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Following the growth of infotech and electronic industries, electromagnetic-wave-absorbing materials play an essential role in the traction of the need for high-precision weaponry and intelligent electronic equipment. The exploitation of high-performance electromagnetic-wave-absorbing materials has emerged as a strategic challenge to be solved in the upgrading of military equipment and civil electromagnetic security. The more maturely studied absorbing materials (carbon, ferrite, etc.) have a single loss mechanism and poor resistance matching, which are already not enough to cover the basic needs. To explore absorbing materials that satisfy both impedance matching and attenuation balance, dielectric nanomaterials have come to the fore. They can realize light weight, thin layer, broad band, and multiband, which have great application prospects. In this review, we start with a summary of typical dielectric loss mechanisms (interfacial polarization, dipole polarization, and conduction loss). Next, diverse carbides, oxides, sulfides, and their composites with dielectric or magnetic materials are described, and the nanostructure advantages and wave-absorbing performance advantages are investigated. Then, the applications of wave-absorbing materials are depicted. Lastly, the challenges faced by dielectric-type materials are outlined, and future development trends are foreseen. Overall, this review offers an overview of the advances in the study of dielectric nanoabsorbing materials. [ABSTRACT FROM AUTHOR]

Size and purity of metal phosphate and metal sulfide colloids can control the solubility, persistence, and bioavailability of metals in environmental systems. Despite their importance, methods for detecting and characterizing the diversity in the elemental composition of these colloids in complex matrices are missing. Here, we develop a single-particle inductively coupled plasma time-of-flight mass spectrometry (sp-icpTOF-MS) approach to characterize the elemental compositions of individual metal phosphate and sulfide colloids extracted from complex matrices. The stoichiometry was accurately determined for particles of known composition with an equivalent spherical diameter of ≥∼200 nm. Assisted by machine learning (ML), the new method could distinguish particles of the copper sulfides covellite (CuS), chalcocite (Cu 2 S), and chalcopyrite particles (CuFeS 2 ) with 75% (for Cu 2 S) to 99% (for CuFeS 2 ) accuracy. Application of the sp-icpTOF-MS method to particles recovered from natural samples revealed that iron sulfide (FeS) particles in lake sediment contained ∼4% copper and zinc impurities, whereas pure pyrite (FeS 2 ) was identified in hydraulic fracturing wastewater and confirmed by selected area electron diffraction. Colloidal mercury in an offshore marine sediment was present as pure mercury sulfide (HgS), whereas geogenic HgS recovered from an industrial process contained ∼0.08 wt % silver per Hg, enabling source apportionment of these colloids using ML. X-ray absorption spectroscopy confirmed that Hg was predominantly present as metacinnabar (β-HgS) in the industrial process sample. The determination of impurities in individual colloids, such as zinc and copper in FeS, and silver in HgS may enable improved assessment of their origin, reactivity, and bioavailability potential.

Coastal zones account for 75% of marine methane emissions, despite covering only 15% of the ocean surface area. In these ecosystems, the tight balance between methane production and oxidation in sediments prevents most methane from escaping into seawater. However, anthropogenic activities could disrupt this balance, leading to an increased methane escape from coastal sediments. To quantify and unravel potential mechanisms underlying this disruption, we used a suite of biogeochemical and microbiological analyses to investigate the impact of anthropogenically induced redox shifts on methane cycling in sediments from three sites with contrasting bottom water redox conditions (oxic-hypoxic-euxinic) in the eutrophic Stockholm Archipelago. Our results indicate that the methane production potential increased under hypoxia and euxinia, while anaerobic oxidation of methane was disrupted under euxinia. Experimental, genomic, and biogeochemical data suggest that the virtual disappearance of methane-oxidizing archaea at the euxinic site occurred due to sulfide toxicity. This could explain a near 7-fold increase in the extent of escape of benthic methane at the euxinic site relative to the hypoxic one. In conclusion, these insights reveal how the development of euxinia could disrupt the coastal methane biofilter, potentially leading to increased methane emissions from coastal zones.

Further reducing total nitrogen (TN) and total phosphorus (TP) in the secondary effluent needs to be realized effectively and in an eco-friendly manner. Herein, four pyrite/sawdust composite-based biofilters were established to treat simulated secondary effluent for 304 days. The results demonstrated that effluent TN and TP concentrations from biofilters under the optimal hydraulic retention time (HRT) of 3.5 h were stable at <2.0 and 0.1 mg/L, respectively, and no significant differences were observed between inoculated sludge sources. The pyrite/sawdust composite-based biofilters had low N 2 O, CH 4 , and CO 2 emissions, and the effluent's DOM was mainly composed of five fluorescence components. Moreover, mixotrophic denitrifiers ( Thiothrix ) and sulfate-reducing bacteria ( Desulfosporosinus ) contributing to microbial nitrogen and sulfur cycles were enriched in the biofilm. Co-occurrence network analysis deciphered that Chlorobaculum and Desulfobacterales were key genera, which formed an obvious sulfur cycle process that strengthened the denitrification capacity. The higher abundances of genes encoding extracellular electron transport (EET) chains/mediators revealed that pyrite not only functioned as an electron conduit to stimulate direct interspecies electron transfer by flagella but also facilitated EET-associated enzymes for denitrification. This study comprehensively evaluates the water-gas-biofilm phases of pyrite/sawdust composite-based biofilters during a long-term study, providing an in-depth understanding of boosted electron transfer in pyrite-based mixotrophic denitrification systems.

Surgical removal of tumor tissue remains the primary clinical approach for addressing breast cancer; however, complete tumor excision is challenging, and the remaining tumor cells can lead to tumor recurrence and metastasis over time, which substantially deteriorates the life quality of the patients. With the aim to improve local cancer radiotherapy, this work reports the fabrication of alginate (Alg) scaffolds containing bovine serum albumin (BSA)-coated bismuth sulfide (Bi 2 S 3 @BSA) nanoradiosensitizers using three-dimensional (3D) printing. Under single-dose X-ray irradiation in vitro, Alg-Bi 2 S 3 @BSA scaffolds significantly increase the formation of reactive oxygen species, enhance the inhibition of breast cancer cells, and suppress their colony formation capacity. In addition, scaffolds implanted under tumor tissue in murine model show high therapeutic efficacy by reducing the tumor volume growth rate under single-dose X-ray irradiation, while histological observation of main organs reveals no cytotoxicity or side effects. 3D-printed Alg-Bi 2 S 3 @BSA scaffolds produced with biocompatible and biodegradable materials may potentially lower the recurrence and metastasis rates in breast cancer patients by inhibiting residual tumor cells following postsurgery as well as exhibit anticancer properties in other solid tumors.

Fluoride anions (F - ) play a crucial role in human physiological processes. However, excessive intake of F - would affect oxygen metabolism and promote the generation of oxygen-free radicals. Hence, it is essential to develop a precise and efficient fluorescent probe for visualizing F - -induced oxidative stress. In this work, we developed the first bifunctional BODIPY-based fluorescent probe dfBDP with p - tert -butyldimethylsilanolate benzyl thioether as the sensing site for the detection of F - and HClO via two distinct reactions, the self-immolative removal and the thioether oxidation, which generate the sensing products with two nonoverlap fluorescence bands: 800-1200 and 500-750 nm, respectively. The probe dfBDP displays rapid response, high specificity, and sensitivity for the detection of F - (LOD, 316.2 nM) and HClO (LOD, 33.9 nM) in vitro. Cellular imaging reveals a correlation between F - -induced oxidative stress and the upregulation of HClO. Finally, probe dfBDP was employed to detect F - and HClO in mice under the stimulation of F - . The experimental results display that the level of HClO elevates in the liver of mice.

Many applications of hydrogels rely on their ability to deliver encapsulated solutes, such as drugs; however, small hydrophilic solutes rapidly leak out of gels by diffusion. A need exists for a way to regulate solute release out of gels─to ensure zero release until a desired time (the OFF state) and thereafter for the release to be switched ON at a high rate. This should ideally be a repeatable switch; i.e., the gel should be cyclable repeatedly between the ON and OFF states. Such perfect, cyclical ON-OFF release of solutes from gels is demonstrated for the first time through a "smart skin" that is synthesized rapidly (in ∼10 min) around an entire gel. The thin (∼100 μm) and transparent polymer skin is endowed with redox-responsive properties through the use of urethane and acrylate monomers, one of which contains a thioether group. Initially, the skin is hydrophobic (water contact angle 102°), and it completely prevents hydrophilic solutes from leaking out of the gel. When contacted with oxidants such as hydrogen peroxide (H 2 O 2 ), the thioethers are converted to sulfoxides, making the skin hydrophilic (water contact angle 42°) and thereby turning ON the release of solutes. Conversely, solute release can be turned OFF subsequently by adding a reducing agent such as vitamin C that reverts the sulfoxides to thioethers and thus returns the skin to its hydrophobic state. The release rate in the ON state can be tuned via the skin thickness as well as the oxidant concentration. The ability to regulate solute delivery from gels using smart skins is likely to prove significant in areas ranging from separations to agriculture and drug delivery.

The effort to modulate challenging protein targets has stimulated interest in ligands that are larger and more complex than typical small-molecule drugs. While combinatorial techniques such as mRNA display routinely produce high-affinity macrocyclic peptides against classically undruggable targets, poor membrane permeability has limited their use toward primarily extracellular targets. Understanding the passive membrane permeability of macrocyclic peptides would, in principle, improve our ability to design libraries whose leads can be more readily optimized against intracellular targets. Here, we investigate the permeabilities of over 200 macrocyclic 10-mers using the thioether cyclization motif commonly found in mRNA display macrocycle libraries. We identified the optimal lipophilicity range for achieving permeability in thioether-cyclized 10-mer cyclic peptide-peptoid hybrid scaffolds and showed that permeability could be maintained upon extensive permutation in the backbone. In one case, changing a single amino acid from d-Pro to d-NMe-Ala, representing the loss of a single methylene group in the side chain, resulted in a highly permeable scaffold in which the low-dielectric conformation shifted from the canonical cross-beta geometry of the parent compounds into a novel saddle-shaped fold in which all four backbone NH groups were sequestered from the solvent. This work provides an example by which pre-existing physicochemical knowledge of a scaffold can benefit the design of macrocyclic peptide mRNA display libraries, pointing toward an approach for biasing libraries toward permeability by design. Moreover, the compounds described herein are a further demonstration that geometrically diverse, highly permeable scaffolds exist well beyond conventional drug-like chemical space.

Nanoparticle-based drug carriers that can respond to oxidative stress in tumor tissue have attracted attention for site-specific drug release. Taking advantage of the characteristic microenvironment in tumors, one of the attractive directions in drug delivery research is to design drug carriers that release drugs upon oxidation. A strategy to incorporate oxidation-sensitive thioether motifs such as thiomorpholine acrylamide (TMAM) to drug carriers has been often used to achieve oxidation-induced dissociation, thereby targeted drug release. However, those delivery systems often suffer from a slow dissociation rate due to the intrinsic hydrophobicity of the thioether structures. In this study, we aimed to enhance the dissociation rate of TMAM-based micelles upon oxidation. The random copolymers of N -isopropylacrylamide and TMAM (P(NIPAM/TMAM)) were designed as an oxidation-sensitive segment that showed a fast response to oxidative stress. We first synthesized P(NIPAM/TMAM) copolymers with different NIPAM:TMAM molar ratios. Those copolymers exhibited low critical solution temperatures (LCSTs) below 32 °C, which shifted to higher temperatures after oxidation. The changes in LCSTs depend on the NIPAM:TMAM molar ratios. At the NIPAM:TMAM molar ratio of 82:18, the LCSTs before and after oxidation were 17 and 54 °C, respectively. We then prepared micelles from the diblock copolymers of poly( N -acryloyl morpholine) (PAM) and P(NIPAM/TMAM). The micelles showed an accelerated dissociation rate upon oxidation compared to the micelles without NIPAM units. Furthermore, the doxorubicin (Dox)-loaded micelles showed enhanced relative toxicity in human colorectal cancer (HT29) cells over human umbilical vein endothelial cells (HUVECs). Our novel strategy to design an oxidation-sensitive micellar core comprising a P(NIPAM/TMAM) segment can be used as a chemotherapeutic delivery system that responds to an oxidative tumor microenvironment in an appropriate time scale.

Rational structure design benefits the development of efficient nanoplatforms for tumor theranostic application. In this work, a multifunctional polydopamine (PDA)-coated manganese sulfide (MnS) nanocluster was prepared. The polyhydroxy structure of PDA enhanced the water interaction with pH-responsive MnS nanoclusters via hydrogen bonds. At pH 5.5 conditions, the spin-lattice relaxation rate of MnS nanoclusters dramatically increased from 5.76 to 19.33 mM -1 ·s -1 after the PDA coating, which can be beneficial for efficient tumor magnetic resonance imaging. In addition, PDA endowed MnS nanoclusters with excellent biocompatibility and good photothermal conversion efficiency, which can be used for efficient tumor photothermal therapy (PTT). Furthermore, MnS nanoclusters possess the ability to release H 2 S in the acidic tumor microenvironment, effectively inhibiting mitochondrial respiration and adenosine triphosphate production. As a result, the expression of heat shock protein was obviously reduced, which can reduce the resistance of tumor cells to photothermal stimulation and enhance the efficacy of PTT. The released Mn 2+ also displayed efficient peroxidase and glutathione oxidase-like activity, effectively inducing tumor cell ferroptosis and apoptosis at the same time. Therefore, this nanoplatform could be a potential nanotheranostic for magnetic resonance contrast enhancement and synergistic ferroptosis-PTT of tumors.

Acridone, a cyclic analogue of benzophenone that undergoes efficient intersystem crossing (ISC) to the triplet-excited state with near-unity quantum yield, was elaborated as a 3-connecting triacid linker, i.e., H 3 AcTA , to develop a photocatalytic metal-organic framework (MOF) for energy transfer applications; the triacid linker inherently features concave shapes, an attribute that is important for the construction of MOFs with significant porosity. Metal ion (Zn 2+ )-assisted self-assembly of the triacid yielded a Zn-MOF, i.e., Zn-AcTA , with a solvent-accessible volume of ca. 31%. The protection of the acridone chromophore in the MOF in conjunction with a wider cross-section of its absorption in the visible region renders the MOF an excellent heterogeneous photosensitizer for singlet oxygen ( 1 O 2 ). It is shown that the Zn-MOF can be applied as a photosensitizing catalyst for visible light-mediated oxidation of various sulfides to sulfoxides and enaminones to amino-esters via 1,2-acyl migration. It is further demonstrated that the photocatalyst can be easily recycled without any loss of catalytic activity and structural integrity. Based on mechanistic investigations, 3 O 2 ). It is shown that the Zn-MOF can be applied as a photosensitizing catalyst for visible light-mediated oxidation of various sulfides to sulfoxides and enaminones to amino-esters via 1,2-acyl migration. It is further demonstrated that the photocatalyst can be easily recycled without any loss of catalytic activity and structural integrity. Based on mechanistic investigations, 1 O 2 is established as the reactive oxygen species in photocatalytic oxidation reactions. The results constitute the first demonstration of rational development of a photocatalytic MOF based on acridone for heterogeneous oxidations mediated by 1 O 2 .

Autoxidation of drugs and drug-like molecules is a major concern in the development of safe and effective therapeutics. Because active pharmaceutical ingredients (APIs) that contain sulfur atoms can form sulfoxides under oxidative stress, predicting oxidative susceptibilities within an organic molecule can have a major impact in accelerating the compound's stability assessment. For investigation of a sulfur atom's oxidative stability, density functional theory (DFT) methods were applied to accurately predict S-O estimated bond dissociation enthalpies (BDEs) of sulfoxides. Our process employed B3LYP/6-31+G(d) for geometry optimization and frequency calculation, and we employed B3P86/6-311++G(2df,2p) to obtain electronic energies from single-point energy calculations. A total of 84 drug-like molecules containing 50 different sulfide scaffolds were used to develop a risk scale. Our results showed that when S-O BDE is less than 69 kcal/mol, the sulfur atom has low oxidative susceptibility. High oxidation risk occurs when the S-O BDE is greater than 75 kcal/mol. The risk scale was successful in predicting the relative propensities of sulfide oxidation among the small organic molecules and commercial drugs examined.

Biological sulfide oxidation is an efficient means to recover elemental sulfur (S 0 ) as a valuable resource from sulfide-bearing wastewater. This work evaluated the autotrophic sulfide oxidation to S 0 in the O 2 -based membrane biofilm reactor (O 2 -MBfR). High recovery of S 0 (80-90% of influent S) and high sulfide oxidation (∼100%) were simultaneously achieved when the ratio of O 2 -delivery capacity to sulfide-to S 0 surface loading (SL) (O 2 /S 2- → S 0 ratio) was around 1.5 (g O 2 /m 2 -day/g O 2 /m 2 -day). On average, most of the produced S 0 was recovered in the MBfR effluent, although the biofilm could be a source or sink for S 0 . Shallow metagenomic analysis of the biofilm showed that the top sulfide-oxidizing genera present in all stages were Thauera , Thiomonas , Thauera&#95;A , and Pseudomonas . Thiomonas or Pseudomonas was the most important genus in stages that produced almost only S 0 (i.e., the O 2 /S 2- → S 0 ratio around 1.5 g of the O 2 /m 2 -day/g O 2 /m 2 -day). With a lower sulfide SL, the S 0 -producing genes were sqr and fccAB in Thiomonas . With a higher sulfide SL, the S 0 -producing genes were in the soxABDXYZ system in Pseudomonas . Thus, the biofilm community of the O 2 -MBfR adapted to different sulfide-to-S 0 SLs and corresponding O 2 -delivery capacities. The results illustrate the potential for S 0 recovery using the O 2 -MBfR.

Further reducing the organic requirements is essential for the sustainable development of partial denitrification/anammox technology. Here, an innovative mixotrophic partial denitrification/anammox (MPD/A) installation fed with pyrite and few organics was realized, and the average nitrogen and phosphorus removal rates were as high as 96.24 ± 0.11% and 79.23 ± 2.06%, respectively, with a C/N ratio of 0.5. To understand the nature by which MPD/A achieves efficient nitrogen removal and organic conservation, the electron transfer-dependent nitrogen escape and energy metabolism were first elucidated using multiomics analysis. Apart from heterotrophic denitrification and anammox, the results revealed some unexpected metabolic couplings of MPD/A systems, in particular, putative nitrate-dependent organic and pyrite oxidation among nominally heterotrophic Denitratisoma (PRO3) strains, which accelerated nitrate gasification with a low-carbon supply. Additionally, Candidatus Brocadia (AMX) employed extracellular solid-state electron acceptors as terminal electron sinks for high-rate ammonium removal. AMX transported ammonium electrons to extracellular γFeO(OH) (generated from pyrite oxidation) through the transient storage of menaquinoline pools, cytoplasmic migration via multiheme cytochrome(s), and OmpA protein/nanowires-mediated electron hopping on cell surfaces. Further investigation observed that extracellular electron flux resulted in the transfer of more energy from the increased oxidation of the electron donor to the ATP, supporting nitrite-independent ammonium removal.

Despite its impact on the climate, the mechanism of methanesulfonic acid (MSA) formation in the oxidation of dimethyl sulfide (DMS) remains unclear. The DMS + OH reaction is known to form methanesulfinic acid (MSIA), methane sulfenic acid (MSEA), the methylthio radical (CH 3 S), and hydroperoxymethyl thioformate (HPMTF). Among them, HPMTF reacts further to form SO 2 and OCS, while the other three form the CH 3 SO 2 radical. Based on theoretical calculations, we find that the CH 3 SO 2 radical can add O 2 to form CH 3 S(O) 2 OO, which can react further to form MSA. The branching ratio is highly temperature sensitive, and the MSA yield increases with decreasing temperature. In warmer regions, SO 2 is the dominant product of DMS oxidation, while in colder regions, large amounts of MSA can form. Global modeling indicates that the proposed temperature-sensitive MSA formation mechanism leads to a substantial increase in the simulated global atmospheric MSA formation and burden.

Deep-sea mining magnifies the release of heavy metals into seawater through oxidative dissolution of seafloor massive sulfide (SMS). At present, there is little information about how the metals released into seawater might be affected by the mineral assemblages, seawater conditions, and solid percentages. Here, leaching experiments were carried out to examine the behavior of three sulfides from the Southwest Indian Ridge, under conditions that replicated deep and shallow seawater environments at three solid-liquid ratios. The results demonstrated that sphalerite dissolved rapidly, and the metals released in both experimental conditions were comparable, potentially reflecting galvanic interactions between the sulfide minerals. Large quantities of the released metals were removed from the solutions when hydrous ferric oxides formed, especially for shallow seawater conditions. A comparison of metal concentrations in the leachates with the baseline metal concentrations in natural seawater indicated that most of the released metals, when diluted with seawater, would not have widespread impacts on ecosystems. Based on the obtained unique oxidative dissolution properties of each SMS at variable solid-liquid ratios, targeted wastewater discharge treatments are proposed to minimize impacts from the dissolved metals. This study will support the development of robust guidelines for deep-sea mining activities.

Polymer micelles/vesicles made of a red-light-responsive Ru(II)-containing block copolymer (PolyRu) are elaborated as a model system for anticancer phototherapy. PolyRu is composed of PEG and a hydrophobic polypeptoid bearing thioether side chains, 40% of which are coordinated with [Ru(2,2':6',2″-terpyridine)(2,2'-biquinoline)](PF 6 ) 2 via the Ru-S bond, resulting in a 67 wt % Ru complex loading capacity. Red-light illumination induces the photocleavage of the Ru-S bond and produces [Ru(2,2':6',2″-terpyridine)(2,2'-biquinoline)(H 2 O)](PF 6 ) 2 . Meanwhile, ROS are generated under the photosensitization of the Ru complex and oxidize hydrophobic thioether to hydrophilic sulfoxide, causing the disruption of micelles/vesicles. During the disruption, ROS generation and Ru complex release are synergistically enhanced. PolyRu micelles/vesicles are taken up by cancer cells while they exhibit very low cytotoxicity in the dark. In contrast, they show much higher cytotoxicity under red-light irradiation. PolyRu micelles/vesicles are promising nanoassembly prototypes that protect metallodrugs in the dark but exhibit light-activated anticancer effects with spatiotemporal control for photoactivated chemotherapy and photodynamic therapy.

Quantum dots (QDs) are widely applied and inevitably released into the environment. The biotransformation of Se in typical CdSe/ZnS QDs coated with glutathione (CdSe/ZnS-GSH) to volatile alkyl selenides and the fate of alkyl selenides in the hydroponically grown rice system were investigated herein. After a 10-day exposure to CdSe/ZnS-GSH (100 nmol L -1 ), seven alkyl selenides, dimethyl selenide (DMSe), dimethyl diselenide (DMDSe), methyl selenol (MSeH), ethylmethyl selenide (EMSe), ethylmethyl diselenide (EMDSe), dimethyl selenenyl sulfide (DMSeS), and ethylmethyl selenenyl sulfide (EMSeS), were detected in the exposure system using the suspect screening strategy. CdSe/ZnS-GSH was first biotransformed to DMSe and DMDSe by plant and microorganisms. The generated DMSe was volatilized to the gas phase, adsorbed and absorbed by leaves and stems, downward transported, and released into the hydroponic solution, whereas DMDSe tended to be adsorbed/absorbed by roots and upward transported to stems. The airborne DMSe and DMDSe also partitioned from the gas phase to the hydroponic solution. DMSe and DMDSe in the exposure system were further transformed to DMSeS, EMSeS, EMSe, EMDSe, and MSeH. This study gives a comprehensive understanding on the behaviors of Se in CdSe/ZnS-GSH in a rice plant system and provides new insights into the environmental fate of CdSe/ZnS QDs.

Anaerobic secondary treatment has the potential to facilitate energy-positive operations at wastewater treatment plants, but post-treatment of the anaerobic effluent is needed to recover dissolved methane and nutrients and remove sulfide. In this study, a life cycle assessment was conducted to compare hypothetical full-scale wastewater treatment trains and direct potable reuse trains that combine the staged anaerobic fluidized membrane bioreactor (SAF-MBR) with appropriate post-treatment. We found that anaerobic wastewater treatment trains typically consumed less energy than conventional aerobic treatment, but overall global warming potentials were not significantly different. Generally, recovery of dissolved methane for energy production resulted in lower life cycle impacts than microbial transformation of methane, and microbial oxidation of sulfide resulted in lower environmental impacts than chemical precipitation. Use of reverse osmosis to produce potable water was also found to be a sustainable method for nutrient removal because direct potable reuse trains with the SAF-MBR consumed less energy and had lower life cycle impacts than activated sludge. Moving forward, dissolved methane recovery, reduced chemical usage, and investments that enable direct potable reuse have been flagged as key research areas for further investigation of anaerobic secondary treatment options.

Understanding biological events associated with H 2 S n rather than mediated by H 2 S is of great significance but remains to be solved due to a lack of high-integrity imaging tools. In this study, we report a chemoselective probe for H 2 S n over H 2 S through the molecular engineering of luminogens. Based on our search for H 2 S n -activatable probes with high selectivity, we fabricate water-soluble and biocompatible nanoprobes. Such a designed nanoprobe shows rare aggregation-induced dual-color fluorescence responses to H 2 S n , lighting up bright emissions at 588 and 750 nm, respectively. By use of this activatable dual-color fluorescence, high-integrity identification of intracellular H 2 S n was successfully realized. Thus, our approach to H 2 S n -activated multicolor fluorescent probes could provide valuable insight into interrogating H 2 S n -mediated biological events.

Galectins play biological roles in immune regulation and tumor progression. Ligands with high affinity for the shallow, hydrophilic galectin-3 ligand binding site rely primarily on a galactose core with appended aryltriazole moieties, making hydrophobic interactions and π-stacking. We designed and synthesized phenyl sulfone, sulfoxide, and sulfide-triazolyl thiogalactoside derivatives to create affinity-enhancing hydrogen bonds, hydrophobic and π-interactions. Crystal structures and thermodynamic analyses revealed that the sulfoxide and sulfone ligands form hydrogen bonds while retaining π-interactions, resulting in improved affinities and unique binding poses. The sulfoxide, bearing one hydrogen bond acceptor, leads to an affinity decrease compared to the sulfide, whereas the corresponding sulfone forms three hydrogen bonds, two directly with Asn and Arg side chains and one water-mediated to an Asp side chain, respectively, which alters the complex structure and increases affinity. These findings highlight that the sulfur oxidation state influences both the interaction thermodynamics and structure.

Point-of-use treatment technologies can increase access to safe drinking water in rural areas. Sustained use of these technologies is uncommon due to oversight of community needs, user-perceived risks, long-term maintenance, and conflict with traditional practices. Nanosilver-enabled ceramic water filters are unique due to the use of locally sourced materials available at or near the target community; however, technical limitations persist (e.g., nanosilver's uncontrolled release and passivation from sulfide or chloride). This work aims to overcome these limitations by impregnating nanosilver onto ceramics with a Navajo pottery rosin, collected from pinyon trees with a third-generation artisan. Here, we investigate this sustainable and novel material for drinking water treatment; the study ranges from a proof of concept to testing under realistic conditions. Results show that when embedded in a thin film, the biopolymer controlled ionic silver dissolution and prevented silver passivation from sulfide and chloride. When applied to ceramic filters, the biopolymer effectively immobilized nanosilver in a range of waters. Over a 25 day study to emulate household-use conditions, this coating method sustained disinfection of a coculture of Gram-positive and Gram-negative bacteria while controlling biofouling. Overall, the use of this Navajo pottery material can facilitate adoption while providing the needed technological advancement to these widely used treatment devices.

A label-free addressable photoelectric immunosensor array was designed for the detection of amyloid β-proteins based on magnetic separation and self-calibration strategies. In this paper, Na 2 Ti 6 O 13 with a flower-like morphology was prepared by the hydrothermal method; after continuously combining Fe 3 O 4 and CdS, it was endowed with magnetism and better photoelectric activity. Subsequently, a series of reactions occurred in the solution, and the magnetic separation method was used to enrich the target. On the other hand, the ITO glass was separated into eight sites (2 × 4) using magnets, and a light shield was utilized to prevent light exposure, resulting in addressable and continuous detection. After the uniform preparation of magnetic photoelectric materials and precise control of testing conditions, the relative errors among different sites have been effectively reduced. Moreover, incorporating a self-calibration strategy has allowed the sensor array to achieve greater accuracy. The proposed photoelectrochemical biosensor exhibits a good relationship with amyloid β-protein ranging from 0.01 to 100 ng mL -1 with a limit of detection of 1.1 pg mL -1 and exhibits excellent specificity, reproducibility, and stability.

Transition-metal chalcogenides with intercalated layered structures are interesting systems in material physics due to their attractive electronic and magnetic properties, with applications in the fields of magnetic refrigerators, catalysts, and thermoelectrics, among others. In this work, we studied in detail the structural, electronic, and magnetic properties of (Fe,Ti)-based sulfides with formula Fe x Ti 2 S 4 ( x = 0.24, 0.32, and 0.42), prepared as polycrystalline materials under high-pressure conditions. They present a layered Heideite-type crystal structure, as assessed by synchrotron X-ray diffraction. A local structure analysis using Fe K -edge extended X-ray-absorption fine structure (EXAFS) data unveiled a conspicuous contraction of the main Fe-S bond in Fe 0.24 Ti 2 S 4 at the vicinity of the magnetic transition 60-80 K. We suggest that this anomaly is related to magnetoelastic coupling effects. The EXAFS analysis allowed extraction of the Einstein temperatures (θ E ), i.e., the phonon contribution to the specific heat, for the two bond pairs Fe-S (1) [θ E ≈318 K; 290 K ( C / T )] and Fe-Ti (1) [θ E ≈218 K; 190 K ( C / T )]. In addition to the structural and local vibrational measurements, we probed the magnetic properties using magneto-calorimetry, magnetometry under applied pressure, magnetoresistance (MR), and Hall effect measurements. We observed the appearance of a broad peak in the specific heat around 120 K in the x = 0.42 compound that we associated with an antiferromagnetic ordering electronic transition. We found that the antiferromagnetic transition temperature is pressure and composition sensitive and reduces at 1.2 GPa by ∼12 and ∼3 K, for the members with x = 0.24 and x = 0.42, respectively. Similarly, the saturation magnetization in the ordered phase depends on both pressure and iron content, reducing its value by 50, 90, and 30% for x = 0.24, 0.32, and 0.42, respectively. We observed clear jumps in the magnetic hysteresis loops, MR, and anomalous Hall effect (AHE) below 2 K at fields around 2-4 T. We associated this observation with the metamagnetic transitions; from the Berry-curvature a decoupling parameter of S H = 0.12 V -1 is determined. Comparison of the results on the temperature-dependent magnetization, MR, and AHE elucidates a strong inelastic scattering contribution to the AHE at higher temperatures due to the cluster spin-glass phase.

Iron (oxyhydr)oxides and organic matter (OM) are intimately associated in natural environments, and their fate might be linked to sulfur during sulfidation-reoxidation cycling. However, the coupling of DOM molecular fractionation with Fe and S transformations following a full sulfidation-reoxidation cycle remains poorly understood. Here, we reacted Fh and Fh-OM associations with S(-II) anaerobically and then exposed the sulfidic systems to air. S(-II) preferentially reacted with Fh to form inorganic S (e.g., mackinawite, S 0 , and S 2 2- ) over being incorporated into OM as organic S and therefore indirectly affected OM fate by altering Fe speciation. Fh sulfidation was inhibited by associated OM, and the main secondary Fe species were mackinawite, Fe(II)-OM compounds, and lepidocrocite. Concomitantly, organic molecules high in unsaturation, aromaticity, and molecular weight were detached from solid-phase Fe species due to their lower affinities for secondary Fe species than for Fh. During the reoxidation stage, the previously formed Fe(II) species were reoxidized to Fh with a stronger aggregation, which recaptured formerly released OM with higher selectivity. Additionally, •OH was generated from Fe(II) oxygenation and degraded a portion of the DOM molecules. Overall, these results have significant implications for Fe, C, and S cycling in S-rich environments characterized by oscillating redox conditions.

Bacterial sulfate reduction plays a crucial role in the mobilization of toxic substances in aquifers. However, the role of bacterial sulfate reduction on iodine mobilization in geogenic high-iodine groundwater systems has been unexplored. In this study, the enrichment of groundwater δ 34 S SO4 (15.56 to 69.31‰) and its significantly positive correlation with iodide and total iodine concentrations in deep groundwater samples of the North China Plain suggested that bacterial sulfate reduction participates in the mobilization of groundwater iodine. Similar significantly positive correlations were further observed between the concentrations of iodide and total iodine and the relative abundance of the dsrB gene by qPCR, as well as the composition and abundance of sulfate-reducing bacteria (SRB) predicted from 16S rRNA gene high-throughput sequencing data. Subsequent batch culture experiments by the SRB Desulfovibrio sp. B304 demonstrated that SRB could facilitate iodine mobilization through the enzyme-driven biotic and sulfide-driven abiotic reduction of iodate to iodide. In addition, the dehalogenation of organoiodine compounds by SRB and the reductive dissolution of iodine-bearing iron minerals by biogenic sulfide could liberate bound or adsorbed iodine into groundwater. The role of bacterial sulfate reduction in iodine mobilization revealed in this study provides new insights into our understanding of iodide enrichment in iodine-rich aquifers worldwide.

Sulfur mustard [HD; bis-(2-chloroethyl) sulfide] and other analogues are a kind of highly toxic vesicant and have been prohibited by the Organization for the Prohibition of Chemical Weapons (OPCW) since 1997. Exposures to HD could generate several adducts in the plasma and hydrolysis products in the urine, which are widely applied as biomarkers to identify HD exposure in forensic analysis. Several methods have been developed for the detection of related biomarkers. However, most methods are based on complex derivatization, and not enough attention is paid to HD analogues. A modified and convenient analytical method reported herein includes simultaneous incubation and organic solvent extraction. The biomarkers such as thiodiglycol and 1,2-bis (2-hydroxyethylthio) are transferred to HD and 1,2-bis(2-chloroethylthio) ethane via hydrochloric acid at the appropriate temperature. The analytes are analyzed by gas chromatography tandem mass spectrometry (GC-MS/MS) with 2-chloroethyl ethyl sulfide (2-CEES) applied as the internal standard. The interday and intraday study according to FDA rules has been achieved to evaluate the accuracy and precision of the method. The two targets are detected with a good linearity ( R 2 > 0.99) in the concentration ranges from 5 to 1000 ng/mL and 10 to 1000 ng/mL, with small relative standard deviations (RSD ≤6.62% and RSD ≤6.93%) and favorable recoveries between 90.3 and 107.3% and between 89.4 and 108.7%, respectively. The established method can be used for retrospective detection of sulfur mustards in biological samples and successfully applied in the biomedical proficiency testing organized by the OPCW.

Removal of hydrogen sulfide (H 2 S) can be achieved using the sustainable biological desulfurization process, where H 2 S is converted to elemental sulfur using sulfide-oxidizing bacteria (SOB). A dual-bioreactor process was recently developed where an anaerobic (sulfidic) bioreactor was used between the absorber column and micro-oxic bioreactor. In the absorber column and sulfidic bioreactor, polysulfides (S x 2- ) are formed due to the chemical equilibrium between H 2 S and sulfur (S 8 ). S x 2- is thought to be the intermediate for SOB to produce sulfur via H 2 S loading rates, and elucidate the relationship between biomass and the observed biological removal of sulfides under anaerobic conditions. A linear relationship was observed between S x 2- , determine their chain-length distribution under high H 2 S loading rates, and elucidate the relationship between biomass and the observed biological removal of sulfides under anaerobic conditions. A linear relationship was observed between S x 2- concentration and H 2 S loading rates at a constant biomass concentration. Increasing biomass concentrations resulted in a lower measured S x 2- concentration at similar H 2 S loading rates in the sulfidic bioreactor. S x 2- of chain length 6 (S 6 2- ) showed a substantial decrease at higher biomass concentrations. Identifying S x 2- concentrations and their chain lengths as a function of biomass concentration and the sulfide loading rate is key in understanding and controlling sulfide uptake by the SOB. This knowledge will contribute to a better understanding of how to reach and maintain a high selectivity for S 8 formation in the dual-reactor biological desulfurization process.

The traditional hydrolysis-cooling-adsorption process for coke oven gas (COG) desulfurization urgently needs to be improved because of its complex nature and high energy consumption. One promising alternative for replacing the last two steps is selective catalytic oxidation. However, most catalysts used in selective catalytic oxidation require a high temperature to achieve effective desulfurization. Herein, a robust 30Fe-MCM41 catalyst is developed for direct desulfurization at medium temperatures after hydrolysis. This catalyst exhibits excellent stability for over 300 h and a high breakthrough sulfur capacity (2327.6 mgS g cat -1 ). Introducing Ag into the 30Fe-MCM41 (30Fe5Ag-MCM41) catalyst further enhances the H 2 S removal efficiency and sulfur selectivity at 120 °C. Its outstanding performance can be attributed to the synergistic effect of Fe-Ag clusters. During H 2 S selective oxidation, Fe serves as the active site for H 2 S adsorption and dissociation, while Ag functions as the catalyst promoter, increasing Fe dispersion, reducing the oxidation capacity of the catalyst, improving the desorption capacity of sulfur, and facilitating the reaction between active oxygen species and [HS]. This process provides a potential route for enhancing COG desulfurization.

Liquid elemental mercury (Hg 0 L ) pollution can remain in soils for decades and, over time, will undergo corrosion, a process in which the droplet surface oxidizes soil constituents to form more reactive phases, such as mercury oxide (HgO). While these reactive coatings may enhance Hg migration in the subsurface, little is known about the transformation potential of corroded Hg 0 L in the presence of reduced inorganic sulfur species to form sparingly soluble HgS particles, a process that enables the long-term sequestration of mercury in soils and generally reduces its mobility and bioavailability. In this study, we investigated the dissolution of corroded Hg 0 L in the presence of sulfide by quantifying rates of aqueous Hg release from corroded Hg 0 L droplets under different sulfide concentrations (expressed as the S:Hg molar ratio). For droplets corroded in ambient air, no differences in soluble Hg release were observed among all sulfide exposure levels (S:Hg mole ratios ranging from 10 -4 to 10). However, for droplets oxidized in the presence of a more reactive oxidant (hydrogen peroxide, H 2 O 2 ), we observed a 10- to 25-fold increase in dissolved Hg when the oxidized droplets were exposed to low sulfide concentrations (S:Hg ratios from 10 -4 to 10 -1 ) relative to droplets exposed to high sulfide concentrations. These results suggest two critical factors that dictate the release of soluble Hg from Hg 0 L in the presence of sulfide: the extent of surface corrosion of the Hg 0 L droplet and sufficient sulfide concentration for the formation of HgS solids. The mobilization of Hg 0 L in porous media, therefore, largely depends on aging conditions in the subsurface and chemical reactivity at the Hg 0 L droplet interface.

The mechanism of the metal centered reduction of metmyoglobin (MbFe III ) by sulfide species (H 2 S/HS - ) under an argon atmosphere has been studied by a combination of spectroscopic, kinetic, and computational methods. Asymmetric S-shaped time-traces for the formation of MbFe II at varying ratios of excess sulfide were observed at pH 5.3 < pH < 8.0 and 25 °C, suggesting an autocatalytic reaction mechanism. An increased rate at more alkaline pHs points to HS - as relevant reactive species for the reduction. The formation of the sulfanyl radical (HS • ) in the slow initial phase was assessed using the spin-trap phenyl N - tert -butyl nitrone. This radical initiates the formation of S-S reactive species as disulfanuidyl/ disulfanudi-idyl radical anions and disulfide (HSSH •- /HSS •2- and HSS - , respectively). The autocatalysis has been ascribed to HSS - , formed after HSSH •- /HSS •2- disproportionation, which behaves as a fast reductant toward the intermediate complex MbFe III (HS - ). We propose a reaction mechanism for the sulfide-mediated reduction of metmyoglobin where only ferric heme iron initiates the oxidation of sulfide species. Beside the chemical interest, this insight into the MbFe III /sulfide reaction under an argon atmosphere is relevant for the interpretation of biochemical aspects of ectopic myoglobins found on hypoxic tissues toward reactive sulfur species.

An efficient and practical route for the synthesis of β-amino sulfides by Lewis acid-mediated electrophilic thiolative difunctionalization of enimides is disclosed. A series of free phenols, electron-rich arene, alcohol, azide, and hydride, are successfully incorporated into the substrates in high regio- and stereoselectivities under mild conditions. The obtained products possess multiple functional groups and can be easily transformed to other valuable molecules.

Herein, we present the BF 3 /BF 4 - mediated activation of diphenyl phosphite for the formation of thionium ions from aldehydes and thiophenols. These reactive species subsequently undergo reaction with in situ generated phenol, resulting in the synthesis of diarylmethyl thioethers. It was demonstrated that the addition of external phenol in the reaction produced unsymmetrical gem -diarylmethyl thioethers in good yields.

Transition metal sulfides have exhibited remarkable advantages in gaseous elemental mercury (Hg 0 ) capture under high SO 2 atmosphere, whereas the weak thermal stability significantly inhibits their practical application. Herein, a novel N , N -dimethylformamide (DMF) insertion strategy via crystal growth engineering was developed to successfully enhance the Hg 0 capture ability of MoS 2 at an elevated temperature for the first time. The DMF-inserted MoS 2 possesses an edge-enriched structure and an expanded interlayer spacing (9.8 Å) and can maintain structural stability at a temperature as high as 272 °C. The saturated Hg 0 adsorption capacities of the DMF-inserted MoS 2 were measured to be 46.91 mg·g -1 at 80 °C and 27.40 mg·g -1 at 160 °C under high SO 2 atmosphere. The inserted DMF molecules chemically bond with MoS 2 , which prevents possible structural collapse at a high temperature. The strong interaction of DMF with MoS 2 nanosheets facilitates the growth of abundant defects and edge sites and enhances the formation of Mo 5+ /Mo 6+ and S 2 2- species, thereby improving the Hg 0 capture activity at a wide temperature range. Particularly, Mo atoms on the (100) plane represent the strongest active sites for Hg 0 oxidation and adsorption. The molecule insertion strategy developed in this work provides new insights into the engineering of advanced environmental materials.

Disulfide bonds have been widely used to develop reduction-responsive drug-delivery systems (DDS) for cancer therapy. We propose that disulfide bonds might be also used as an oxidation-responsive linkage just like thioether bonds, which can be oxidized to hydrophilic sulfoxide or sulphone in the presence of oxidation stimuli. To test our hypothesis, we design three novel paclitaxel-citronellol conjugates linked via different lengths of disulfide-bond-containing carbon chain. The prodrugs can self-assemble into uniform-size nanoparticles with impressively high drug loading (>55%). As expected, the disulfide-bond-bridged prodrug nanoparticles show redox dual-responsive drug release. More interestingly, the position of disulfide bonds in the carbon chain linkage has profound impacts on the redox dual responsiveness, thereby affecting the drug release, cytotoxicity, pharmacokinetics, biodistribution, and in vivo antitumor efficacy of prodrug nanoassemblies. The redox dual-responsive mechanism is elucidated, and how the position of disulfide bonds in the carbon chain affects the redox dual responsiveness and antitumor efficiency of prodrug nanoassemblies is also clarified. Our findings give new insight into the stimuli responsiveness of disulfide bonds and provide a good foundation for the development of novel redox dual-responsive DDS for cancer therapy. [ABSTRACT FROM AUTHOR]

A general and efficient Pd/phosphoramidite thioether complex-catalyzed asymmetric N-allylic alkylation of hydrazones with allylic acetates has been developed for the first time. The reaction allows for the preparation of various valuable N-substituted hydrazones with generally good yields and excellent enantioselectivities. Minor structural modification of the ligand resulted in opposite enantiomers, enabling enantiodivergent synthesis of products by the same catalytic system. [ABSTRACT FROM AUTHOR]

The development of the global economy leads to a rising demand for light olefins, which are the basic chemical raw materials. Recently, a series of bifunctional catalysts consisting of metal oxide and zeolite have been reported to perform excellent light olefin selectivity from syngas and attract much attention. In this article, a new sulfide (MoS2)-zeolite (SAPO-34) composite catalyst was studied for syngas conversion to light olefins. It was found that the side reaction of methanation and hydrogenation of olefins to paraffins was suppressed by the introduction of potassium. Characterization results showed that the introduction of potassium could enhance the formation of K-Mo-S structure, at which the alcohol precursor formed. The optimized bifunctional catalyst MoS2-0.6K + SAPO-34 performed 12.5% CO conversion and 61.2% C2-C4 olefin selectivity. [ABSTRACT FROM AUTHOR]

A cascade radical cyclization of 2-isocyanoaryl thioethers with H-phosphorus oxides, organoboronic acids, or alkyl radical precursors has been efficiently developed, providing a novel and highly efficient methodology to structurally diverse C2-substituted benzothiazole derivatives with broad functional group tolerance and good yields. This cascade radical process achieves the first cycloaddition of an imidoyl radical from isocyanide to sulfur atom, rending C(sp²)-S bond formation. [ABSTRACT FROM AUTHOR]

An efficient cascade reaction of propargyl amines with AgSCF3 and KBr is developed, affording allenyl thiocyanates at room temperature in high yields. This transformation proceeds via the in situ formation of isothiocyanate intermediates, followed by a [3,3]-sigmatropic rearrangement. The resulting allenyl thiocyanates bearing 3-(electro-donating phenyl) substitutions without isolation can then be reacted with di-tert-butyl peroxide and AgSCF3 under reflux to generate novel allenyl trifluoromethylthioether compounds in moderate to good yields via a "one-pot" three-step process. [ABSTRACT FROM AUTHOR]

The N-H . . . S hydrogen bond, even though classified as an unconventional hydrogen bond, is found to bear important structural implications on protein structure and folding. In this article, we report a gas-phase study of the N-H…S hydrogen bond between the model compounds of histidine (benzimidazole, denoted BIM) and methionine (dimethyl sulfide, diethyl sulfide, and tetrahydrothiophene, denoted Me2S, Et2S, and THT, respectively). A combination of laser spectroscopic methods such as laser-induced fluorescence (LIF), two-color resonant two-photon ionization (2cR2PI), and fluorescence depletion by infrared spectroscopy (FDIR) is used in conjunction with DFT and ab initio calculations to characterize the nature of this prevalent H-bonding interaction in simple bimolecular complexes. A single conformer was found to exist for the BIM-Me2S complex, whereas the BIM-Et2S and BIM-THT complexes showed the presence of three and two conformers, respectively. These conformers were characterized on the basis of IR spectroscopic results and electronic structure calculations. Quantum theory of atoms in molecules (QTAIM), natural bond orbital (NBO), and energy decomposition (NEDA) analyses were performed to investigate the nature of the N-H…S H-bond. Comparison of the results with the N-H…O type of interactions in BIM and indole revealed that the strength of the N-H…S H-bond is similar to N-H…O in these binary gas-phase complexes. [ABSTRACT FROM AUTHOR]

The successful construction of porphyrin functionalized metallacycle in the confined cavity of mesoporous carbon FDU-16 (3⊂C) is presented in this study. Because of high dispersity of metallacycles within the mesoporous cavities, the stability and activity of porphyrin-containing metallacycles were obviously improved. For example, 1O2 generation efficiency of 3⊂C is ca. 6-fold faster than that of free metallaycles in solution. Thus, the resultant hybrid material has been successfully employed as a heterogeneous catalyst for photooxidation of sulfides. [ABSTRACT FROM AUTHOR]

In this paper, Bi1-xPbxCuOS samples (0 ≤ x ≤ 0.05) have been synthesized with a simple and scalable ball-milling process, followed by a reactive Spark Plasma Sintering. Our results highlight that, Pb for Bi substitution increases the charge carriers concentration by more than 2 orders of magnitude from 1.4 x 1017 cm-3 to 2.6 x 1019 cm-3 for x = 0 and x = 0.05, respectively. As a result, the electrical resistivity is divided by more than 50 at room temperature and the Seebeck coefficient drops from 707 μV K-1 to 265 μV K-1 where our experimental results are supported with density functional theory (DFT) calculations. Electronic structure calculations show that, just below the top of the valence band, several other bands are present and may contribute to the transport properties with appropriate tuning of the heavy-light valence band and the position of the Fermi level. Pb doping increases the number of holes pockets and several band degeneracies appear around the Fermi level, leading to a drastic enhancement of the power factor up to 0.2 mW m-1 K-2 at 700 K. This is 5 times higher than the value of the pristine compound. The intrinsically low thermal conductivity of 0.7 W m-1 K-1 at 700 K is interpreted on the basis of vibrational properties calculations within the Density Functional Perturbation Theory (DFPT) approach. It indicates that soft acoustic modes along the Γ-Z direction suggest weak interatomic bonding between the layers and possible strong anharmonicity. The power factor being enhanced with a minimal impact on the thermal conductivity, the figure of merit ZT reaches 0.2 at 700 K for x = 0.05. To the best of our knowledge, it is considered the best reported value among the family of oxysulfides [ABSTRACT FROM AUTHOR]

Pyrite is the most common sulfide in nature, and it is well-known for its roles in acid mine drainage, flotation separation of useful metal (Cu, Pb, Zn, and Mo) sulfide minerals, optoelectronic and photovoltaic application, pneumoconiosis, and even in the origin of life. However, the detailed oxidation behaviors of pyrite are still unclear and not well-understood. New oxidation pathways by O2 on the pyrite (100) surface have been found in this work for the first time using density functional theory simulation; that is, besides Fe sites, S sites are also possible oxidation sites in the initial oxidation state of pyrite, where easier and stronger oxidation may occur. This is the first time to confirm the other researchers' conjecture on the direct oxidation of S sites, which explains the isotopic composition experiments that a minor amount of O2 is permanently incorporated into SO42- during pyrite oxidation (O in SO42- is mainly derived from water). We constructed various H2O-O2 coadsorption models on the pyrite surface by considering the adsorption sequence of H2O and O2. It is found that the H2O molecule undergoes step-wise dissociation in the presence of the O2 molecule. Hydroxyl radical •OH is the reactive oxygen species during H2O dissociation. Cyclic voltammetric measurements confirm the presence of •OH. In addition, H2O2 may also be formed on the surface in terms of H2O-then-O2 sequence adsorption. [ABSTRACT FROM AUTHOR]

A broken symmetry density functional theory (BS-DFT) magnetic analysis of the S2, S2YZ•, and S3 states of Nature's oxygen evolving complex is performed for both the native Ca and Sr substituted forms. Good agreement with experiment is observed between the tyrosyl calculated g-tensor and ¹H hyperfine couplings for the native Ca form. Changes in the hydrogen bonding environment of the tyrosyl radical in S2YZ• caused by Sr substitution lead to notable changes in the calculated g-tensor of the tyrosyl radical. Comparison of calculated and experimental 55Mn hyperfine couplings for the S3 state presently favors an open cubane form of the complex with an additional OH ligand coordinating to MnD. In Ca models, this additional ligation can arise by closed-cubane form deprotonation of the Ca ligand W3 in the S2YZ• state accompanied by spontaneous movement to the vacant Mn coordination site or by addition of an external OH group. For the Sr form, no spontaneous movement of W3 to the vacant Mn coordination site is observed in contrast to the native Ca form, a difference which may lead to the reduced catalytic activity of the Sr substituted form. BS-DFT studies on peroxo models of S3 as indicated by a recent X-ray free electron laser (XFEL) crystallography study give rise to a structural model compatible with experimental data and an S = 3 ground state compatible with EPR studies. [ABSTRACT FROM AUTHOR]

Reactions of samarium cations with carbonyl sulfide are examined using a guided ion beam tandem mass spectrometer and a variable temperature selected ion flow tube apparatus. Formation of SmS+ + CO is observed in both instruments with a kinetic energy and temperature dependence demonstrating a barrierless reaction occurring with an efficiency of 26 ± 9%. Formation of SmO+ + CS is also observed at high kinetic energies and exhibits a threshold determined as 2.81 ± 0.32 eV, substantially higher than expected from known thermochemistry. The potential energy surfaces for these reactions along sextet and octet spin surfaces are also examined theoretically at the MP2 and CCSD(T) levels. The observed barrier for oxidation is shown to likely correspond to the energy of the crossing between surfaces corresponding to the ground state electronic configuration of Sm+ (8F,4f66s¹) and an excited surface having two electrons in the valence space (excluding 4f), which are needed to form the strong SmO+ bond. In contrast, the S-CO bond is activated much more readily because this crossing occurs at much lower energies. This result is attributed to the much weaker S-CO bond energy as well as the ability of sulfur to bind effectively at different angles. Although both reactions are spin-forbidden, evidence for a more efficient spin-allowed process is also observed in the SmS+ + CO cross section. [ABSTRACT FROM AUTHOR]

A convenient method for the preparation of unsymmetrical trisulfides using 9-fluorenylmethyl (Fm) disulfide as the precursors is reported. This method gives the desired trisulfides in good yields under mild conditions. [ABSTRACT FROM AUTHOR]

The C -- H addition of sulfides to alkenes is an atom-efficient route for the functionalization and modification of sulfide compounds through C -- C bond formation, but this transformation is highly challenging. We report here the regioselective a-C(sp3) -- H addition of a wide range of methyl sulfides to a variety of olefins and dienes by a half-sandwich scandium catalyst. This protocol provides a unique route for the synthesis of diverse sulfide derivatives through C -- C bond formation at a sulfur-adjacent carbon atom in a 100% atom efficient fashion. [ABSTRACT FROM AUTHOR]

This Letter describes the development of a catalytic decarbonylative C-S coupling reaction that transforms thioesters into thioethers. Both Pd- and Ni-based catalysts are developed and applied to the construction of diaryl, aryl alkyl, and heterocycle-containing thioethers. [ABSTRACT FROM AUTHOR]

Bovine pulmonary artery endothelial cells (BPAEC) respond in a dose-dependent manner to millimolar (0-10) levels of sodium sulfide (NaHS). No measurable increase in caspase-3 activity and no change in the extent of autophagy (or mitophagy) were observed in BPAEC. However, lactate dehydrogenase levels increased in the BPAEC exposed NaHS, which indicated necrotic cell death. In the case of galactose-conditioned BPAEC, the toxicity of NaHS was increased by 30% compared to that observed in BPAEC maintained in the regular glucose-containing culture medium, which indicated a link between mitochondrial oxidative phosphorylation and the mechanism of toxicant action. This is consistent with the widely held view that cytochrome c oxidase (complex IV of the mitochondrial electron-transport system) is the principal molecular target involved in the acute toxicity of "sulfide" (H2S/HS-). In support of this view, elevated NO (which can reverse cytochrome c oxidase inhibition) ameliorated the toxicity of NaHS and, conversely, suppression of endogenous NO production exacerbated the observed toxicity. Respirometric measurements showed the BPAEC to possess a robust sulfide oxidizing system, which was able to out-compete cytochrome c oxidase for available H2S/HS- at micromolar concentrations. This detoxification system has previously been reported by other groups in several cell types, but notably, not neurons. The findings appear to provide some insight into the question of why human survivors of H2S inhalation frequently present at the clinic with respiratory insufficiency/pulmonary edema, while acutely poisoned laboratory animals tend to either succumb to cardiopulmonary paralysis or fully recover without any intervention. [ABSTRACT FROM AUTHOR]

In the present work, we use β-casein as a model protein to prepare a smart β-casein stabilized Pt nanoparticle (CM-PtNP) with peroxidase mimicking activity and systematically investigate sulfide-mediated switching effect and mechanism of CM-PtNP nanozyme's activity. Sulfide-mediated activity switching effect depends heavily on the physicochemical properties of nanozymes and the identity of substrate. On one hand, the binding of sulfide to a Pt nanozyme surface leads to the transform from Pt2+ to Pt0, resulting in more active sites and the activity "switching on"; on the other hand, the binding of sulfide ions via Pt-S interaction blocks the active sites, resulting in the activity "switching off". For substrates 3,3',5,5'-tetramethylbenzidine and 2,2'-azinobis(3-ethylbenzthiazoline-6-sulfonic acid) diammonium salt, the two factors play different decisive roles since the interaction of substrate molecules with nanozyme allows their different distributions on nanozyme surfaces. By virtue of this specific response, excellent sulfide colorimetric sensors with different limits of detection were developed based on CM-PtNP with different substrates. This is the first report about a fundamental understanding of how substrates influence the anion-mediated activity switching effect by illuminating the nature of anion-nanozyme interaction and nanozyme-substrate interaction. This may be useful to rationally predict the environment factors on the activities of the nanozyme and to design an effective signal amplification based on target-induced nanozyme deactivation/activation. [ABSTRACT FROM AUTHOR]