Protonation,alkylation, addition and redox reactions of 16, 17 and 18 valence electron [Mo(L)(NO)('S4')] complexes [L = SPh,PMe3, NO; 'S4'2– = 1,2-Bis-(2-mercaptophenylthio)ethane(2-)]

In the quest for complexes modelling functional characteristics of metal sulfur oxidoreductases, a series of molybdenum nitrosyl complexes with sulfur-dominated coordination sphere was synthesized. Treatment of the 16, 17 and 18 valence electron (VE) complexes [Mo(L)(NO)('S₄')] (1–3) [L?=?SPh (1), PMe₃ (2), NO (3), 'S₄'^2–?=?1,2-bis-(2-mercaptophenylthio) ethane(2-)] with the Brönsted acid HBF₄ resulted in formation of different types of products. 1 and 3 were reversibly protonated at one thiolate atom of the 'S₄'^2– ligand;2, however, yielded the phosphonium salt [HPMe₃]BF₄ and the dinuclear [Mo(NO)('S₄')]₂. Alkylation of 1, 2 and 3 by Me₃OBF₄ or Et₃OBF₄ uniformly resulted in high yields of [Mo(L)(NO)(R-'S₄')]BF₄ complexes [L?=?SPh: R?=?Me (5), Et (6); L?=?PMe₃: R?=?Me (7); L?=?NO: R?=?Me (8), Et (9)] in which one thiolate atom of the 'S₄'^2– ligand had become alkylated; the NMR spectra of 5, 6, 8 and 9 indicated that only one out of four theoretically possible diastereoisomers had formed. 5 and 6 were characterized also by single-crystal X-ray structure analyses. A comparison of ν(NO) bands and redox potentials (cyclic voltammetry) of parent complexes and alkylated derivatives showed that alkylation leads to a decrease in electron density at the molybdenum center and to a positive shift in redox potentials. The 16 VE complex 1 could be reduced, also chemically, to give the corresponding 17 VE anion [1]^–, and inserted elemental sulfur into the Mo-SPh bond, forming the 18 VE phenylperthio complex [Mo(η²–SSPh)(NO)('S₄')] (11) which, upon reaction with PPh₃, gave SPPh₃ and regenerated the parent complex 1. These results are discussed with regard to the sequence of proton and electron transfer steps occurring in substrate conversions catalyzed by metal sulfur oxidoreductases.     

Selenium uptake,translocation, assimilation and metabolic fate in plants

The chemical and physical resemblance between selenium (Se) and sulfur (S) establishes that both these elements share common metabolic pathways in plants. The presence of isologous Se and S compounds indicates that these elements compete in biochemical processes that affect uptake, translocation and assimilation throughout plant development. Yet, minor but crucial differences in reactivity and other metabolic interactions infer that some biochemical processes involving Se may be excluded from those relating to S. This review examines the current understanding of physiological and biochemical relationships between S and Se metabolism by highlighting their similarities and differences in relation to uptake, transport and assimilation pathways as observed in Se hyperaccumulator and non-accumulator plant species. The exploitation of genetic resources used in bioengineering strategies of plants is illuminating the function of sulfate transporters and key enzymes of the S assimilatory pathway in relation to Se accumulation and final metabolic fate. These strategies are providing the basic framework by which to resolve questions relating to the essentiality of Se in plants and the mechanisms utilized by Se hyperaccumulators to circumvent toxicity. In addition, such approaches may assist in the future application of genetically engineered Se accumulating plants for environmental renewal and human health objectives.     

Exploring Coal Biodesulfurization Potential of a Novel Organic Sulfur Metabolizing Rhodococcus spp. (Eu-32) – A Case Study

Coal is one of the most abundant nonrenewable fossil fuels, in Pakistan. However, in general, the quality of coal is too low to offset the practical, economic, and regulatory barriers to its utilization. High sulfur content comes up as one of the bottlenecks in productive usage of indigenous coal. Biotechnology can emerge as a panacea for upgrading the huge reserves of high sulfur coal. In current study, the sulfur removal potential of Rhodococcus spp. (Eu-32) was investigated using coal from Dukki, Baluchistan, Pakistan. Biodesulfurization process was optimized for various parameters and maximum decrease of 40% and 60% in total and organic sulfur contents, respectively were achieved in 15 days. The Langmuir and Brunauer–Emmett–Teller (BET) surface areas of the biotreated coal were increased by 20 and 16 times, respectively. Scanning electron microscope showed higher tendency of attachment of bacterial cells to the coal particles. Our results revealed that Eu-32 could remove significant amounts of organic sulfur from coal and could be used in the pre-combustion operations with appropriate arrangements.     

Polymorphic Variants of Human Rhodanese Exhibit Differences in Thermal Stability and Sulfur Transfer Kinetics

Rhodanese is a component of the mitochondrial H₂S oxidation pathway. Rhodanese catalyzes the transfer of sulfane sulfur from glutathione persulfide (GSSH) to sulfite generating thiosulfate and from thiosulfate to cyanide generating thiocyanate. Two polymorphic variations have been identified in the rhodanese coding sequence in the French Caucasian population. The first, 306A→C, has an allelic frequency of 1% and results in an E102D substitution in the encoded protein. The second polymorphism, 853C→G, has an allelic frequency of 5% and leads to a P285A substitution. In this study, we have examined differences in the stability between wild-type rhodanese and the E102D and P285A variants and in the kinetics of the sulfur transfer reactions. The Asp-102 and Ala-285 variants are more stable than wild-type rhodanese and exhibit k_cat/K_m,CN values that are 17- and 1.6-fold higher, respectively. All three rhodanese forms preferentially catalyze sulfur transfer from GSSH to sulfite, generating thiosulfate and glutathione. The k_cat/K_m,sulfite values for the variants in the sulfur transfer reaction from GSSH to sulfite were 1.6- (Asp-102) and 4-fold (Ala-285) lower than for wild-type rhodanese, whereas the k_cat/K_m,GSSH values were similar for all three enzymes. Thiosulfate-dependent H₂S production in murine liver lysate is low, consistent with a role for rhodanese in sulfide oxidation. Our studies show that polymorphic variations that are distant from the active site differentially modulate the sulfurtransferase activity of human rhodanese to cyanide versus sulfite and might be important in differences in susceptibility to diseases where rhodanese dysfunction has been implicated, e.g. inflammatory bowel diseases.     

Structures of Arg‐ and Gln‐type bacterial cysteine dioxygenase homologs

In some bacteria, cysteine is converted to cysteine sulfinic acid by cysteine dioxygenases (CDO) that are only ～15–30% identical in sequence to mammalian CDOs. Among bacterial proteins having this range of sequence similarity to mammalian CDO are some that conserve an active site Arg residue (“Arg‐type” enzymes) and some having a Gln substituted for this Arg (“Gln‐type” enzymes). Here, we describe a structure from each of these enzyme types by analyzing structures originally solved by structural genomics groups but not published: a Bacillus subtilis “Arg‐type” enzyme that has cysteine dioxygenase activity (BsCDO), and a Ralstonia eutropha “Gln‐type” CDO homolog of uncharacterized activity (ReCDOhom). The BsCDO active site is well conserved with mammalian CDO, and a cysteine complex captured in the active site confirms that the cysteine binding mode is also similar. The ReCDOhom structure reveals a new active site Arg residue that is hydrogen bonding to an iron‐bound diatomic molecule we have interpreted as dioxygen. Notably, the Arg position is not compatible with the mode of Cys binding seen in both rat CDO and BsCDO. As sequence alignments show that this newly discovered active site Arg is well conserved among “Gln‐type” CDO enzymes, we conclude that the “Gln‐type” CDO homologs are not authentic CDOs but will have substrate specificity more similar to 3‐mercaptopropionate dioxygenases.     

施硫对‘豫麦50’籽粒灌浆特性及产量的影响

选用弱筋小麦品种‘豫麦50’为材料,通过大田试验研究了较高供氮水平下(施纯氮330 kg/hm2)施用低量(S 20 kg/hm2)、中量(S 60 kg/hm2)和高量(S 100 kg/hm2)硫肥对小麦籽粒灌浆特性和产量的影响.结果显示,不同施硫处理的小麦籽粒灌浆进程均“呈慢—快—慢”的S型曲线,拟合的Logistic方程决定系数均大于0.993 2,并达到极显著水平;灌浆持续期(T)、渐增期平均灌浆速率(V1),快增期和缓增期持续期(T2、T3)、灌浆期各阶段干物质积累量(m1、m2、m3)和理论最大千粒重(K)均随施硫量增加而提高,并以中硫处理的各项灌浆参数表现较优;中硫处理的千粒重(46.47 g)和籽粒产量(7 416.0 kg/hm2)显著高于低硫处理,极显著高于对照(不施硫)和高硫处理.表明在当前较高施氮水平下,每公顷施纯硫60 kg可有效改善小麦灌浆特性,显著提高籽粒产量.     

Revisiting the Role of Conductivity and Polarity of Host Materials for Long‐Life Lithium–Sulfur Battery

Despite their high theoretical energy density and low cost, lithium–sulfur batteries (LSBs) suffer from poor cycle life and low energy efficiency owing to the polysulfides shuttle and the electronic insulating nature of sulfur. Conductivity and polarity are two critical parameters for the search of optimal sulfur host materials. However, their role in immobilizing polysulfides and enhancing redox kinetics for long‐life LSBs are not fully understood. This work has conducted an evaluation on the role of polarity over conductivity by using a polar but nonconductive platelet ordered mesoporous silica (pOMS) and its replica platelet ordered mesoporous carbon (pOMC), which is conductive but nonpolar. It is found that the polar pOMS/S cathode with a sulfur mass fraction of 80 wt% demonstrates outstanding long‐term cycle stability for 2000 cycles even at a high current density of 2C. Furthermore, the pOMS/S cathode with a high sulfur loading of 6.5 mg cm^?2 illustrates high areal and volumetric capacities with high capacity retention. Complementary physical and electrochemical probes clearly show that surface polarity and structure are more dominant factors for sulfur utilization efficiency and long‐life, while the conductivity can be compensated by the conductive agent involved as a required electrode material during electrode preparation. The present findings shed new light on the design principles of sulfur hosts towards long‐life and highly efficient LSBs.     

New Lithium Salt Forms Interphases Suppressing Both Li Dendrite and Polysulfide Shuttling

Lithium–sulfur batteries (LSBs) are considered promising candidates for the next‐generation energy‐storage systems due to their high theoretical capacity and prevalent abundance of sulfur. Their reversible operation, however, encounters challenges from both the anode, where dendritic and dead Li‐metal form, and the cathode, where polysulfides dissolve and become parasitic shuttles. Both issues arise from the imperfection of interphases between electrolyte and electrode. Herein, a new lithium salt based on an imide anion with fluorination and unsaturation in its structure is reported, whose interphasial chemistries resolve these issues simultaneously. Lithium 1, 1, 2, 2, 3, 3‐hexafluoropropane‐1, 3‐disulfonimide (LiHFDF) forms highly fluorinated interphases at both anode and cathode surfaces, which effectively suppress formation of Li‐dendrites and dissolution/shuttling of polysulfides, and significantly improves the electrochemical reversibility of LSBs. In a broader context, this new Li salt offers a new perspective for diversified beyond Li‐ion chemistries that rely on a Li‐metal anode and active cathode materials.     

34S/32S and 18O/16O Fractionation During Sulfur Disproportionation by Desulfobulbus propionicus

In the present study, coupled stable sulfur and oxygen isotope fractionation during elemental sulfur disproportionation according to the overall reaction: 4H₂O + 4S^? → 3H₂S + SO₄ ^{2 ?} + 2H⁺, was experimentally investigated for the first time using a pure culture of the sulfate reducer Desulfobulbus propionicus at 35^?C. Bacterial disproportionation of elemental sulfur is an important process in the sulfur cycle of natural surface sediments and leads to the simultaneous formation of sulfide and sulfate. A dual-isotope approach considering both sulfur and oxygen isotope discrimination has been shown to be most effective in evaluating specific microbial reactions. The influence of iron- and manganese bearing-solids (Fe(II)CO₃, Fe(III)OOH, Mn(IV)O₂) acting in natural sediments as scavengers for hydrogen sulfide, was considered, too. Disproportionation of elemental sulfur was observed in the presence of iron solids at a cell-specific sulfur disproportionation rate of about 10^{? 9.5± 0.4} μ mol S^? cell^{? 1} h^{? 1}. No disproportionation, however, was observed with MnO₂. In the presence of iron solids, newly formed sulfate was enriched in ¹⁸ O compared to water by about +21‰ (≡ ? _H2O ), in agreement with a suggested oxygen isotope exchange via traces of intra- or extracellular sulfite that is formed as a disproportionation intermediate. Dissolved sulfate was also enriched in ³⁴S compared to elemental sulfur by up to +35%. Isotope fractionation by Desulfobulbus propionicusis highest for all disproportionating bacteria investigated, so far, and may impact on the development of isotope signals at the redox boundary of surface sediments.     

微生物硫代谢及其驱动下建立的生物生态关系

硫在环境中广泛存在,是生物细胞的主要构成元素,微生物、动物和植物的硫基础代谢途径之间存在着广泛联系.本文以微生物硫代谢为主线,全面总结了硫在3类生物中的4条主要代谢途径,并重点阐明了其共性、区别及联系.微生物参与了所有硫的主要代谢,是驱动硫生物循环的主要动力.微生物异化硫还原降低了环境中甲烷的挥发,微生物、植物实施的同...