Sulfur speciation and bioaccumulation in camphor tree leaves as atmospheric sulfur indicator analyzed by synchrotron radiation XRF and XANES

Analyzing and understanding the effects of ambient pollution on plants is getting more and more attention as a topic of environmental biology.A method based on synchrotron radiation X-ray fluorescence and X-ray absorption near edge structure spectroscopy was established to analyze the sulfur concentration and speciation in mature camphor tree leaves （CTLs）,which were sampled from 5 local fields in Shanghai,China.Annual SO2 concentration,SO42-concentration in atmospheric particulate,SO42-and sulfur concentration in soil were also analyzed to explore the relationship between ambient sulfur sources and the sulfur nutrient cycling in CTLs.Total sulfur concentration in mature camphor tree leaves was 766-1704 mg/kg.The mainly detected sulfur states and their corresponding compounds were ＋6 （sulfate,include inorganic sulfate and organic sulfate）,＋5.2 （sulfonate）,＋2.2 （suloxides）,＋0.6 （thiols and thiothers）,＋0.2 （organic sulfides）.Total sulfur concentration was strongly correlated with sulfate proportion with a linear correlation coefficient up to 0.977,which suggested that sulfur accumulated in CTLs as sulfate form.Reduced sulfur compounds （organic sulfides,thiols,thioethers,sulfoxide and sulfonate） assimilation was sufficed to meet the nutrient requirement for growth at a balanced level around 526 mg/kg.The sulfate accumulation mainly caused by atmospheric sulfur pollution such as SO2 and airborne sulfate particulate instead of soil contamination.From urban to suburb place,sulfate in mature CTLs decreased as the atmospheric sulfur pollution reduced,but a dramatic increase presented near the seashore,where the marine sulfate emission and maritime activity pollution were significant.The sulfur concentration and speciation in mature CTLs effectively represented the long-term biological accumulation of atmospheric sulfur pollution in local environment.

Sulfur speciation defined subcellular localization of coumarin derivatives:Correlation of structural relationship to biological behaviors

Targeted-delivery is of great importance to molecular probes and drugs for cell biology study. Herein we reported 11 sulfur-containing coumarins as cell imaging probes. Different sulfur speciation of the 4 representative coumarins SC1-SC4 renders them significantly different subcellular localizations and cellular uptake pathways： SC1 containing thioether group located in lysosomes, while sulfoxide and sulfone compounds SC2 and SC3 distributed in the whole cell. Furthermore, the cationic sulfonium containing compound SC4 was internalized by clathrin-mediated endocytosis and localized at mitochondria. By analyzing the molecular parameters of all 11 coumarins, we found that different sulfur speciation affected their lipophilicity and electrostatic surface potential. These two key factors play roles in altering biological behaviors of the coumarins. The results revealed the importance of sulfur speciation on the physicochemical properties and thus subcellular localization of bioprobes. This is useful for designing new functional bioprobes.

Lithium polysulfide solvation and speciation in the aprotic lithium-sulfur batteries

Fingerprinting sulfur speciation in aprotic electrolytes is a key to understand fundamental chemistry and design well-performing lithium–sulfur(Li–S)batteries.Lithium polysulfide(LiPS)dissolution and deposition in ether-based electrolytes during redox reactions have been probed and established by spectroscopy and microscopy.However,detailed LiPS structure and solvation properties influenced by conventional and newly developed electrolytes remain elusive,which exert fundamental challenges and practical difficulties in decoupling battery performance from electrolyte volume.This perspective aims to provide timely information to uncover underlying mechanisms that rein in sulfur speciation by considering the charge density of LiPSs and the coordination strength of solvents/salts.The discussion starts with unlocking the baseline electrolyte formulation to investigate its role in LiPS formation and compatibility.After that,the term coordination strength is used instead of donor number and dielectric constant to describe interactions between solvents and LiPSs and to reveal LiPS structure evolution.This work is expected to encourage the discovery of new electrolyte working mechanisms to develop energy-dense and power-intensive Li–S batteries.

Differential utilization and speciation transformation of orthorhombic α-S_8 and amorphous μ-S by substrate-acclimated mesophilic Acidithiobacillus ferrooxidans

The utilization and speciation transformation of α-S8 and μ-S by the typical mesophilic acidophilic strain Acidithiobacillus ferrooxidans ATCC 23270 were investigated.A.ferrooxidans cells first acclimated to the energy source α-S8 or μ-S,respectively.The results of cell growth and sulfur oxidation behavior showed that the strain grown on α-S8 entered slowly（about 1 d later） into the exponential phase,while grew faster in the exponential phase and attained higher maximal cell density and lower p H value than that on μ-S.After bio-corrosion,both of the two sulfur samples were evidently eroded and modified by A.ferrooxidans cells.After growth of A.ferrooxidans,the surface composition of amorphous μ-S became 63.1% μ-S and 36.9% α-S8,and that of orthorhombic α-S8 became 68.3% α-S8 and 31.7% μ-S,while the surface compositions of α-S8 and μ-S in sterile experiment were not changed,indicating that these two elemental sulfur species can be interconverted by A.ferrooxidans.

The Oxidation State of Sulfur Detected in Na_2O-CaO-SiO_2 Float Glass by X-ray Absorption Near Edge Structure Spectra

The oxidation state of sulfur is detected in Na20-CaO-SiO2 float glass by synchrotron radiation X-ray absorption near edge structure （XANES） spectra at the sulfur K edge. The measured spectra show the only presence of S^6＋ in the Na20-CaO-SiO2 float glass and the oxidation state of sulfur do not change with the increase of glass depth. It is also found that, after the melt has gone through the molten tin bath, the S^6＋ is the dominant species, but S^2- is also present on both surfaces. It is not certain whether cation bonds to S^2- or not, because there are many cations dissolved in the melted tin which makes the spectrum complicated.

Unraveling Shuttle Effect and Suppression Strategy in Lithium/Sulfur Cells by In Situ/Operando X-ray Absorption Spectroscopic Characterization

The polysulfides shuttle effect represents a great challenge in achieving high capacity and long lifespan of lithium/sulfur(Li/S)cells.A comprehensive understanding of the shuttle-related sulfur speciation and diffusion process is vital for addressing this issue.Herein,we employed in situ/operando X-ray absorption spectroscopy(XAS)to trace the migration of polysulfides across the Li/S cells by precisely monitoring the sulfur chemical speciation at the cathodic electrolyte-separator and electrolyte-anode interfaces,respectively,in a real-time condition.After we adopted a shuttle-suppressing strategy by introducing an electrocatalytic layer of twinborn bismuth sulfide/bismuth oxide nanoclusters in a carbon matrix(BSOC),we found the Li/S cell showed greatly improved sulfur utilization and longer life span.The operando S Kedge XAS results revealed that the BSOC modification was bi-functional:trapping polysulfides and catalyzing conversion of sulfur species simultaneously.We elucidated that the polysulfide trapping-and-catalyzing effect of the BSOC electrocatalytic layer resulted in an effective lithium anode protection.Our results could offer potential stratagem for designing more advanced Li/S cells.