4) in acidified ferric sulphate Fe2(SO4)3-H2SO4 at a solution pH of 1.8 and a temperature of 25 or 50 °C. The addition of Fe3O4 to CuFeS2 forms a galvanic couple, which positively impacts the dissolution of Cu. The results showed that the presence of Fe3O4 led to high and fast Cu dissolution rates and decreased significantly the activation energy, from 83 to 57 kJ/mol. In addition to that, the solid residues revealed that CuFeS2 dissolution produced intermediate Cu-S-rich phases: CuS, Cu2S and Cu5FeS4, which appeared to envelop CuFeS2, had no observable intermediate phase while in the presence of Fe3O4. The results showed that 94% of Cu could be recovered after 5 h of leaching at 50 °C at a Fe3O4/CuFeS2 ratio of 4:1 and a 460 mV Ag/AgCl solution potential. The findings of this study present an option for efficient Cu dissolution from CuFeS2 in ferric sulphate at atmospheric pressure. [ABSTRACT FROM AUTHOR]

The expansion induced by sulfate attack on cement-treated aggregates (SACA) is a well-known problem that can be solved. It causes obvious heaves in road bases and railway subgrades. In this paper, the effects of the sodium sulfate content, cement content, degree of compaction, sulfate types, attack types, aluminum ion supply, concentration of curing sulfate solution, and temperature on the expansion behavior induced by SACA were investigated over 60 days in the laboratory. Based on the Sobol sensitivity analysis method, the influence of the sensitivity of each factor on the expansion was quantitatively analyzed, and the dominant factor of expansion was proposed. Results show that sulfate content is the domain factor of expansion that is induced by SACA, and it presents a logarithmic function relationship with strain. The 0.5% sodium sulfate content is the minimum sulfate content which causes the expansion that is induced by SACA. When the sulfate content is less than 1%, the expansion induced by SACA is minor. When the sulfate content is between 1% and 3%, the expansion behavior is expressed in four stages as follows: rapid strain increase, followed by a short stagnation period, then a significant strain increase and, finally, constant strain. When the sulfate content is greater than 5%, there are two stages comprising the expansion behavior as follows: the rapid strain increases and constant strain occurs. Greater sulfate content, greater degree of compaction, and lower temperature have positive effects on the expansion induced by SACA. The cement content does not have a consistent effect on expansion behavior. Compared with a sodium sulfate attack, both the reaction rate and expansion of cement-treated aggregates that are attacked by gypsum are smaller, and the attack period is also longer. When the sulfate content is greater than 1%, the addition of kaolin promotes the progression of the expansion induced by SACA. A small amount of water is sufficient for the demand for the sulfate attack. When the sulfate content is at a certain level, the expansion induced by SACA that is under external attack is much smaller than the expansion that is under internal attack. This study is expected to serve as a reference for future research on the mechanics of SACA, and it attempts to provide theoretical support for amending expansions that are induced by SACA. [ABSTRACT FROM AUTHOR]

In this research, a novel Brønsted-acidic ionic liquid 1,3-(4,4′-bipyridinium disulfonic acid)-propane-dihydrogen sulfate (BPDSPDH) was synthesized as a bi-functional catalyst. BPDSPDH was characterized using various analytical techniques such as FTIR, TGA, 13CNMR, 1HNMR, and mass spectrometry. Afterward, the catalytic ability of BPDSPDH was explored in the synthesis of chromeno[4,3-b]chromene and pyrido[2,3-d:6,5-d′]dipyrimidine derivatives. BPDSPDH is an ionic liquid catalyst with advantages such as having a high catalytic activity due to its acidic and basic sites, the use of affordable and easily accessible starting materials for catalyst production, recyclability of the catalyst up to 4 times without significant loss in catalytic activity, short reaction time, high yields and moderate reaction conditions. [ABSTRACT FROM AUTHOR]

A Biopharmaceutics Classification System (BCS)-based biowaiver monograph is presented for isavuconazonium sulfate. A BCS-based biowaiver is a regulatory option to substitute appropriate in vitro data for in vivo bioequivalence studies. Isavuconazonium sulfate is the prodrug of isavuconazole, a broad-spectrum azole antifungal indicated for invasive fungal infections. While the prodrug can be classified as a BCS Class III drug with high solubility but low permeability, the parent drug can be classified as a BCS Class II drug with low solubility but high permeability. Interestingly, the in vivo behavior of both is additive and leads isavuconazonium sulfate to act like a BCS class I drug substance after oral administration. In this work, experimental solubility and dissolution data were evaluated and compared with available literature data to investigate whether it is feasible to approve immediate release solid oral dosage forms containing isavuconazonium sulfate according to official guidance from the FDA, EMA and/or ICH. The risks associated with waiving a prodrug according to the BCS-based biowaiver guidelines are reviewed and discussed, noting that current regulations are quite restrictive on this point. Further, results show high solubility but instability of isavuconazonium sulfate in aqueous media. Although experiments on the dissolution of the capsule contents confirmed 'very rapid' dissolution of the active pharmaceutical ingredient (API) isavuconazonium sulfate, its release from the commercial marketed capsule formulation Cresemba is limited by the choice of capsule shell material, providing an additional impediment to approval of generic versions via the BCS-Biowaiver approach. [ABSTRACT FROM AUTHOR]

In the Late Permian Zechstein Sea of Central Europe, up to 2000 m of evaporitic rocks were deposited in at least four consecutive cycles. The age of these evaporitic rocks could not yet be precisely determined, because they are virtually fossil-free and do not contain radiometrically datable volcanic layers. A chemostratigraphic age of the succession can be determined by comparing 87Sr/86Sr ratios of marine gypsum and anhydrite to the worldwide marine strontium evolution curve. Unfortunately, published 87Sr/86Sr data of the Zechstein succession are characterized by frequent outliers towards higher ratios, making an age assignment challenging. The scatter in 87Sr/86Sr ratios might be induced by different processes like the contribution of meteoric water to the brine, in-situ Rb decay, or post-depositional hydrothermal or diagenetic overprint. Here, we present a dataset of 26 new gypsum and anhydrite 87Sr/86Sr ratios from drill cores situated at "Alter Stolberg" in the northernmost Thuringian Basin. Evaporites of the Werra-, Staßfurt-, and Leine cycles were sampled. The close proximity of the drillings allows a very accurate assignment of the stratigraphic position of each sample, so that trends and outliers in 87Sr/86Sr ratios can easily be recognized. While the entire Werra Formation obviously revealed non-marine 87Sr/86Sr ratios, the lowermost 87Sr/86Sr ratios in the Staßfurt and Leine Formations can be assumed to represent marine ratios and allow estimating a chemostratigraphic age of 257‒254 Ma. The combination of the 87Sr/86Sr data with the mineral composition of the samples suggests a contribution of meteoric water, probably river water, to the Zechstein Sea as the main reason for the observed increase in 87Sr/86Sr ratios. Additional in-situ Rb decay, related to the riverine input of clay minerals, cannot be excluded. Modelling the amounts of sea water and meteoric water in the brine indicates that 83‒99% of meteoric water would be necessary to explain the highest 87Sr/86Sr ratios observed in the Werra Formation. [ABSTRACT FROM AUTHOR]