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At least 145 records · Page 8

Integrated data-driven and experimental approaches to accelerate lead optimization targeting SARS-CoV- 2 main protease

Identification of potential therapeutic candidates can be expedited by integrating computational modeling with domain aware machine learning (ML) approaches followed by experimental validation. Generative deep learning models have been recently developed that can generate thousands of new candidates, but their physiochemical properties are typically not optimized. Using our deep learning models and a scaffold as a starting point, we generated tens of thousands of compounds for SARS-CoV-2 M pro that preserve the core scaffold. Here we utilized and implemented several computational tools such as structural alert and toxicity analysis, high throughput virtual screening, ML-based 3D quantitative structure–activity relationships, multi-parameter optimization, and graph neural networks on libraries of generated candidates to predict biological activity and binding affinity a priori. From these collective computational results, eight promising candidates were identified and tested experimentally using Native Mass Spectrometry (MS) and FRET-based functional assays. Two compounds, with quinazoline-2-thiol and acetylpiperidine core moiety showed IC 50 values in the low micromolar range: 2.95±0.0017 µM and 3.41±0.0015 µM, respectively. The molecular dynamics simulations further highlight that binding of these compounds results in allosteric modulations in the chain B and the interface domains of the M pro . The key fragments from these top hits can be used as input for closed loop lead optimization in the integrated pipeline.

60 APPLIED LIFE SCIENCES↗

Tuning crosslinking of hybrid preceramic polymers in vat photopolymerization toward controlled ceramic yields

Control of preceramic polymer crosslinking for UV-curable processing is essential for fine 3D printing with high ceramic conversion for sustainable polymer-derived ceramics (PDC) engineering. While various factors influencing ceramic yield have been studied, the systematic exploration of the relationship between crosslinking and ceramic yield, especially when crosslinking increases volatile elements, remains open for further investigation. This study addresses this gap by utilizing vat photopolymerization (VP) additive manufacturing (AM) as a versatile platform for controlling preceramic crosslinking and ceramic yield. By rationally designing and tuning the photochemical crosslinking through digital light processing (DLP), we demonstrate that the ceramic yield can be enhanced from 64% to over 86%, even with added volatile elements. We reveal that the post-pyrolysis ceramic yield can be closely correlated with the pre-pyrolysis crosslinking of the preceramic network represented by its stiffness. This correlation thereby suggests a fast, energy-efficient, non-destructive methodology to predict and improve ceramic yield. Combined with these findings, our one-pot thiol-ene hybridization of polycarbosilane and polycarbosiloxane via DLP offers an exemplary method to generate hybrid preceramic polymers with tailored material properties toward target applications, and potentially even higher ceramic yields. This study thus contributes to achieving better resource- and energy-efficient preceramic polymer and PDC processing routes toward sustainable, advanced organic–inorganic materials manufacturing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Copper transformation, speciation, and detoxification in anoxic and suboxic freshwater sediments

The complex chemistry of copper (Cu) in freshwater sediments at low concentrations is not well understood. We evaluated the transformation processes of Cu added to freshwater sediments under suboxic and anoxic conditions. Freshwater sediments from three sources in Michigan with different characteristics (Spring Creek, River Raisin, and Maple Lake) were spiked with 30 or 60 mg kg -1 Cu and incubated under a nitrogen atmosphere. After 28-d, each treatment subset was amended with organic matter (OM) to promote anoxic conditions and evaluate its effects on Cu speciation. OM addition triggered a shift from suboxic to anoxic conditions, and sequential extractions showed that Cu accordingly shifted from acid-soluble to oxidizable fractions. Extended X-ray absorption fine-structure (EXAFS) spectroscopy revealed that Cu sulfides dominated all anoxic samples except for Spring Creek 30 mg kg -1 , where Cu(I) was predominantly complexed to thiol groups of OM. Covellite and chalcopyrite (CuFeS 2 ) were the predominant Cu species in nearly all anoxic samples, as determined by Raman spectroscopy, scanning electron microscopy, and X-ray absorption near-edge structure (XANES) spectroscopy. Copper reduction also occurred under suboxic conditions: for two of three sediments, around 80% had been reduced to Cu(I), while the remaining 20% persisted as Cu(II) complexed to OM. However, in the third coarsest (i.e., Spring Creek), around 50% of the Cu had been reduced, forming Cu(I)-OM complexes, while the remainder was Cu(II)-OM complexes. Toxicity tests showed that survival of H. azteca and D. magna were significantly lower in suboxic treatments. Anoxic sediments triggered a near-complete transformation of Cu to sulfide minerals, reducing its toxicity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A biohybrid strategy for enabling photoredox catalysis with low-energy light

Natural systems drive the high-energy reactions of photosynthesis with efficient and broadband energy capture. Transition-metal photocatalysts similarly convert light into chemical reactivity, and yet suffer from light-limited operation and require blue-to-UV excitation. In photosynthesis, both light capture and reactivity have been optimized by separation into distinct sites. In this work, inspired by this modular architecture, we synthesized a biohybrid photocatalyst by covalent attachment of the photosynthetic light-harvesting protein R-phycoerythrin (RPE) to the transition-metal photocatalyst tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy) 3 ] 2+ ). Spectroscopic investigation found that absorbed photoenergy was efficiently funneled from RPE to [Ru(bpy) 3 ] 2+ . The utility of the biohybrid photocatalyst was demonstrated via an increase in yields for a thiol-ene coupling reaction and a cysteinyl-desulfurization reaction, including recovered reactivity at red wavelengths where [Ru(bpy) 3 ] 2+ alone does not absorb.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of copper thiolate organometallic compound as thermal sensitive coating for energy storage system safety

Safety and reliability are primary concerns for the deployment of lithium-ion batteries, especially in electric vehicles (EV) and larger-scale energy storage systems (ESS). Current technology in battery management systems (BMS) includes cell voltage monitoring and positioning temperature sensors in selected locations. For a system with hundreds to thousands of individual batteries, single-point temperature monitoring is inadequate to detect hot spots and cell overheating, which could lead to thermal runaway. Here, we have developed a temperature-sensitive copper-thiol compound that can be directly coated onto battery pouch foils to enable early detection of thermal runaway. Upon reaching specific temperatures, this compound releases a sulfur-containing detectable gas, which can be identified using chemically specific gas sensors to trigger an early warning signal. Such a signal propagate through air offers broad signal coverage and enables a more comprehensive approach to large-area temperature monitoring. The Cu-ethanethiol coating is designed to release volatile gases when the substrate surface temperature exceeds 70 °C, with continuous outgassing as the temperature increases. The compound is composed of Cu, S, Cl, hydrocarbons and trace amounts of oxygen. Upon heating, the oxidation state of Cu(I) transitions to Cu (II), accompanied by gas release. Thermogravimetric analysis coupled with mass spectrometry correlated well with the onset of gas release temperature and emission of sulfur-containing volatile gases. Additionally, an acrylic overcoat is applied to enhance the adhesion of the thermally sensitive compound film to the battery pouch foil. This coating is expected to offer an additional safety layer for ESS, alerting possible thermal runaway events before a failure occurs, thereby allowing sufficient time to implement a mitigation plan.

Early warning systems↗

Investigation of the structure, filler interaction and degradation of disulfide elastomers made by Reversible Radical Recombination Polymerization (R3P)

In this paper we report the synthesis and analysis of cyclic polydisulfides, their redox depolymerization as well as their interaction with carbon black. Cyclic poly(3,6-dioxa-1,8-octanedithiol)s (pDODT) were synthesized by Reversible Radical Recombination Polymerization (R3P). R3P is a scalable “green” polymerization process using triethylamine (TEA), H 2 O 2 and air for the polymerization of dithiol monomers. pDODTs were synthesized in 5 and 20 g batches. The effect of peroxide concentration (3, 5, 10, 20, 30%) was investigated. It was found that the molecular weights increased exponentially with increasing peroxide concentrations. At 30% peroxide concentration pDODTs with M n up to 400,000 g/mol and polydispersity of 2 were obtained. 700 and 800 MHz NMR were used for investigating the chemical structure of the polymers. The absence of thiol end group signals in polymers made with > 10wt % H 2 O 2 and M n < 100,000 g/mol, including a sample of a fractionated polymer with starting Mn = 600,000 g/mol, verified cyclic structures. Dithiothreitol reduced the polymers to monomer and a small percentage of oligomers. Carbon black was shown to increase the moduli of high molecular weight pDODTs. Swelling tests in chloroform showed that polymers made with 20 and 30w% peroxide swelled 14 and 10 times of their starting weight without dissolving, indicating chemical interaction between the polymers and carbon black. In conclusion, further analysis of these interesting elastomers, available at the 20 g scale, is in progress.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modifying the resolving cysteine affects the structure and hydrogen peroxide reactivity of peroxiredoxin 2

Peroxiredoxin 2 (Prdx2) is a thiol peroxidase with an active site Cys (C52) that reacts rapidly with H 2 O 2 and other peroxides. The sulfenic acid product condenses with the resolving Cys (C172) to form a disulfide which is recycled by thioredoxin or GSH via mixed disulfide intermediates or undergoes hyperoxidation to the sulfinic acid. C172 lies near the C terminus, outside the active site. It is not established whether structural changes in this region, such as mixed disulfide formation, affect H 2 O 2 reactivity. To investigate, we designed mutants to cause minimal (C172S) or substantial (C172D and C172W) structural disruption. Stopped flow kinetics and mass spectrometry showed that mutation to Ser had minimal effect on rates of oxidation and hyperoxidation, whereas Asp and Trp decreased both by 100-fold. To relate to structural changes, we solved the crystal structures of reduced WT and C172S Prdx2. The WT structure is highly similar to that of the published hyperoxidized form. C172S is closely related but more flexible and as demonstrated by size exclusion chromatography and analytical ultracentrifugation, a weaker decamer. Size exclusion chromatography and analytical ultracentrifugation showed that the C172D and C172W mutants are also weaker decamers than WT, and small-angle X-ray scattering analysis indicated greater flexibility with partially unstructured regions consistent with C-terminal unfolding. We propose that these structural changes around C172 negatively impact the active site geometry to decrease reactivity with H 2 O 2 . This is relevant for Prdx turnover as intermediate mixed disulfides with C172 would also be disruptive and could potentially react with peroxides before resolution is complete.

59 BASIC BIOLOGICAL SCIENCES↗

Sorption kinetics and stability of conventional adsorbents for mercury remediation

In-situ remediation of mercury at numerous contaminated sites worldwide is a challenging and costly endeavor due to the persistency of this contaminant. In this study, we evaluated eight commercially available sorbent media ranging from carbon-, clays- and silica-based materials (PBC– Biochar, eSorb – Sorbster, nsPAC – Powdered Activated Carbon, fsPAC – Powdered Activated Carbon with Mackinawite, F300 – Filtrasorb 300, Si-SH – Silica Thiol, eBind – RemBind, Q-Clay – Organoclay PM-199), for their effectiveness in sorbing mercury (Hg 2+ ) and mercury complexed with dissolved organic matter (Hg-DOM). Under the chosen experimental conditions of this study, results showed that in the absence of DOM, the kinetic rates of Hg 2+ sorption onto the evaluated sorbents were in the order of 0.31 min-1 (Si-SH) to 2.98 min -1 (nsPAC), whereas in the presence of DOM, the rates varied from 0.16 min-1 (F300) to 0.95 min -1 (nsPAC). The measured sorption capacity for Hg 2+ in the absence of DOM varied from 3.02 mg/g (Q-Clay) to 35.15 mg/g (Si-SH), whereas in the presence of DOM, calculated partition coefficient (KD) ranged from 69.7 mL/g (Q-Clay) to 41,510 mL/g (Si-SH). Furthermore, kinetic data suggest liquid film diffusion was the rate-limiting steps governing mercury sorption onto the studied media. Overall, the obtained study parameters (kinetics/isotherm) are particularly important in informing robust engineering designs for deployment of the vast majority of evaluated sorbents. Thus, sorbent-based strategies offer viable solutions for cost-effective cleanup of mercury at industrially contaminated sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mutation of an active site-adjacent residue in VIM indirectly dictates interactions with and blunts inhibition by D-captopril

Activity assays and X-ray crystallographic studies were undertaken to elucidate the inhibitory mechanism of captopril stereoisomers on Verona integron-encoded metallo-β-lactamases, specifically VIM-20, VIM-31, and VIM-15. All three VIM-2-like variants (VIM-20, VIM-31, and VIM-15) and VIM-2 expressed in Escherichia coli exhibited catalytic activity with comparable steady-state kinetic parameters. Among the tested thiol drugs (L- and D-captopril, D,L-thiorphan, and 2,3-dimercaprol), IC50 analyses indicated that D-captopril and 2,3-dimercaprol were more potent inhibitors against the VIM enzymes examined in this study. Notably, the IC50 value of D-captopril against VIM-31 was an exception, closely resembling that of L-captopril. To elucidate this exceptional inhibitory potency of D-captopril and its binding mode in the active site of VIM-31, high-resolution crystal structures of VIM-20, VIM-31, and VIM-15 in complex with both L- and D-captopril are reported. These findings will help evaluate whether the identified potent inhibitor D-captopril could be further developed as a pan inhibitor targeting the VIM-family enzymes.

Silwal, Surendra Bikram↗

One-pot ternary sequential reactions for photopatterned gradient multimaterials

Seamless multimaterial construction is a common motif in animal physiology. Such continuous mechanical gradients remain challenging to reproduce in engineered systems, as current resin chemistries typically result in a single fixed set of properties. As an alternative to single-property materials, we introduce a thiol-ene-epoxy-based photothermal reaction scheme that produces multimaterials by altering the polymer microstructure within a single resin. In this system, the photodosage during the first stage of processing dictates the extent of conversion for each subsequent reaction. As a result, our photochemistry can exhibit a diverse range of soft (Young’s modulus, E ~ 400 kPa; elongation, dL/L0 ~ 300%) and stiff (E ~ 1.6 GPa; dL/L 0 ~ 3%) mechanical properties. Furthermore, we pattern photostable and mechanically robust modulus gradients (d[E r, stiff /E r , soft] /dx > 1,000 mm -1 ) that exceed those found in squid beaks and human knee entheses. We demonstrate the ability to build intricate multimaterial architectures including a soft, wearable braille display.

36 MATERIALS SCIENCE↗

Design of a bifunctional TEMPO-tertiary amine mesoporous silica catalyst for the three-step cascade synthesis of a chromene derivative

A key challenge is design of materials and processes whereby competing reagents or conditions do not harm the multi-step sequence, thus allowing for more efficient chemical synthesis with elimination of work-up and separation steps. In this work, a three-step reaction cascade is performed using a porous bifunctional dimethylpropylamine-TEMPO-MCM41 catalyst, converting the commodity chemicals benzyl alcohol, sodium hypochlorite, and malononitrile to a biologically active anti-cancer, and anti-malarial 2-amino-chromene derivative. The cascade first utilizes a TEMPO-catalyzed oxidation of benzyl alcohol to benzaldehyde with NaOCl as the terminal oxidant. This is followed by a two-step, dual base catalyzed Knoevenagel condensation with malononitrile followed by a Michael addition with lawsone. Optimal conditions converting benzyl alcohol to 2-amino-5,10-dioxo-4-phenyl-5,10-dihydro-4H-benzo[g]chromene-3-carbonitrile include the delayed addition of malononitrile and lawsone during the three-step reaction sequence, which results in a 2-amino-chromene yield of over 80%. The importance of stepwise reagent addition is rationalized due to the unfavorable adsorption of acidic lawsone on the surface-grafted base catalyst. Tertiary Brønsted base sites of dimethylpropylamine outperform the more Lewis basic primary propylamine functionalized catalyst. This work outlines a simple and effective method for generating mesoporous materials with two types of active sites via co-condensation and thiol-ene coupling procedures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Liquid chromatography at critical conditions (LCCC): Capabilities and limitations for polymer analysis

This paper investigates liquid chromatography at critical condition (LCCC) for polymer analysis. Based on controversial claims on the separation of cyclic polymers from linear analogues in the literature, the efficiency of LCCC for separation and purity analysis is questioned. Polyisobutylene (PIB) and poly(3,6-dioxa-1,8-octanedithiols) (polyDODT) were used for the study. Here, the structure of low molecular weight cyclic and linear polyDODT was demonstrated by MALDI-ToF. NMR did not show the presence of thiol end groups in higher molecular weight PIB-disulfide and polyDODT samples, so they were considered cyclic polymers. When a low molecular weight polyDODT oligomer with only traces of cycles, as demonstrated by MALDI-ToF, was mixed with an M n = 27K g/mol cyclic sample, LCCC did not detect the presence of linear oligomers at 6 wt%. Based on the data presented here, it can be concluded that the LCCC method is not capable of measuring < 6 wt% linear contamination so earlier claims for cyclic polystyrene (PS) samples purified by LCCC having < 3 % linear contaminants are questioned.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Trithiol ligand provides tumor-targeting 191 Pt-complexes with high molar activity and promising in vivo properties

The Auger electron-emitting radionuclide 191 Pt is a promising candidate for radiopharmaceutical therapy. Herein, we explored novel labeling methods for 191 Pt using thiol-containing ligands to improve the in vivo stability and targeting ability of 191 Pt-labeled complexes. We synthesized dithiol-containing N 2 S 2 and NS 2 ligands, and a trithiol ligand, and then compared their radiochemical reactivity with 191 Pt. [ 191 Pt]Pt-trithiol was synthesized and its biodistribution was evaluated in mice and compared with free 191 Pt. Finally, a 191 Pt-trithiol complex targeting prostate-specific membrane antigen (PSMA): [ 191 Pt]Pt-trithiol-PSMA was developed and evaluated in mice bearing tumor xenografts and compared with a 191 Pt-complex labeled via monothiol-containing Cys ([ 191 Pt]Pt-Cys-PSMA). A comparison of N 2 S 2 , NS 2 , and trithiol showed that the trithiol ligand is the best for producing 191 Pt-labeled compounds in high yield and as a single peak in preparative HPLC. Notably, the trithiol ligand made 191 Pt-labeled compounds and precursors separatable, achieving 191 Pt-labeled products with a high molar activity: 200–400 mCi/μmol (7.4–14.8 GBq/μmol) at EOS. Additionally, [ 191 Pt]Pt-trithiol and [ 191 Pt]Pt-trithiol-PSMA were stable in vivo with rapid clearance compared with free 191 Pt and [ 191 Pt]Pt-Cys-PSMA. [ 191 Pt]Pt-trithiol-PSMA resulted in a low uptake in most normal organs and a high uptake in the kidneys and prostate cancer with PSMA expression. Furthermore, this study demonstrated that a labeling method with trithiol for Pt radionuclides achieves 191 Pt-labeled products with high molar activity. 191 Pt-trithiol-PSMA showed promising in vivo stability and tumor-targeting specificity, which should facilitate the pharmaceutical development of Pt radionuclides for radiopharmaceutical therapy, especially Auger electron cancer therapy.

Auger emitters↗

Aging of UV curable PDMS developed for large-scale, high viscosity stereolithography

Polydimethylsiloxane (PDMS) elastomers are silicone rubbers that find widespread application in both academic and industrial settings. This study investigates the use of photosensitive platinum catalysts for UV-activated hydrosilylation of PDMS, which enables the additive manufacturing of PDMS objects through techniques such as stereolithography. Specifically, this study focuses on understanding the aging behavior of Pt-catalyzed, UV-curable PDMS samples, including their mechanical behavior under thermal and UV-accelerated aging conditions. The results show that the Pt-catalyzed, UV-curable PDMS introduced in this research is ‘under-cured’ after being printed and will slowly evolve over time resulting in increased stiffness and decreased elongation, likely due to the formation of additional crosslinks. FTIR spectroscopy indicates that no new chemical bonds or functional groups are generated through the aging process, suggesting that no thermal degradation or polymer chain scissions occur in the polymer matrix. Overall, this PDMS formulation exhibits greater mechanical strength and significantly less reduction in strength with aging, compared with the commonly used, UV-curable thiol-ene PDMS.

36 MATERIALS SCIENCE↗

Correlating structure, self-assembly chemistry and conductivity of trithiocyanuric acid on Au(111)

The majority of candidates for simple model molecular-electronic components consist of a conductive π-conjugated hydrocarbon linker attached to at least two anchoring groups, such as thiols or isocyanides. It has been found that select molecules self-assemble on gold surfaces, creating one-dimensional conductive structures that act as “molecular wires”. Furthermore, these oligomers can form molecular bridges between gold nanoparticles, leading to the creation of simple molecular-electronic devices. This raises the question whether other π-conjugated molecular linkers could exhibit similar behavior that might offer a broader range of candidates for fabricating electronic devices. Trithiocyanuric acid (1,3,5-triazine-2,4,6-trithiol, TTCA) provides a possible candidate. TTCA (C3N3(SH)3) can exist as a trithiol or as a trithione in which hydrogens transfer to the sulfurs so that they are present with three C=N groups within the ring. TTCA exists naturally in the trithione form but converts into a trithiol when adsorbed onto an Ag(111) where it is vertically oriented. The structure of TTCA adsorbed on Au(111) is studied here using reflection-absorption infrared spectroscopy (RAIRS) where it is found to remain as the trithione isomer, but changes orientation as the coverage increases. Scanning-tunneling microscopy (STM) reveals that TTCA oligomerizes on Au(111) to form chains and triangular structures. The influence on molecular conductivity due to the differences in the adsorbate's isomeric structure was investigated using devices comprising either silver or gold nanoparticles deposited in the gap between gold nanoelectrodes. Both devices were found to conduct when dosed with TTCA, but the devices fabricated using silver were about 13 time more conductive than those made from gold nanoparticles, consistent with the π-conjugated structure formed on silver but not on gold. This implies that oligomers form both on silver and on gold and potentially increases the range of molecule-metal combinations that might be used to fabricate molecular-electronic devices.

Molecular electronics↗

Structural and Mechanistic Advances in the Chemistry of Methyl-Coenzyme M Reductase (MCR)

Methane represents 34% of U.S. energy consumption and is a major greenhouse gas related to the global carbon cycle and energy production. However, current industrial practices significantly increase atmospheric methane levels, necessitating a deeper understanding of its biosynthesis and oxidation. Methyl-coenzyme M reductase (MCR) is central to biological methane metabolism, catalyzing the final step of methanogenesis and the first step in anaerobic methane oxidation. It is also a key target for strategies to capture and transform methane into value-added chemicals.The active site of MCR is a buried Ni-based cofactor only accessible by the substrates via a 50 Å long tunnel. Although the Ni(I) state is required to initiate catalysis, capturing this state remains a challenge for the current structural techniques. Recent advances in structural biology using X-ray Free-Electron Laser serial crystallography have provided insights into MCR's inactive Ni(II) state at room temperature and show promise for capturing its active Ni(I) form.Our team has established several critical aspects of the MCR mechanism using a combination of experimental and computational studies. MCR uses CH 3 -SCoM and CoBSH as substrates, producing methane and a disulfide product CoMSSCoB. Kinetic analysis showed that productive substrate binding requires CH 3 -SCoM to bind first, inducing conformational changes that optimize the active site for subsequent CoBSH binding. Following substrate binding, four proposed methane production/oxidation mechanisms were examined, establishing whether the reaction proceeds through an organometallic methyl-nickel(III), methyl anion ion, or methyl radical intermediate. Experimental measurements using CoBSH analogs successfully slowed the reaction, allowing for mechanistic insight that demonstrated the methyl radical pathway, where the initial interactions involve homolytic cleavage of the methyl-sulfur bond, generating a methyl radical that quickly abstracts the thiol hydrogen atom of CoBSH to form methane. Computational studies further confirmed that, compared to other mechanisms, the methyl radical mechanism is thermodynamically more favorable and accessible under physiological conditions.Spectroscopic and computational studies challenged the conventional understanding of substrate binding in MCR by proposing an alternative positioning of CH 3 -SCoM and CoMSSCoB in the active site pocket. The research suggested that CH 3 -SCoM (substrate) and CoMSSCoB (product) bind via their sulfonate groups to the Ni(I) center of cofactor F 430 . This binding allows for the reaction without substrate reorganization in the pocket but would require a long-range electron transfer. Altogether, the work summarized in this review reflects our current understanding of the enzyme's catalytic mechanism and structural dynamics. This is essential for developing efficient methane conversion technologies that could mitigate its environmental impact while harnessing energy-storage properties.

03 NATURAL GAS↗

Tellurite Adsorption onto Bacterial Surfaces

Tellurium (Te) is an emerging contaminant and its chemical transformation in the environment is strongly influenced by microbial processes. In this study, we investigated the adsorption of tellurite [Te(IV), TeO 3 2- ] onto the common soil bacterium Bacillus subtilis. Thiol-blocking experiments were carried out to investigate the role of cell surface sulfhydryl sites in tellurite binding, and extended X-ray absorption fine structure (EXAFS) spectroscopy was performed to determine the chemical speciation of the adsorbed tellurite. The results indicate that tellurite reacts with sulfhydryl functional groups in the extracellular polymeric substances (EPS) produced by B. subtilis. Upon binding to sulfhydryl sites in the EPS, the Te changes from Te-O bonds to Te-S coordination. Further analysis of the surface-associated molecules shows that the EPS of B. subtilis contain proteins. Removal of the proteinaceous EPS dramatically decreases tellurite adsorption and the sulfhydryl surface site concentration. These findings indicate that sulfhydryl binding in EPS plays a key role in tellurite adsorption on bacterial surfaces.

54 ENVIRONMENTAL SCIENCES↗

Selenite and Selenate Sequestration during Coprecipitation with Barite: Insights from Mineralization Processes of Adsorption, Nucleation, and Growth

Coprecipitation of selenium oxyanions with barite is a facile way to sequester Se in the environments. However, the chemical composition of Se-barite coprecipitates usually deviates from that predicted from thermodynamic calculations. This discrepancy was resolved by considering variations in nucleation and growth rates controlled by ion–mineral interactions, solubility, and interfacial energy. For homogeneous precipitation, ~10% of sulfate, higher than thermodynamic predictions (<0.3%), was substituted by Se(IV) or Se(VI) oxyanion, which was attributed to adsorption-induced entrapment during crystal growth. For heterogeneous precipitation, thiol- and carboxylic-based organic films, utilized as model interfaces to mimic the natural organic-abundant environments, further enhanced the sequestration of Se(VI) oxyanions (up to 41–92%) with barite. Such enhancement was kinetically driven by increased nucleation rates of selenate-rich barite having a lower interfacial energy than pure barite. In contrast, only small amounts of Se(IV) oxyanions (~1%) were detected in heterogeneous coprecipitates mainly due to a lower saturation index of BaSeO 3 and deprotonation degree of Se(IV) oxyanion at pH 5.6. Finally, these roles of nanoscale mineralization mechanisms observed during composition selection of Se-barite could mark important steps toward the remediation of contaminants through coprecipitation.

54 ENVIRONMENTAL SCIENCES↗