Sulfur K-edge X-ray Absorption Spectroscopy Research Articles

In Solution Identification of the Lysine-Cysteine Redox Switch with a NOS Bridge in Transaldolase by Sulfur K-Edge X-ray Absorption Spectroscopy.

A novel covalent post-translational modification (lysine-NOS-cysteine) was discovered in proteins, initially in the enzyme transaldolase of Neisseria gonorrhoeae (NgTAL) [Nature 2021, 593, 460-464], acting as a redox switch. The identification of this novel linkage in solution was unprecedented until now. We present detection of the NOS redox switch in solution using sulfur K-edge X-ray absorption spectroscopy (XAS). The oxidized NgTAL spectrum shows a distinct shoulder on the low-energy side of the rising edge, corresponding to a dipole-allowed transition from the sulfur 1s core to the unoccupied σ* orbital of the S-O group in the NOS bridge. This feature is absent in the XAS spectrum of reduced NgTAL, where Lys-NOS-Cys is absent. Our experimental and calculated XAS data support the presence of a NOS bridge in solution, thus potentially facilitating future studies on enzyme activity regulation mediated by the NOS redox switches, drug discovery, biocatalytic applications, and protein design.

Probing Substituent Effect on Nickel-Sulfur Bond Covalency in Ni(II)-Dithiophosphinate Complexes by Sulfur K-Edge XAS and DFT Calculations.

Complexes of Ni(II) with a series of aryl or alkyl substituent dithiophosphinic acids were characterized by crystallographic structure, sulfur K-edge X-ray absorption spectroscopy (XAS), and density functional theory (DFT). In these complexes, Ni(II) coordinates with four sulfur atoms from two dithiophosphinate anions form a well-defined square-planar structure. Despite the minor differences in the geometry parameters among the complexes, the electronic structure is affected significantly by the substituent group attached to dithiophosphinic acid. In particular, the addition of ortho-CF3 group to the aryl ring constrains the orientation of the aryl ring and enhances the conjugation between the aryl ring and the coordinating core. Sulfur K-edge XAS spectra help further reveal the electronic structure of the complexes. Both the pre-edge feature and rising-edge feature provide abundant information on the molecular orbitals and show a distinctive effect of the substituent groups on the electronic structure of the complexes, which is supposedly relevant to the ligand's performance in Ln(III)/An(III) separation.

Simulated sulfur K-edge X-ray absorption spectroscopy database of lithium thiophosphate solid electrolytes

X-ray absorption spectroscopy (XAS) is a premier technique for materials characterization, providing key information about the local chemical environment of the absorber atom. In this work, we develop a database of sulfur K-edge XAS spectra of crystalline and amorphous lithium thiophosphate materials based on the atomic structures reported in Chem. Mater., 34, 6702 (2022). The XAS database is based on simulations using the excited electron and core-hole pseudopotential approach implemented in the Vienna Ab initio Simulation Package. Our database contains 2681 S K-edge XAS spectra for 66 crystalline and glassy structure models, making it the largest collection of first-principles computational XAS spectra for glass/ceramic lithium thiophosphates to date. This database can be used to correlate S spectral features with distinct S species based on their local coordination and short-range ordering in sulfide-based solid electrolytes. The data is openly distributed via the Materials Cloud, allowing researchers to access it for free and use it for further analysis, such as spectral fingerprinting, matching with experiments, and developing machine learning models.

Tetrathiafulvalene-2,3,6,7-tetrathiolate linker redox-state elucidation via S K-edge X-ray absorption spectroscopy.

Sulfur K-edge XAS data provide a unique tool to examine oxidation states and covalency in electronically complex S-based ligands. We present sulfur K-edge X-ray absorption spectroscopy on a discrete redox-series of Ni-based tetrathiafulvalene tetrathiolate (TTFtt) complexes as well as on a 1D coordination polymer (CP), NiTTFtt. Experiment and theory suggest that Ni-S covalency decreases with oxidation which has implications for charge transport pathways.

Covalency between the uranyl ion and dithiophosphinate by sulfur K-edge X-ray absorption spectroscopy and density functional theory.

The dithiophosphinic acids (HS2PR2) have been used for the selective separation of trivalent actinides (AnIII) from lanthanides (LnIII) over the past decades. The substituents on the dithiophosphinic acids dramatically impact the separation performance, but the mechanism is still open for debate. In this work, two dithiophosphinic acids with significantly different AnIII/LnIII separation performance, i.e. diphenyl dithiophosphinic acid (HS2PPh2) and bis(ortho-trifluoromethylphenyl) dithiophosphinic acid [HS2P(o-CF3C6H4)2], are employed to understand the substituent effect on the bonding covalency between the S2PR2- anions (R = Ph and o-CF3C6H4) and the uranyl ion by sulfur K-edge X-ray absorption spectroscopy (XAS) in combination with density functional theory calculations. The two UO2(S2PR2)(EtOH) complexes display similar XAS spectra, in which the first pre-edge feature with an intensity of 0.16 is entirely attributed to the transitions from S 1s orbitals to the unoccupied molecular orbitals due to the mixing between U 5f and S 3p orbitals. The Mulliken population analysis indicates that the amount of \% S 3p character inthese orbitals is essentially identical for the UO2(S2PPh2)2(EtOH) and UO2[S2P(o-CF3C6H4)2]2(EtOH) complexes, which is lower than that in the U 6d-based orbitals. The essentially identical covalency in U-S bonds for the two UO2(S2PR2)2(EtOH) complexes are contradictory to the significantly different AnIII/LnIII separation performance of the two dithiophosphinic acids, thus the covalency seems to be unable to account for substituent effects in the AnIII/LnIII separation by the dithiophosphinic acids. The results in this work provide valuable insight into the understanding of the mechanism in the AnIII/LnIII separation by the dithiophosphinic acids.

Electronic structure of (MePh3P)2[NiII(bdtCl2)2]·2(CH3)2SO and (MePh3P)[NiIII(bdtCl2)2] (bdtCl2 = 3,6-dichlorobenzene-1,2-dithiolate)

High-resolution X-ray diffraction experiments, theoretical calculations and atom-specific X-ray absorption experiments were used to investigate two nickel complexes, (MePh3P)2[NiII(bdtCl2)2]·2(CH3)2SO [complex (1)] and (MePh3P)[NiIII(bdtCl2)2] [complex (2)]. Combining the techniques of nickel K- and sulfur K-edge X-ray absorption spectroscopy with high-resolution X-ray charge density modeling, together with theoretical calculations, the actual oxidation states of the central Ni atoms in these two complexes are investigated. Ni ions in two complexes are clearly in different oxidation states: the Ni ion of complex (1) is formally NiII; that of complex (2) should be formally NiIII, yet it is best described as a combination of Ni2+ and Ni3+, due to the involvement of the non-innocent ligand in the Ni—L bond. A detailed description of Ni—S bond character (σ,π) is presented.

All-Solid-State Lithium–Sulfur Batteries Enhanced by Redox Mediators

Redox mediators (RMs) play a vital role in some liquid electrolyte-based electrochemical energy storage systems. However, the concept of redox mediator in solid-state batteries remains unexplored. Here, we selected a group of RM candidates and investigated their behaviors and roles in all-solid-state lithium-sulfur batteries (ASSLSBs). The soluble-type quinone-based RM (AQT) shows the most favorable redox potential and the best redox reversibility that functions well for lithium sulfide (Li2S) oxidation in solid polymer electrolytes. Accordingly, Li2S cathodes with AQT RMs present a significantly reduced energy barrier (average oxidation potential of 2.4 V) during initial charging at 0.1 C at 60 °C and the following discharge capacity of 1133 mAh gs-1. Using operando sulfur K-edge X-ray absorption spectroscopy, we directly tracked the sulfur speciation in ASSLSBs and proved that the solid-polysulfide-solid reaction of Li2S cathodes with RMs facilitated Li2S oxidation. In contrast, for bare Li2S cathodes, the solid-solid Li2S-sulfur direct conversion in the first charge cycle results in a high energy barrier for activation (charge to ∼4 V) and low sulfur utilization. The Li2S@AQT cell demonstrates superior cycling stability (average Coulombic efficiency 98.9% for 150 cycles) and rate capability owing to the effective AQT-enhanced Li-S reaction kinetics. This work reveals the evolution of sulfur species in ASSLSBs and realizes the fast Li-S reaction kinetics by designing an effective sulfur speciation pathway.

Ground electronic state description of thiourea coordination in homoleptic Zn2+, Ni2+ and Co2+ complexes using sulfur K-edge X-ray absorption spectroscopy.

Sulfur K-edge X-ray absorption spectroscopy (XAS) was employed to experimentally characterize the coordinative bond between the thiourea (TU) or thiocarbamide ligand and transition metal (TM) ions Zn2+, Co2+ and Ni2+ in distorted tetrahedral and octahedral homoleptic coordination environments. Comparisons of XAS spectra of the free TU ligand and [Zn(TU)4]2+, [Co(TU)4]2+ and [Ni(TU)6]2+ complexes clearly identify spectral features unique to TM2+-S(TU) bonding. Quantitative analysis of pre-edge intensities describes the covalency of Ni2+-S(TU) and Co2+-S(TU) bonding to be at most 21% and 9% as expressed by the S 3p contributions per TM 3d electron hole. Using relevant Ni2+ complexes with dithiocarbamate and thioether ligands, we evaluated the empirical S 1s → 3p transition dipole integrals developed for S-donor ligands and their dependence on heteroatom substitutions. With the aid of density functional theory-based ground electronic state calculations, we found evidence for the need of using a transition dipole that is dependent on the presence of conjugated heteroatom (N) substitution in these S-donor ligands.

Organic sulfur fluxes and geomorphic control of sulfur isotope ratios in rivers

Pyrite oxidation plays a critical role in the relationship between weathering and climate, and its impact on the global carbon cycle has previously been constrained through inversion models utilizing observations of river sulfate (SO42−) and its 34S/32S isotope ratio (δ34SSO4). However, measurements from some rivers have suggested that δ34SSO4 can be substantially impacted by processes such as microbial sulfate reduction and/or sulfur assimilation and cycling, rather than simply reflecting a weighted mixture of lithologic sulfur sources. To study the prevalence and controls on SO42− transformations, we measured dissolved major element concentrations and δ34SSO4 in river water samples from throughout western Iceland. Our analyses focused on samples from a small catchment hosting the Efri Haukadalsá river, a system with relatively uniform and isotopically constrained basaltic bedrock. We also measured sediment δ34S and sulfur speciation using sulfur K-edge X-ray absorption spectroscopy on sediment and vegetation samples from this catchment. Values of dissolved δ34SSO4 in the Efri Haukadalsá ranged from 2.5‰ to 23.7‰ and had a linear relationship with Cl−/SO42− ratios, indicating that SO42− predominantly derived from basalt weathering and meteoric precipitation. The lower δ34SSO4 values were found in fluvial valleys with V-shaped cross sections, while higher values of δ34SSO4 occurred in U-shaped, glacially eroded valleys with thick alluvial fills blanketing the valley floor. Spectroscopic observations identified organic sulfur phases in suspended river sediment, floodplain deposits, and vegetation. Mass balance calculations quantified the organic sulfur flux as less than 10% of SO42− export, and sediment δ34S values were comparable to river δ34SSO4. We interpreted these isotopic and chemical patterns as reflecting differences in the availability of unweathered bedrock across the Efri Haukadalsá catchment, with V-shaped valleys having greater access to fresh sulfide-bearing minerals than alluviated U-shaped valleys; this interpretation is in contrast to one in which the elevated δ34SSO4 values reflect fractionation during sulfur transformations along alluvial reaches. These results validated the application of river inversion models for constraining weathering fluxes and affirmed that pyrite oxidation globally, even in the presence of river sulfur cycling, modulates the abundance of atmospheric carbon dioxide.

Nature of S-N Bonding in Sulfonamides and Related Compounds: Insights into π-Bonding Contributions from Sulfur K-Edge X-ray Absorption Spectroscopy.

Molecules containing sulfur-nitrogen bonds, like sulfonamides, have long been of interest because of their many uses and interesting chemical properties. Understanding the factors that cause sulfonamide reactivity is important, yet there continues to be controversy regarding the relevance of S-N π bonding in describing these species. In this paper, we use sulfur K-edge X-ray absorption spectroscopy (XAS) in conjunction with density functional theory (DFT) to investigate the role of S3p contributions to π-bonding in sulfonamides, sulfinamides, and sulfenamides. We explore the nature of the electron distribution of the sulfur atom to its nearest neighbors and widen our scope to its effects on rotational barriers along the sulfur-nitrogen axis. The experimental XAS data together with time-dependent DFT calculations confirm that sulfonamides-and the other sulfinated amides in this series-have essentially no S-N π bonding involving S3p contributions and that electron repulsion is the dominant force affecting rotational barriers along the S-N axis.

Sulfur Kβ X-ray emission spectroscopy: comparison with sulfur K-edge X-ray absorption spectroscopy for speciation of organosulfur compounds.

Until recently, sulfur was known as a "spectroscopically silent" element because of a paucity of convenient spectroscopic probes suitable for in situ chemical speciation. In recent years the technique of sulfur K-edge X-ray absorption spectroscopy (XAS) has been used extensively in sulfur speciation in a variety of different fields. With an initial focus on reduced forms of organic sulfur, we have explored a complementary X-ray based spectroscopy - sulfur Kβ X-ray emission spectroscopy (XES) - as a potential analytical tool for sulfur speciation in complex samples. We compare and contrast the sensitivity of sulfur Kβ XES with that of sulfur K-edge XAS, and find differing sensitivities for the two techniques. In some cases an approach involving both sulfur K-edge XAS and sulfur Kβ XES may be a powerful combination for deducing sulfur speciation in samples containing complex mixtures.

Selenite Sorption on Hydrated CEM-V/A Cement in the Presence of Steel Corrosion Products: Redox vs Nonredox Sorption.

Reinforced cementitious structures in nuclear waste repositories will act as barriers that limit the mobility of radionuclides (RNs) in case of eventual leakage. CEM-V/A cement, a ternary blended cement with blast furnace slag (BFS) and fly ash (FA), could be qualified and used in nuclear waste disposal. Chemical interactions between the cement and RNs are critical but not completely understood. Here, we combined wet chemistry methods, synchrotron-based X-ray techniques, and thermodynamic modeling to explore redox interactions and nonredox sorption processes in simulated steel-reinforced CEM-V/A hydration systems using selenite as a molecular probe. Among all of the steel corrosion products analyzed, only the addition of Fe0 can obviously enhance the reducing ability of cement toward selenite. In comparison, steel corrosion products showed stronger reducing power in the absence of cement hydrates. Selenium K-edge X-ray absorption spectroscopy (XAS) revealed that selenite immobilization mechanisms included nonredox inner-/outer-sphere complexations and reductive precipitations of FeSe and/or Se(0). Importantly, the hydrated pristine cement showed a good reducing ability, driven by ferrous phases and (bi)sulfides (as shown by sulfur K-edge XAS) originated from BFS and FA. The overall redox potential imposed by hydrated CEM-V/A was determined, hinting to a redox shift in underground cementitious structures.

Biological sulfur in the blood cells of Ascidia ceratodes: XAS spectroscopy and a cellular-enzymatic hypothesis for vanadium reduction in the ascidians

Two samples of living blood cells and of cleared blood plasma from the Phlebobranch tunicate Ascidia ceratodes from Bodega Bay, California, and one of fresh Henze solution from A. ceratodes of Monterey Bay, California, have been examined using sulfur K-edge x-ray absorption spectroscopy (XAS). Biological sulfur included sulfate esters, sulfate and bisulfate ions, benzothiazole, thianthrene, epi-sulfide, thiol and disulfide. Glutathione dominated reduced sulfur, from which an average intracellular Voltage of −0.21 V was calculated. Sulfate-bisulfate ratios yielded blood cell pH values of 2.0 and 2.8. Total blood cell [sulfur] was 373±9 mM or 296±73 mM from BaSO4 gravimetry. Two plasma samples (pH 6.9 or 7.0; [S] = 33±6 mM or 26±4 mM) were dominated by sulfate and disulfide. Fresh Henze solution evidenced a sulfur inventory similar to blood cells, with calculated pH = 2.7. A V(III)-sulfonate fraction varied systematically with intracellular pH across six independent blood cell samples, implying a vanadium mobilization pathway. Bodega Bay and Monterey Bay A. ceratodes appear to maintain alternative suites of low-valent sulfur. The significance of the vanabins to vanadium metabolism is critically examined in terms of known protein – V(IV) biochemistry. Finally, a detailed hypothesis for the reduction of [VO4]3− to V(III) in ascidians is introduced. A vanadium oxido-reductase is proposed to span the signet ring membrane and to release V(III) into the inner acidic vacuole. The V(V) to V(III) reduction is predicted require an inner-sphere mechanism, a thiol reductant, 7-coordinate V(III), a biologically accessible Voltage, and proton-facilitated release of V(III).

The influences of carbon donor ligands on biomimetic multi-iron complexes for N2 reduction.

The active site clusters of nitrogenase enzymes possess the only examples of carbides in biology. These are the only biological FeS clusters that are capable of reducing N2 to NH4+, implicating the central carbon and its interaction with Fe as important in the mechanism of N2 reduction. This biological question motivates study of the influence of carbon donors on the electronic structure and reactivity of unsaturated, high-spin iron centers. Here, we present functional and structural models that test the impacts of carbon donors and sulfide donors in simpler iron compounds. We report the first example of a diiron complex that is bridged by an alkylidene and a sulfide, which serves as a high-fidelity structural and spectroscopic model of a two-iron portion of the active-site cluster (FeMoco) in the resting state of Mo-nitrogenase. The model complexes have antiferromagnetically coupled pairs of high-spin iron centers, and sulfur K-edge X-ray absorption spectroscopy shows comparable covalency of the sulfide for C and S bridged species. The sulfur-bridged compound does not interact with N2 even upon reduction, but upon removal of the sulfide it becomes capable of reducing N2 to NH4+ with the addition of protons and electrons. This provides synthetic support for sulfide extrusion in the activation of nitrogenase cofactors.

Visualizing sulfur with X-rays: From molecules to tissues

Sulfur is sometimes called a spectroscopically silent element because there are so few tools for probing its chemistry. This paper will review how sulfur K-edge X-ray absorption spectroscopy and related methods can be used to overcome this limitation, using examples from the authors’ research. X-rays from synchrotron radiation sources provide the means to study essentially any element in a variety of systems, ranging from pure compounds, to complex mixtures and even structured systems such as biological tissues. We show that sulfur K-edge X-ray absorption spectroscopy provides an important spectroscopic probe of sulfur chemistry in a range of systems, including those containing reactive species. Using a micro-focused X-ray beam, chemically-dependent X-ray fluorescence imaging can be used to image different sulfur species at a variety of spatial resolutions from microscopic to macroscopic. Increased sensitivity and deeper insights into electronic structure will be available in future studies using a suite of methods that are collectively known as advanced X-ray spectroscopy.

XAS combined with Py-GC study on the effects of temperatures and atmospheres on sulfur release and its transformation behavior during coal pyrolysis

YanZhou (YZ) coal with comparably high organic sulfur and high pyrite content was selected to investigate the effects of temperatures on sulfur release and its transformation during pyrolysis under Ar and CO2 atmospheres. Pyrolysis connected with gas chromatography (Py-GC) was used to analyze the sulfur containing gases of H2S, COS and SO2, and the sulfur transformation during pyrolysis was measured by Sulfur K-edge X-ray absorption spectroscopy (S-XAS). For YZ raw, deashed and depyrited coals, desulfurization ratios gradually increase with the increasing temperatures, while their char yields gradually decrease under both atmospheres. Under Ar atmosphere, minerals in YZ coal have catalytic effect on the decomposition of sulfurs. However, the effect of minerals on sulfur decomposition is different under CO2 atmosphere. Under CO2 atmosphere, the release amounts of H2S, COS and SO2 for each sample are higher than that under the Ar atmosphere and the difference becomes more significant after 600 °C. This suggests that CO2 atmosphere is more helpful for the decomposition of stable sulfur at comparatively higher temperatures. Based on the analysis of Sulfur K-edge XAS, CO2 atmosphere can promote the decomposition of stable FeS and thiophenes during pyrolysis. Thus, based on the analysis of Py-GC and Sulfur K-edge XAS, CO2 atmosphere is more beneficial for the release of sulfur containing gases and for the decomposition of stable sulfur than Ar atmosphere. This provides detailed information about the effects of temperatures on sulfur release and transformation behavior during pyrolysis under CO2 atmosphere.

Transformation and regulation of sulfur during pyrolysis of coal blend with high organic-sulfur fat coal

Sulfur transformation and distribution during pyrolysis of an industrial coking coal blend with a high organic-sulfur fat coal was studied in a fixed-bed reactor. Sulfur K-edge X-ray absorption spectroscopy was used to study the sulfur speciation in cokes. Two coals with high volatiles were selected to regulate the sulfur transformation behavior during pyrolysis and the interactions between volatile matters and nascent cokes were investigated. The addition of high organic-sulfur fat coal to coal blend resulted in the increase of sulfur content in coke, but the desulfurization rate also increased during coal blend pyrolysis. Higher amount of sulfur-containing radicals in volatile matters from high organic-sulfur fat coal promoted the interactions with nascent coke and resulted in the higher sulfur retention on the coke surface. Adding high volatile coal into coal blend affected the interactions between different coals and the sulfur transformation. The interactions between sulfur-containing radicals and nascent coke could be inhibited by volatile matters from high volatile coals. Further characterizations confirmed that the volatile matters from high volatile coal, which had a more overlapping temperature range to sulfur release in coal blend, leading to the lower sulfur content in coke, higher desulfurization and weaker S K-edge spectral intensity. The interactions between external volatile matters and nascent coke primarily occurred on the coke outer surface.

Sulfur K-Edge X-ray Absorption Spectroscopy of Aryl and Aryl-Alkyl Sulfides.

Aryl and mixed aryl-alkyl organic sulfides are important species in a variety of fields, including the drug and food industries. They also are present in fossil fuels, where they contribute to the range of sulfur compounds that must be removed by the fuel industry. We have used sulfur K-edge X-ray absorption spectroscopy, in combination with density functional theory calculations, to study the aryl sulfide diphenyl sulfide and two different aryl-alkyl sulfides. The sulfur K near-edge X-ray absorption spectra are strongly affected by the coordination of the phenyl ring and are distinct from spectra of the alkyl sulfides. For diphenyl sulfide the spectra are predicted to be sensitive to rotation about the S-C bonds, with experimental spectra corresponding to a sum of thermally accessible conformations. We also have investigated the vapor-phase spectrum of diphenyl sulfide, which is found to be very similar to that of toluene solutions of the compound.

Exploring reaction dynamics in lithium-sulfur batteries by time-resolved operando sulfur K-edge X-ray absorption spectroscopy.

A time-resolved operando X-ray absorption spectroscopy experiment was successfully designed to explore the sulfur reaction dynamics in lithium-sulfur (Li-S) batteries. It presents direct real-time experimental evidence for the distinct sulfur dynamics at different discharge rates, deepening the understanding of reaction mechanisms in Li-S batteries.

Sulfur K-edge XAS study of sulfur transformation behavior during pyrolysis and co-pyrolysis of biomass and coals under different atmospheres

Three low rank coals and one biomass, YiMa (YM) and Chifeng (CF) with comparatively high FeS2, and Ximeng (XM) coals with high organic sulfur contents, and sawdust (SD), were selected to investigate sulfur transformation behavior during pyrolysis and co-pyrolysis under Ar and CO2 atmospheres. The sulfur transformation of those samples was investigated by X-ray absorption spectroscopy (XAS) combined with X-ray fluorescence (XRF). For SD, the coals and their mixtures, the subordinate peak of CaS is formed during pyrolysis under Ar atmosphere, but not under CO2 atmosphere. For XM and CF coals, sulfate peak of their chars and the chars of their mixture becomes more intense after pyrolysis under Ar atmosphere, while remain low under CO2 atmosphere. This indicates that CO2 atmosphere can impede the formation of CaS and sulfate. In addition, CO2 atmosphere and SD can promote the decomposition of FeS in CF coal before 900 °C, while SD has no significant effect on FeS in YM coal at the ratio of 3:1 (YM:SD). However, SD can also help the decomposition of FeS in YM coal at the ratio of 1:1. This suggests that SD is not enough for FeS to decompose at the ratio of 3:1. Thiophene peaks of all samples are more intense under CO2 atmosphere than under Ar atmosphere, meaning that more stable organic sulfur is formed and retained in the char after pyrolysis and co-pyrolysis under CO2 atmosphere.