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The benzimidazole scaffold is an important pharmacophore and one of the preferred structures in medicinal chemistry due to the wide range of biological activities of its derivatives. Here in this article, the synthesis of two series of compounds, namely bis(thiobenzimidazol-2-yl)methane derivatives and analogs (4a-e) and bis(benzimidazol-2-yl)dithiol derivatives and analogs (5a-e) are described. These compounds were synthesized by first designing 2-mercaptobenzimidazole derivatives and analogs (2a-e) by action of orthophenylenediamine and analogs (1a-e) with carbon disulfide. Reaction of thiols (2a-e) with diiodomethane leads to bis(thiobenzimidazol-2-yl)methane derivatives and analogs (4a-e). Their treatment in glacial acetic acid led to their oxidation to bis(benzimidazol-2-yl)dithiol derivatives and analogs (5a-e). The structures of the synthesized compounds were characterized by 1H, 13C Nuclear Magnetic Resonance (NMR), and High-Resolution Mass Spectrometry (HRMS) analyses.

A disintegrin and metalloproteinase 17 (ADAM17) is a zinc-dependent enzyme that catalyzes the cleavage of the extracellular domains of various transmembrane proteins. ADAM17 is regarded as a promising drug target for the suppression of various diseases, including cancer metastasis. We synthesized a new ADAM17 inhibitor, SN-4, composed of a zinc-binding dithiol moiety and an appendage that specifically binds to a pocket of ADAM17. We show that SN-4 inhibits the ability of ADAM17 to cleave tumor necrosis factor α (TNF-α) in vitro. This activity was reduced by the addition of zinc, indicating the importance of the zinc chelating dithiol moiety. Inhibition of TNF-α cleavage by SN-4 in cells was also observed, and with an IC50 of 3.22 µM, SN-4 showed slightly higher activity than the well-studied ADAM17 inhibitor marimastat. Furthermore, SN-4 was shown to inhibit cleavage of CD44 by ADAM17, but not by ADAM10, and to suppress cell invasion. Molecular docking showed good fitting of the specificity pocket-binding group and one SH of SN-4 and hinted at possible means of structural optimization. This study provides clues for the development of potent and selective ADAM17 inhibitors.

Various optoelectronic properties of 10-(1,3-Dithiol-2-ylidene)anthracene based organic light harvesters were probe at solid state bulk surface. Effect of diverse conjugated π-donor-acceptor bridge...

Gold nanorods possess optical properties that are tunable and highly sensitive to variations in their aspect ratio (length/width). Therefore, the development of a sensing platform where the gold nanorod morphology (i.e., aspect ratio) is modulated in response to an analyte holds promise in achieving ultralow detection limits. Here, we use a dithiol peptide as an enzyme substrate during nanorod growth. The sensing mechanism is enabled by the substrate design, where the dithiol peptide contains an enzyme cleavage site in-between cysteine amino acids. When cleaved, the peptide dramatically impacts gold nanorod growth and the resulting optical properties. We demonstrate that the optical response can be correlated with enzyme concentration and achieve a 45 pM limit of detection. Furthermore, we extend this sensing platform to colorimetrically detect tumor-associated inhibitors in a biologically relevant medium. Overall, these results present a subnanomolar method to detect proteases that are critical biomarkers found in cancers, infectious diseases, and inflammatory disorders.

Interfacial modular assembly has emerged as an adaptable strategy for engineering the surface properties of substrates in biomedicine, photonics, and catalysis. Herein, we report a versatile and robust coating (pBDT-TA), self-assembled from tannic acid (TA) and a self-polymerizing aromatic dithiol (i.e., benzene-1,4-dithiol, BDT), that can be engineered on diverse substrates with a precisely tuned thickness (5-40 nm) by varying the concentration of BDT used. The pBDT-TA coating is stabilized by covalent (disulfide) bonds and supramolecular (π-π) interactions, endowing the coating with high stability in various harsh aqueous environments across ionic strength, pH, temperature (e.g., 100 mM NaCl, HCl (pH 1) or NaOH (pH 13), and water at 100 °C), as well as surfactant solution (e.g., 100 mM Triton X-100) and biological buffer (e.g., Dulbecco's phosphate-buffered saline), as validated by experiments and simulations. Moreover, the reported pBDT-TA coating enables secondary reactions on the coating for engineering hybrid adlayers (e.g., ZIF-8 shells) via phenolic-mediated adhesion, and the facile integration of aromatic fluorescent dyes (e.g., rhodamine B) via π interactions without requiring elaborate synthetic processes.

Diversity-oriented synthesis (DOS) is a rich source for novel lead structures in Medicinal Chemistry. In this study, we present a DOS-compatible method for synthesis of compounds bearing a free thiol moiety. The procedure relies on Rh(II)-catalyzed coupling of dithiols to diazo building blocks. The synthetized library was probed against metallo-β-lactamases (MBLs) NDM-1 and VIM-1. Biochemical and biological evaluation led to identification of novel potent MBL inhibitors with antibiotic adjuvant activity.

An amperometric chemosensor for the detection of hydrogen peroxide is reported. The sensor is based on 1,4-benzoquinone immobilized on the gold electrode using self-assembled monolayer of short chain symmetrical dithiol as an anchor layer. Sensor analysis was performed by cyclic voltammetry at the potential range from −0.6 V till +0.9 V as well as in the anodic or cathodic potential ranges only. The results indicate oxidative electrochemical decomposition of hydrogen peroxide at the potential of ∼+0.4 V leading to the formation of oxygen while at cathodic potentials a reduction of the formed oxygen as well as of the hydrogen peroxide occur. A decrease in the oxidation potential of hydrogen peroxide on the gold electrode coated by self-assembled monolayer with 1,4-benzoquinone in comparison with that measured on the electrodes coated by the same self-assembled monolayer without 1,4-benzoquinone, indicates electrocatalytic effect of this moiety on oxidative decomposition of hydrogen peroxide. Analytical evaluation of the sensor performance was done in the voltammetric as well as in the chronoamperometric mode. The sensor exhibited linear response over the concentration range till 2.5 mM with a limit of detection ∼4 μM.

The transfer of multiple electrons and protons is of crucial importance in many reactions relevant in biology and chemistry. Natural redox-active cofactors are capable of storing and releasing electrons and protons under relatively mild conditions and thus serve as blueprints for synthetic proton-coupled electron transfer (PCET) reagents. Inspired by the prominence of the 2e-/2H+ disulfide/dithiol couple in biology, we investigate herein the diverse PCET reactivity of a Re complex equipped with a bipyridine ligand featuring a unique SH···-S moiety in the backbone. The disulfide bond in fac-[Re(S-Sbpy)(CO)3Cl] (1, S-Sbpy = [1,2]dithiino[4,3-b:5,6-b']dipyridine) undergoes two successive reductions at equal potentials of -1.16 V vs Fc+|0 at room temperature forming [Re(S2bpy)(CO)3Cl]2- (12-, S2bpy = [2,2'-bipyridine]-3,3'-bis(thiolate)). 12- has two adjacent thiolate functions at the bpy periphery, which can be protonated forming the S-H···-S unit, 1H-. The disulfide/dithiol switch exhibits a rich PCET reactivity and can release a proton (ΔG°H+ = 34 kcal mol-1, pKa = 24.7), an H atom (ΔG°H• = 59 kcal mol-1), or a hydride ion (ΔG°H- = 60 kcal mol-1) as demonstrated in the reactivity with various organic test substrates.

A scalable synthesis of high refractive index, optically transparent photopolymers from a family of low-viscosity multifunctional thiol and alkyne monomers via thiol-yne "click" is described herein. The monomers designed to incorporate high refractive index cores consisting of aryl and sulfide groups with high intrinsic molar refraction were synthesized starting from commercially available low-cost raw materials. The low-viscosity (

Gold nanoparticles (GNPs) protected by poly(2-ethyl-2-oxazoline) (POZ) of different molecular weights (Mw = 5, 50, 200 and 500 kDa) were synthesised and characterised by dynamic light scattering, nanoparticle tracking analysis, zeta potential measurement and transmission electron microscopy. It was established that the use of POZ with 50 kDa resulted in formation of GNPs with low polydispersity while POZ with greater molecular weights led to formation of more polydisperse GNPs. Fluorescent labelling of these nanoparticles was achieved through their reaction with polyethyleneglycol dithiol (8-12 kDa) as a linker molecule with subsequent reaction with 6-(iodoacetamido) fluorescein. The fluorescent nature of obtained GNPs was confirmed by the appearance of the fluorescence peak at 510 nm that is typical for fluorescein molecules and glowing of the aqueous solution under the UV irradiaton. The fluorescently-labelled GNPs are promising tool in biomedical application to monitor the biological systems using fluorescent microscopy.

The emerging promise of few-atom metal catalysts has driven the need for developing metal nanoclusters (NCs) with ultrasmall core size. However, the preparation of metal NCs with single-digit metallic atoms and atomic precision is a major challenge for materials chemists, particularly for Ag, where the structure of such NCs remains unknown. In this study, we developed a shape-controlled synthesis strategy based on an isomeric dithiol ligand to yield the smallest crystallized Ag NC to date: [Ag9(1,2-BDT)6]3– (1,2-BDT = 1,2-benzenedithiolate). The NC’s crystal structure reveals the self-assembly of two Ag square pyramids through preferential pyramidal vertex sharing of a single metallic Ag atom, while all other Ag atoms are incorporated in a motif with thiolate ligands, resulting in an elongated body-centered Ag9 skeleton. Steric hindrance and arrangement of the dithiolated ligands on the surface favor the formation of an anisotropic shape. Time-dependent density functional theory based calculations reproduce the experimental optical absorption features and identify the molecular orbitals responsible for the electronic transitions. Our findings will open new avenues for the design of novel single-digit metal NCs with directional self-assembled building blocks., An isomeric dithiol-based synthesis strategy is used to synthesize the smallest crystallized Ag nanocluster, [Ag9(1,2-BDT)6]3−. The single-digit cluster reveals novel bonding modes and building blocks, which include the self-assembly of two Ag square pyramids sharing a common vertex and six bidentate thiolate motifs.

The new segmented poly(thiourethane-urethane)s (PTURs) based on 1,1′-methanediylbis(4-isocyanatocyclohexane) (HMDI, Desmodur W®), polycarbonate diol (PCD, Desmophen C2200) and (methanediyldibenzene-4,1-diyl)dimethanethiol were synthesized by one-step melt polyaddition method. The obtained PTURs, with a content of 30–60 wt% of the hard segments (HS), were tested in which the influence of changes in the HS content on their properties was determined. The polymers were characterized by Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), thermal analysis (DSC, TGA) and thermomechanical analysis (DMTA). Additionally, tensile strength, optical (refractive index, UV-VIS and color) and surface properties of the obtained polymers (contact angle and surface free energy) and adhesion to copper were examined. FTIR analysis verified the supposed structure of the polymers obtained and showed a complete conversion of the isocyanate groups. TGA analysis confirmed the relatively good thermal stability of the polymers. On the other hand, after performing the DSC analysis, it was possible to state that the obtained materials were partially or completely amorphous, and the microphase separation decreased with increasing HS content in the polymer. Similar observations were made from the DMTA data. In addition, the hardness, tensile strength, modulus of elasticity, storage modulus, adhesion to copper, refractive index and total free surface energy increased with increasing HS content in the polymer.

We report quantitative analysis of tunneling conductance in molecular junctions based on self-assembled monolayers (SAMs) of oligophenylene dimethanethiols (OPDMn) in which −CH2– spacers flank eith...

Cellulose nanofibrils (CNFs) produced through processes involving oxidation (e.g. TEMPO oxidation) present reactive groups that allow for straightforward modification in aqueous suspension. CNFs fabricated through mechanical refinement alone can be challenging to modify for subsequent reactions due to only having hydroxyl groups present on the surface. To address these issues, CNFs with only hydroxyl groups present were functionalized with norbornene groups in their native aqueous suspension to achieve up to 10% functionalization per anhydroglucose unit. Since quantification of surface functionalization of CNFs is challenging through most methods, a degradation and subsequent nuclear magnetic resonance analysis method was developed to quantify norbornene functionalization. The norbornene functionalized CNFs (nCNFs) were cross-linked through UV and thermally initiated thiol-ene click reactions to create robust CNF hydrogels. By varying the reaction conditions, hydrogels made from nCNFs and a dithiol cross-linker could achieve compression modulus values up to 25 kPa. The materials were stable in aqueous suspensions and the cross-linked hydrogels still exhibited shear thinning behavior with high recovery, which demonstrated that even though effective cross-links were formed, a complete network was not. Through this study, thiol-norbornene crosslinking of CNFs could create robust hydrogels and improve aqueous stability that could have applications in sustainable materials and biomaterials.

In this study, a simple and low-cost electrochemical immunosensor for the detection of tumor markers (carcinoembryonic antigen, CEA, as a model) was investigated. The self-polymerization of dopamine was used to provide a secondary reaction platform, and a more stable dithiol compound (thioctic acid) as a spacer was fixed on the platform via the Michael's addition reaction. A dithiol-functionalized platform was used for the covalent immobilization of antibodies, and the structure showed significant changes in the atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) images. The electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV) measurements were performed to test the performance of a double-antibody sandwich structure. The designed CEA immunosensor exhibited a linear response over a concentration range of 0.05–80 ng mL−1 with a low detection limit of 1.21 pg mL−1, and the results demonstrated a potential application for clinical diagnosis.

Nitric oxide (NO) binds to soluble guanylyl cyclase (GC1) and stimulates its catalytic activity to produce cGMP. Despite the key role of the NO-cGMP signaling in cardiovascular physiology, the mechanisms of GC1 activation remain ill-defined. It is believed that conserved cysteines (Cys) in GC1 modulate the enzyme's activity through thiol-redox modifications. We previously showed that GC1 activity is modulated via mixed-disulfide bond by protein disulfide isomerase and thioredoxin 1. Herein we investigated the novel concept that NO-stimulated GC1 activity is mediated by thiol/disulfide switches and aimed to map the specific Cys that are involved. First, we showed that the dithiol reducing agent Tris (2-carboxyethyl)-phosphine reduces GC1 response to NO, indicating the significance of Cys oxidation in NO activation. Second, using dibromobimane, which fluoresces when crosslinking two vicinal Cys thiols, we demonstrated decreased fluorescence in NO-stimulated GC1 compared to unstimulated conditions. This suggested that NO-stimulated GC1 contained more bound Cys, potentially disulfide bonds. Third, to identify NO-regulated Cys oxidation using mass spectrometry, we compared the redox status of all Cys identified in tryptic peptides, among which, ten were oxidized and two were reduced in NO-stimulated GC1. Fourth, we resorted to computational modeling to narrow down the Cys candidates potentially involved in disulfide bond and identified Cys489 and Cys571. Fifth, our mutational studies showed that Cys489 and Cys571 were involved in GC1'response to NO, potentially as a thiol/disulfide switch. These findings imply that specific GC1 Cys sensitivity to redox environment is critical for NO signaling in cardiovascular physiology.

A quantitative imaging strategy for the vicinal dithiol (VD) of arsenic-binding proteins in the mouse brain is reported. 2-p-Aminophenyl-1,3,2-dithiarsenolane (PAO-EDT) couples to gold nanoclusters Au22(GSH)18 to form conjugate Au22-PAO-EDT (APE). PAO-EDT in APE selectively binds VD with 1 : 1 stoichiometry. After tagging the mouse brain with APE, VD imaging is realized by laser ablation ICP-MS. VD correlates linearly with 197Au in APE offering a 22-fold amplification and a LOD of 5.43 nM. It is found that the cerebral cortex and hippocampus are most affected in an arsenic poisoned mouse brain. This study provides useful information for further understanding the mechanisms underlying the biological effects of arsenic on the living body.

Herein, we report a facile method for the synthesis of Ni–NiO heterojunction nanoparticles, which we utilized for the nuclear halogenation reaction of phenol and substituted phenols using N-bromosuccinimide (NBS). A remarkable para-selectivity was achieved for the halogenated products under semi-aqueous conditions. Interestingly, blocking of the para-position of phenol offered ortho-selective halogenation. In addition, the Ni–NiO nanoparticles catalyzed the oxidative esterification of carbonyl compounds with alcohol, diol or dithiol in the presence of a catalytic amount of NBS. It was observed that the aromatic carbonyls substituted with an electron-donating group favoured nuclear halogenation, whereas an electron-withdrawing group substitution in carbonyl compounds facilitated the oxidation reaction. In addition, the catalyst was magnetically separated and recycled 10 times. The tuned electronic structure at the Ni–NiO heterojunction controlled selectivity and activity as no such para-selectivity was observed with commercially available NiO or Ni nanoparticles.

Regulation of the morphology of supramolecular polymers is a challenging task although the morphology of supramolecular polymers plays an important role in their properties and functions. Here, we report a simple and efficient method to control the morphologies of metallacycle-cored supramolecular polymers. An allyl-functionalized hexagonal metallacycle is cross-linked by poly(ethylene glycol) (PEG) dithiol to form metallacycle-cored supramolecular polymers. The morphologies of the supramolecular polymers can be finely regulated by the length of PEG as well as the solvent. In methanol, the polymers form rod-like structures with shorter PEG chains, which gradually change into sheets as the chain length is increased. In tetrahydrofuran, thin films are observed using short linkers, which gradually transform into vesicles and nanorings when the length of PEG is increased. This study not only provides a convenient method for the preparation of fluorescent metallacycle-cored supramolecular polymers via the thiol–ene reaction, but also reveals the influence of the length of the linker and the solvent on their morphology, which will pave a way for the preparation of supramolecular polymers with the desired morphology for diverse applications.

A clickable initiator, pentafluoro benzyl bromide, has been investigated for the cationic ring opening polymerization of poly(2-oxazolines). Additionally, the clickable alpha end group was then utilized in a para-fluoro-thiol click reaction to synthesise linear diblock, tetrablock, multiblock copolymers as well as star shaped poly(2-oxazoline)s using dithiol compounds as terminating agents. Thus, a one-pot approach combining the para-fluoro-thiol click reaction and direct termination of the poly(2-oxazoline) living chain end with 4,4-thiobisbenzenethiol has been performed to prepare multiblock copolymers of poly(2-ethyl-2-oxazoline) (PEtOx) and poly((2-ethyl-2-oxazoline)-b-(2-methyl-2-oxazoline) (PEtOx-mb-PMeOx). All obtained polymers were characterized by Size Exclusion Chromatography (SEC), 1H Nuclear Magnetic Resonance (NMR) and Matrix-Assisted Laser Desorption/Ionization-Time of Flight (MALDI-ToF) mass spectrometry. Last but not least, the self-assembly properties of prepared amphiphilic polymers were studied with DLS and TEM. Nanoparticles with a diameter ranging from 184 nm to 250 nm were observed in TEM for PEtOx-mb-PMeOx copolymers.

The establishment of both mechanically robust yet facile healable and recyclable epoxy resin systems are highly desirable and still present significant challenges. Herein, by fully utilizing epoxidized vegetable oils and dithiol modified boronic ester via the thermally-induced “thiol–epoxy” click reaction, novel plant oil-based epoxy resins were successfully synthesized by incorporating units of dioxaborolane metathesis, transesterification and disulfide metathesis. Reasonably tuning the content of the flexible long fatty acid chains and phenylboronic ester, the plant oil-based epoxy resins possessed highly crosslinking structures and comparable mechanical properties to the conventional epoxy resins, with the tensile strength of up to 43.2 MPa and the elongation at break up to 25%. Moreover, the epoxy resins well embodied dynamic dioxaborolane, disulfide bonds and soft long fatty acid chains, which facilitated facile healing ability and reprocessability at mild conditions. The self-healing efficiency of bio-based epoxy resins could reach 90% at room temperature in 24 h. Further, the mechanical properties of the recycled resins were maintained at 80% of original resins even after 9 times repeated reprocessing.

A promising strategy for new electrically conductive coordination polymers is the combination of d10 metal ions, which tolerate short metal···metal distances, with dithiolene linkers, known for their "non-innocent" redox behavior. This study explores the coordination chemistry of 2,3-pyrazinedithiol (H2pdt) toward Cu+ and Ag+ ions, highlighting similarities and differences. The synthetic approach, starting with the fully protonated ligand, allowed the isolation of a homoleptic bis(dithiolene) complex with formal CuI atoms, [Cu(H2pdt)2]Cl (1). This complex was further transformed to a 1D coordination polymer with short metal···metal distances, 1D[Cu(Hpdt)] (2Cu). The larger Ag+ ion directly built up a very similar coordination polymer, 1D[Ag(Hpdt)] (2Ag), without any appearance of an intermediate metal complex. The coordination polymer 1D[Cu(H2pdt)I] (4), like complex 1, bears fully protonated H2pdt ligands in their dithione form. Upon heating, both compounds underwent auto-oxidation coupled with a dehydrogenation of the ligand to form the open-shell neutral copper(II) complex [Cu(Hpdt)2] (3) and the coordination polymer 1D[Cu2I2(H2pdt)(Hpdt)] (5), respectively. For all presented compounds, crystal structures are discussed in-depth. Furthermore, properties of 1, 3, and those of the three 1D coordination polymers, 2Ag, 2Cu, and 4, were investigated by UV-vis-NIR spectroscopy, cyclic voltammetry, and variable-temperature magnetic susceptibility, and direct current (dc)-conductivity measurements. The experimental results are compared and discussed with the aid of DFT simulations.

Technology for the transformation of waste feathers to quality regenerated filaments has been developed. Regardless of superior properties of natural keratin materials, previously developed regenerated materials from keratin had tensile properties much lower than their natural counterparts due to backbone hydrolysis and inefficient reconstruction of disulfide crosslinkages. In this work, tough keratin filaments have been regenerated from white duck feathers via efficient restoration of disulfide crosslinkages using a dithiol reducing agent. Dithiol substantially reserves free thiol groups in the extraction and formed lengthy intermolecular crosslinkages in regenerated keratin filaments. Due to the high degree of intermolecular reconstruction of disulfide bonds and formation of lengthy crosslinkages via dithiol chain-extension, the keratin filaments exhibited considerable improvements in mechanical properties, especially for ductility and water stability. The tenacity and elongation at break were 160.7 MPa and 14%, respectively. The filaments retained about 80% of the tenacity of natural feathers at either dry or wet conditions and demonstrated stretchability 150% higher than natural feathers. The fiber regeneration technology makes it possible to substitute primary fiber sources by renewable poultry feathers. Successful filament substitution or addition can bring more than 88-billion-dollar revenue. The technology not only contributes to a sustainable fiber and poultry industry but adds substantial values to poultry feathers.

We report a facile strategy for engineering diverse particles based on the supramolecular assembly of natural polyphenols and a self-polymerizable aromatic dithiol. In aqueous conditions, uniform and size-tunable supramolecular particles are assembled through π–π interactions as mediated by polyphenols. Owing to the high binding affinity of phenolic motifs present at the surface, these particles allow for the subsequent deposition of various materials (i.e., organic, inorganic, and hybrid components), producing a variety of monodisperse functional particles. Moreover, the solvent-dependent disassembly of the supramolecular networks enables their removal, generating a wide range of corresponding hollow structures including capsules and yolk–shell structures. The versatility of these supramolecular networks, combined with their negligible cytotoxicity provides a pathway for the rational design of a range of particle systems (including core–shell, hollow, and yolk–shell) with potential in biomedical and environmental applications., Monodisperse colloidal particles with tunable properties show promise for biomedical, energy, and environmental applications and simple routes for fabricating these particles are of interest. Here, the authors report a facile strategy for fabrication of diverse particles based on the supramolecular assembly of phenols and self-polymerizable thiols

Structures of monothiol and dithiol glutaredoxin-1 from C. oremlandii are reported. Monothiol glutaredoxin-1 formed domain-swapped structures, one of which was in a hetero-oligomer complex., Protein dimerization or oligomerization resulting from swapping part of the protein between neighboring polypeptide chains is known to play a key role in the regulation of protein function and in the formation of protein aggregates. Glutaredoxin-1 from Clostridium oremlandii (cGrx1) was used as a model to explore the formation of multiple domain-swapped conformations, which were made possible by modulating several hinge-loop residues that can form a pivot for domain swapping. Specifically, two alternative domain-swapped structures were generated and analyzed using nuclear magnetic resonance (NMR), X-ray crystallography, circular-dichroism spectroscopy and hydrogen/deuterium-exchange (HDX) mass spectrometry. The first domain-swapped structure (β3-swap) was formed by the hexameric cGrx1–cMsrA complex. The second domain-swapped structure (β1-swap) was formed by monothiol cGrx1 (C16S) alone. In summary, the first domain-swapped structure of an oxidoreductase in a hetero-oligomeric complex is presented. In particular, a single point mutation of a key cysteine residue to serine led to the formation of an intramolecular disulfide bond, as opposed to an intermolecular disulfide bond, and resulted in modulation of the underlying free-energy landscape of protein oligomerization.

We demonstrated the solution-processed CuIn(S,Se)2 solar cells using a diamine/dithiol cosolvent. Compared to the traditional CIGS materials made with the Selenization process, we fabricated CISSe ...

The synthesis and crystal structure are reported for a five-coordinate cobalt di­thiol­ene-phosphine complex [Co(pdt)2(PTA)] (pdt = phenyl­dithiol­ene; S2C2Ph2), produced by PTA ligand-induced cleavage of the cobalt bis­(di­thiol­ene) dimer [Co2(pdt)4]., The title compound, bis­(1,2-diphenyl-2-sulfanyl­idene­ethane­thiol­ato-κ2 S,S′)(1,3,5-tri­aza-7-phosphaadamantane-κP)cobalt(II) dichloromethane hemisolvate, [Co(pdt)2(PTA)]·0.5C2H4Cl2 or [Co(C14H10S2)2(C6H12N3P)]·0.5C2H4Cl2, contains two phenyl­dithiol­ene (pdt) ligands and a 1,3,5-tri­aza-7-phosphaadamantane (PTA) ligand bound to cobalt with the solvent 1,2-di­chloro­ethane mol­ecule located on an inversion center. The cobalt core exhibits an approximately square-pyramidal geometry with partially reduced thienyl radical monoanionic ligands. The supra­molecular network is consolidated by hydrogen-bonding inter­actions primarily with nitro­gen, sulfur and chlorine atoms, as well as parallel displaced π-stacking of the aryl rings. The UV–vis, IR, and CV data are also consistent with monoanionic di­thiol­ene ligands and an overall CoII oxidation state.

International audience; We synthesized a generation of water-soluble, atomically precise gold nanoclusters (Au NCs) with anisotropic surface containing a short dithiol pegylated chain (AuMHA/TDT). The AuMHA/TDT exhibit a high brightness (QY ∼ 6%) in the shortwave infrared (SWIR) spectrum with a detection above 1250 nm. Furthermore, they show an extended half-life in blood (t 1/2ß = 19.54 ± 0.05 h) and a very weak accumulation in organs. We also developed a non-invasive, whole-body vascular imaging system in the SWIR window with high-resolution, benefiting from a series of Monte Carlo image processing. The imaging process enabled to improve contrast by 1 order of magnitude and enhance the spatial resolution by 59%. After systemic administration of these nanoprobes in mice, we can quantify vessel complexity in depth (>4 mm), allowing to detect very subtle vascular disorders non-invasively in bone morphogenetic protein 9 (Bmp9)-deficient mice. The combination of these anisotropic surface charged Au NCs plus an improved SWIR imaging device allows a precise mapping at high-resolution and an in depth understanding of the organization of the vascular network in live animals. KEYWORDS: shortwave infrared fluorescence, gold nanoclusters, vascular disorder, Monte Carlo restoration imaging processing, bone morphogenetic protein 9 (Bmp9)

Thiol-ene cationic and radical reactions were conducted for 1:1 addition between a thiol and vinyl ether, and also for cyclization and step-growth polymerization between a dithiol and divinyl ether. p-Toluenesulfonic acid (PTSA) induced a cationic thiol-ene reaction to generate a thioacetal in high yield, whereas 2,2'-azobisisobutyronitrile resulted in a radical thiol-ene reaction to give a thioether, also in high yield. The cationic and radical addition reactions between a dithiol and divinyl ether with oxyethylene units yielded amorphous poly(thioacetal)s and crystalline poly(thioether)s, respectively. Under high-dilution conditions, the cationic and radical reactions resulted in 16- and 18-membered cyclic thioacetal and thioether products, respectively. Furthermore, concurrent cationic and radical step-growth polymerizations were realized using PTSA under UV irradiation to produce polymers having both thioacetal and thioether linkages in the main chain.

A new series of 2-(dialkylamino)-1,3-dithiol-2-ylium cations derived from acetophenones and propiophenones was synthesized by the intramolecular condensation of appropriate substituted dithiocarbamates. The structural characterization of the new compounds has been performed by NMR and IR analysis. The structure of 1,3-dithiol-2-ylium perchlorate 3e has been proved by X-Ray analysis.

Naphthalenediimides (NDI) fused with two 2-(1,3-dithiol-2-ylidene)acetonitrile moieties (NDI-DTYA2), a novel strong electron-deficient monomer, was designed and readily synthesized by aromatic nucleophilic substitution to develop n-type polymers. Two NDI-DTYA2 based donor–acceptor (D–A) polymers P(NDI-DTYA2–1T) and P(NDI-DTYA2–2T) have been prepared (1T = thiophene, 2T = 2,2′-bithiophene) and showed low-lying LUMO energies (