Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

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

ABSTRACT: 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.

SUBMITTER: Zhou R

PROVIDER: S-EPMC6764258 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

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

Zhou Rong R Li Jiesheng J Cheo Han Wen HW Chua Rachel R Zhan Gu G Hou Zhaomin Z Wu Jie J

Chemical science 20190708 31

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 D<sub>2</sub>O 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 wa ...[more]

PMID: 31588300

Similar Datasets

Visible Light-Mediated Organoboron-Catalyzed Metal-Free Synthesis of Silanols from Silanes.

Project description:Herein, a four-coordinated organoboron compound, aminoquinoline diarylboron (AQDAB), is utilized as the photocatalyst in the oxidation of silane to silanol. This strategy effectively oxidizes Si-H bonds, affording Si-O bonds. Generally, the corresponding silanols can be obtained in moderate to good yields at room temperature under oxygen atmospheres, representing a green protocol to complement the existing preparation methods for silanols.

| S-EPMC10222655 | 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

Visible-Light-Mediated Electrocatalytic Activity in Reduced Graphene Oxide-Supported Bismuth Ferrite.

Project description:Reduced graphene oxide (RGO)-supported bismuth ferrite (BiFeO3) (RGO-BFO) nanocomposite is synthesized via a two-step chemical route for photoelectrochemical (PEC) water splitting and photocatalytic dye degradation. The detailed structural analysis, chemical coupling, and morphology of BFO- and RGO-supported BFO are established through X-ray diffraction, Raman and X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy studies. The modified band structure in RGO-BFO is obtained from the UV-vis spectroscopy study and supported by density functional theory (DFT). The photocatalytic degradation of Rhodamine B dye achieved under 120 min visible-light illumination is 94% by the RGO-BFO composite with a degradation rate of 1.86 × 10-2 min-1, which is 3.8 times faster than the BFO nanoparticles. The chemical oxygen demand (COD) study further confirmed the mineralization of an organic dye in presence of the RGO-BFO catalyst. The RGO-BFO composite shows excellent PEC performance toward water splitting, with a photocurrent density of 10.2 mA·cm-2, a solar-to-hydrogen conversion efficiency of 3.3%, and a hole injection efficiency of 98% at 1 V (vs Ag/AgCl). The enhanced catalytic activity of RGO-BFO is explained on the basis of the modified band structure and chemical coupling between BFO and RGO, leading to the fast charge transport through the interfacial layers, hindering the recombination of the photogenerated electron-hole pair and ensuring the availability of free charge carriers to assist the catalytic activity.

| S-EPMC6045476 | biostudies-literature

Effect of deuterium oxide on Arabidopsis gene expression

2009-09-18 | GSE18153 | GEO

Successive redox-mediated visible-light ferrophotovoltaics.

Project description:Titanium oxide materials have multiple functions such as photocatalytic and photovoltaic effects. Ferroelectrics provide access to light energy conversion that delivers above-bandgap voltages arising from spatial inversion symmetry breaking, whereas their wide bandgap leads to poor absorption of visible light. Bandgap narrowing offers a potential solution, but this material modification suppresses spontaneous polarization and, hence, sacrifices photovoltages. Here, we report successive-redox mediated ferrophotovoltaics that exhibit a robust visible-light response. Our single-crystal experiments and ab initio calculations, along with photo-luminescence analysis, demonstrate that divalent Fe2+ and trivalent Fe3+ coexisted in a prototypical ferroelectric barium titanate BaTiO3 introduce donor and acceptor levels, respectively, and that two sequential Fe3+/Fe2+ redox reactions enhance the photogenerated power not only under visible light but also at photon energies greater than the bandgap. Our approach opens a promising route to the visible-light activation of photovoltaics and, potentially, of photocatalysts.

| S-EPMC7031293 | biostudies-literature

Visible-light-induced chemo-, diastereo- and enantioselective α-C(sp<sup>3</sup>)-H functionalization of alkyl silanes.

Project description:A catalytic asymmetric α-C(sp3)-H functionalization of alkyl silanes with benzosultams was realized by merging photoredox and chiral Lewis acid catalysis. The key to success was the choice of photocatalyst with an appropriate redox potential and non-nucleophilic solvent, providing a novel entry to chiral organosilanes containing two adjacent tri- and tetra-substituted stereocenters with high to efficient diastereo- and enantioselectivity (up to 99% ee, 94 : 6 dr) under mild reaction conditions. Based on the control experiment and spectral analysis, an initial single electron transfer reduction of a benzosultam-triggered simultaneous or stepwise electron transfer/proton transfer process was proposed to rationalize the favored C(sp3)-H functionalization rather than desilylation.

| S-EPMC10155911 | biostudies-literature

Graphene Oxide/BiOCl Nanocomposite Films as Efficient Visible Light Photocatalysts.

Project description:A novel graphene oxide/BiOCl (GO/BiOCl) nanocomposite film was prepared via a spread coating method. In visible-light photocatalytically degrading Rhodamine B (RhB) experiments, 2 wt% GO/BiOCl could degrade 99% of RhB within 1.5 h and the rate constant was 12.2 times higher than that of pure BiOCl. The degradation efficiency still kept at 80% even after 4 recycles, evidencing the relatively good recyclability. The enhancement was attributed to the improvement of visible light adsorption and charge separation. Holes and superoxide radicals· O2- played a major role as reactive species. The values of conduction band and valence band for GO and BiOCl were calculated and a new photocatalytic mechanism of GO/BiOCl nanocomposite was proposed.

| S-EPMC6066524 | biostudies-literature

Transcription profiling of Arabidopsis after deuterium oxide treatment

Project description:2H2O has a long history as a protein or amino acid labeling techinique, and such labeling systems have proven effective for many different types of studies. A disadvantage of a 2H2O labeling system is that plant growth is inhibited as the percentage of deuterium in the medium increases. However the molecular effects of 2H2O on plant growth has not previoulsly been investigated. To assist with the experimental design of proteomic 2H2O labeling studies, we used microarrays to determine the global effects of 2H2O on gene expression and to indentify genes which genes are effected by 2H2O treatment. Experiment Overall Design: RNA was prepared from Arabidopsis seedlings grown for seven days on either H2O control media or 30% 2H2O to examine the long-term effects of 2H2O treatment,and from seedlings shifted from H2O media to either 2H2O or H2O for 4 h to examine short-term effects on gene expression, and seedlings shifted from 2H2O to H2O for 4 h to examine recovery effects on gene expression.

2009-09-25 | E-GEOD-18153 | biostudies-arrayexpress

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

Direct sulfonylation of anilines mediated by visible light.

Project description:Sulfones feature prominently in biologically active molecules and are key functional groups for organic synthesis. We report a mild, photoredox-catalyzed reaction for sulfonylation of aniline derivatives with sulfinate salts, and demonstrate the utility of the method by the late-stage functionalization of drugs. Key features of the method are the straightforward generation of sulfonyl radicals from bench-stable sulfinate salts and the use of simple aniline derivatives as convenient readily available coupling partners.

| S-EPMC5868301 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data