Browse
Submit Data
Databases
API
Help

Dataset Information

10 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Defective Ultrathin ZnIn₂ S₄ for Photoreductive Deuteration of Carbonyls Using D₂ O as the Deuterium Source.

ABSTRACT: Deuterium (D) labeling is of great value in organic synthesis, pharmaceutical industry, and materials science. However, the state-of-the-art deuteration methods generally require noble metal catalysts, expensive deuterium sources, or harsh reaction conditions. Herein, noble metal-free and ultrathin ZnIn₂ S₄ (ZIS) is reported as an effective photocatalyst for visible light-driven reductive deuteration of carbonyls to produce deuterated alcohols using heavy water (D₂ O) as the sole deuterium source. Defective two-dimensional ZIS nanosheets (D-ZIS) are prepared in a surfactant assisted bottom-up route exhibited much enhanced performance than the pristine ZIS counterpart. A systematic study is carried out to elucidate the contributing factors and it is found that the in situ surfactant modification enabled D-ZIS to expose more defect sites for charge carrier separation and active D-species generation, as well as high specific surface area, all of which are beneficial for the desirable deuteration reaction. This work highlights the great potential in developing low-cost semiconductor-based photocatalysts for organic deuteration in D₂ O, circumventing expensive deuterium reagents and harsh conditions.

SUBMITTER: Han C

PROVIDER: S-EPMC8787392 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Mild, Selective Ru-Catalyzed Deuteration Using D2 O as a Deuterium Source.

Project description:A method for the selective deuteration of polyfunctional organic molecules using catalytic amounts of [RuCl2 (PPh3 )3 ] and D2 O as a deuterium source is presented. Through variation of additives like CuI, KOH, and various amounts of zinc powder, orthogonal chemoselectivities in the deuteration process are observed. Mechanistic investigation indicates the presence of different, defined Ru-complexes under the given specific conditions.

| S-EPMC6972544 | biostudies-literature

Visible-light-mediated deuteration of silanes with deuterium oxide.

Project description:Isotopically labeled compounds are highly desirable as they can serve as both mechanistic probes in chemistry and diagnostic tools in medicinal research. Herein, we report an unprecedented visible-light-mediated metal-free deuteration of silanes using D2O as an inexpensive, readily available, and easy to handle deuterium source. A broad range of aryl- and alkyl-substituted silanes were deuterated with high deuterium incorporations and yields. Furthermore, a 100 gram-scale synthesis was demonstrated using continuous-flow micro-tubing reactors, where enhanced reaction efficiency was obtained. The photoredox-catalyzed polarity matched hydrogen atom transfer (HAT) between silanes and the thiol HAT catalyst was responsible for the efficient deuteration.

| S-EPMC6764258 | biostudies-literature

Benzylic deuteration of alkylnitroaromatics via amine-base catalysed exchange with deuterium oxide.

Project description:This paper describes the deuterium-labelling of alkylnitroaromatics by base-catalysed exchange with deuterium oxide. As the alkyl protons alpha to the aromatic ring are the most acidic sites in the molecule, regioselective hydrogen isotope exchange at this benzylic location leads to a regiospecifically deuterated product. The exchange labelling takes place in good yields and with high atom% abundance in the presence of an appropriate nitrogen base. Alkylated 2,4-dinitrobenzenes deuterate at room temperature under catalysis by triethylamine, whilst alkylated 2-nitro- or 4-nitrobenzenes and related mono-nitroaromatics require higher temperatures and catalysis by 1,5-diazobicyclo[4.3.0]non-5-ene (DBN). The labelling reactions require an inert gas atmosphere, but otherwise are simple and high yielding with no obvious byproducts. Those compounds in which the benzylic protons are in an ortho-orientation with respect to the nitro group label somewhat more slowly than the analogues where there is a para relationship. In addition, higher alkyl homologues undergo benzylic deuteration at slower rates than methyl.

| S-EPMC10107807 | biostudies-literature

Hexicon 2: automated processing of hydrogen-deuterium exchange mass spectrometry data with improved deuteration distribution estimation.

Project description:Hydrogen-deuterium exchange (HDX) experiments analyzed by mass spectrometry (MS) provide information about the dynamics and the solvent accessibility of protein backbone amide hydrogen atoms. Continuous improvement of MS instrumentation has contributed to the increasing popularity of this method; however, comprehensive automated data analysis is only beginning to mature. We present Hexicon 2, an automated pipeline for data analysis and visualization based on the previously published program Hexicon (Lou et al. 2010). Hexicon 2 employs the sensitive NITPICK peak detection algorithm of its predecessor in a divide-and-conquer strategy and adds new features, such as chromatogram alignment and improved peptide sequence assignment. The unique feature of deuteration distribution estimation was retained in Hexicon 2 and improved using an iterative deconvolution algorithm that is robust even to noisy data. In addition, Hexicon 2 provides a data browser that facilitates quality control and provides convenient access to common data visualization tasks. Analysis of a benchmark dataset demonstrates superior performance of Hexicon 2 compared with its predecessor in terms of deuteration centroid recovery and deuteration distribution estimation. Hexicon 2 greatly reduces data analysis time compared with manual analysis, whereas the increased number of peptides provides redundant coverage of the entire protein sequence. Hexicon 2 is a standalone application available free of charge under http://hx2.mpimf-heidelberg.mpg.de.

| S-EPMC4018513 | biostudies-literature

Enhanced Photocatalytic Hydrogen Production of ZnIn2S4 by Using Surface-Engineered Ti3C2Tx MXene as a Cocatalyst.

Project description:Developing efficient and stable photocatalysts is crucial for photocatalytic hydrogen production. Cocatalyst loading is one of the effective strategies for improving photocatalytic efficiency. Here, Ti3C2Tx (Tx = F, OH, O) nanosheets have been adopted as promising cocatalysts for photocatalytic hydrogen production due to their metallic conductivity and unique 2D characterization. In particular, surface functionalized Ti3C2(OH)x and Ti3C2Ox cocatalysts were synthesized through the alkalization treatment with NaOH and a mild oxidation treatment of Ti3C2Fx, respectively. ZnIn2S4/Ti3C2Tx composites, which were fabricated by the in-situ growth of ZnIn2S4 nanosheets on the Ti3C2Tx surface, exhibited the promoted photocatalytic performance, compared with the parent ZnIn2S4. The enhanced photocatalytic performance can be further optimized through the surface functionalization of Ti3C2Fx. As a result, the optimized ZnIn2S4/Ti3C2Ox composite with oxygen functionalized Ti3C2Ox cocatalyst demonstrated excellent photocatalytic hydrogen evolution activity. The characterizations and density functional theory calculation suggested that O-terminated Ti3C2Ox could effectively facilitate the transfer and separation of photogenerated electrons and holes due to the formation of a Schottky junction, with the largest difference in work function between ZnIn2S4 and Ti3C2Ox. This work paves the way for photocatalytic applications of MXene-based photocatalysts by tuning their surface termination groups.

| S-EPMC10059248 | biostudies-literature

Surface modification of ZnIn2S4 layers to realize energy-transfer-mediated photocatalysis.

Project description:Photocatalytic selective aerobic oxidation reactions are crucial in designing advanced organic intermediates, but suffer from low conversion efficiency. Hence, activating O2 to create suitable reactive oxygen species, such as singlet oxygen (1O2), can significantly increase the yield of desired products. Herein, using ZnIn2S4 nanosheets as a model system, we build a surface-modified theoretical structure, where a surface-covered non-conductive macromolecular chain, polyvinyl pyrrolidone (PVP), is bound to ZnIn2S4 and influences the O2 adsorption process. PVP on the surface significantly changes the electronic structure and suppresses electron conduction of ZnIn2S4 nanosheets. Therefore, abundantly photogenerated and long-lived species transfer their energy to physically absorbed O2 to efficiently generate 1O2, which can oxidize sulphides into their corresponding sulphoxides. For sulphoxidation of different sulphides, surface modification brings a 3-9-fold increase in conversion efficiency and high selectivities ≥98%. This study provides a feasible way of boosting 1O2-generation-related photocatalytic reactions.

| S-EPMC9671662 | biostudies-literature

Continuous-Flow Synthesis of Deuterium-Labeled Antidiabetic Chalcones: Studies towards the Selective Deuteration of the Alkynone Core.

Project description:Flow chemistry-based syntheses of deuterium-labeled analogs of important antidiabetic chalcones were achieved via highly controlled partial C?C bond deuteration of the corresponding 1,3-diphenylalkynones. The benefits of a scalable continuous process in combination with on-demand electrolytic D2 gas generation were exploited to suppress undesired over-reactions and to maximize reaction rates simultaneously. The novel deuterium-containing chalcone derivatives may have interesting biological effects and improved metabolic properties as compared with the parent compounds.

| S-EPMC6273355 | biostudies-literature

Protruding Pt single-sites on hexagonal ZnIn2S4 to accelerate photocatalytic hydrogen evolution.

Project description:Single-site cocatalysts engineered on supports offer a cost-efficient pathway to utilize precious metals, yet improving the performance further with minimal catalyst loading is still highly desirable. Here we have conducted a photochemical reaction to stabilize ultralow Pt co-catalysts (0.26 wt%) onto the basal plane of hexagonal ZnIn2S4 nanosheets (PtSS-ZIS) to form a Pt-S3 protrusion tetrahedron coordination structure. Compared with the traditional defect-trapped Pt single-site counterparts, the protruding Pt single-sites on h-ZIS photocatalyst enhance the H2 evolution yield rate by a factor of 2.2, which could reach 17.5 mmol g-1 h-1 under visible light irradiation. Importantly, through simple drop-casting, a thin PtSS-ZIS film is prepared, and large amount of observable H2 bubbles are generated, providing great potential for practical solar-light-driven H2 production. The protruding single Pt atoms in PtSS-ZIS could inhibit the recombination of electron-hole pairs and cause a tip effect to optimize the adsorption/desorption behavior of H through effective proton mass transfer, which synergistically promote reaction thermodynamics and kinetics.

| S-EPMC8917206 | biostudies-literature

Surface Coordination of Pd/ZnIn2S4 toward Enhanced Photocatalytic Activity for Pyridine Denitrification.

Project description:New surface coordination photocatalytic systems that are inspired by natural photosynthesis have significant potential to boost fuel denitrification. Despite this, the direct synthesis of efficient surface coordination photocatalysts remains a major challenge. Herein, it is verified that a coordination photocatalyst can be constructed by coupling Pd and CTAB-modified ZnIn2S4 semiconductors. The optimized Pd/ZnIn2S4 showed a superior degradation rate of 81% for fuel denitrification within 240 min, which was 2.25 times higher than that of ZnIn2S4. From the in situ FTIR and XPS spectra of 1% Pd/ZnIn2S4 before and after pyridine adsorption, we find that pyridine can be selectively adsorbed and form Zn⋅⋅⋅C-N or In⋅⋅⋅C-N on the surface of Pd/ZnIn2S4. Meanwhile, the superior electrical conductivity of Pd can be combined with ZnIn2S4 to promote photocatalytic denitrification. This work also explains the surface/interface coordination effect of metal/nanosheets at the molecular level, playing an important role in photocatalytic fuel denitrification.

| S-EPMC9822349 | biostudies-literature

Stereoretentive Deuteration of α-Chiral Amines with D2O.

Project description:We present the direct and stereoretentive deuteration of primary amines using Ru-bMepi (bMepi = 1,3-(6'-methyl-2'-pyridylimino)isoindolate) complexes and D2O. High deuterium incorporation occurs at the α-carbon (70-99%). For α-chiral amines, complete retention of stereochemistry is achieved when using an electron-deficient Ru catalyst. The retention of enantiomeric purity is attributed to a high binding affinity of an imine intermediate with ruthenium, as well as to a fast H/D exchange relative to ligand dissociation.

| S-EPMC6578574 | biostudies-literature