Engineering Thermally Reduced Graphene Oxide for Synchronously Enhancing Photocatalytic Activity and Photothermal Effect.

The structural composition of reduced graphene oxide (rGO) can be modified and controlled by appropriate reduction methods to modulate its electronic structure, rendering it a versatile platform for tailoring optoelectronic and catalytic properties. Nevertheless, it is uncommon to concurrently amplify the photocatalytic and photothermal effects when regulating and utilizing pure rGO. Here, we investigate the impact of structural variations in thermally reduced graphene oxide (TGO) on its photocatalytic and photothermal properties.

Heterogeneity of dispersed species in nickel-loaded carbon-based catalysts for near-infrared photoresponsive synergistic antimicrobial therapy.

The development of novel efficient, safe antimicrobial strategies is an urgent need, as the misuse of antibiotics has become a significant threat to human health. Therefore, we have loaded metal Ni with environmentally friendly carbon black as a substrate, with species varying from single atoms to nanoclusters and nanoparticles. The results obtained from the antimicrobial systems and the role of different types of metal species in the photosensitized antimicrobial reactions were compared to better understand the catalytic behavior of different metal entities (single atoms, nanoclusters, and nanoparticles).

Unraveling the atomic-level vacancy modulation in CuS for NIR-driven efficient inhibition of drug-resistant bacteria: Key role of Cu vacancy position.

CuS possesses high hole concentration and potential superior electrical conductivity as a novel p-type semiconductor, whose biological applications remain largely unexploited. Encouraged by our recent work that CuS has enzyme-like antibacterial activity in the absence of light, which may further enhance the near infrared (NIR) antibacterial performance. Moreover, vacancy engineering can modulate the electronic structure of the nanomaterials and thus optimize their photocatalytic antibacterial activities.

A "Pre-Division Metal Clusters" Strategy to Mediate Efficient Dual-Active Sites ORR Catalyst for Ultralong Rechargeable Zn-Air Battery.

To conquer the bottleneck of sluggish kinetics in cathodic oxygen reduction reaction (ORR) of metal-air batteries, catalysts with dual-active centers have stood out. Here, a "pre-division metal clusters" strategy is firstly conceived to fabricate a N,S-dual doped honeycomb-like carbon matrix inlaid with CoN sites and wrapped Co P nanoclusters as dual-active centers (Co P/CoN @NSC-500). A crystalline {Co } coordination cluster divided by periphery second organic layers is well-designed to realize delocalized dispersion before calcination.

Vacancy-Modulated of CuS for Highly Antibacterial Efficiency via Photothermal/Photodynamic Synergetic Therapy.

Cu-based nanomaterials have been developed to alleviate the problem of antibiotic resistance due to their superior properties and good biocompatibility. Defects in nanomaterials have a major role in improving photocatalytic performance. Herein, two CuS nanospheres with predominant V and V vacancy (abbreviated as CuS and CuS-T150, respectively) characterized by positron annihilation spectra are synthesized.

Homochiral Eu@MOF Composite for the Enantioselective Detection and Separation of (/)-Ornidazole.

The development of homochiral materials for the enantioselective detection and separation of chiral drugs is in high demand for the pharmaceutical industry. Herein, an anionic homochiral metal-organic framework (HMOF) with generated [MeNH] counterions, {[MeNH][Zn(d-L)(HCO)(OH)]·5HO} (HMOF-), was synthesized using a d-camphorate-derived enantiopure dicarboxylate ligand, 4,4'-[[(1,3)-1,2,2-trimethylcyclopentane-1,3-dicarbonyl]bis(azanediyl)]dibenzoic acid (d-HL) via a simple solvothermal method. Interestingly, HMOF- could be used as a parent framework to encapsulate Eu cations via an ion-exchange process, yielding an Eu@HMOF- composite with dual-luminescent centers.

Efficient photothermal and photodynamic synergistic antibacterial therapy of CuS nanosheets regulated by facet engineering.

The surface arrangements of nanomaterials can regulate their electronic structure, which will tune physicochemical properties of materials to various applications. In this study, two CuS nanosheets with (304) and (224) exposed facets were synthesized, respectively, and their antibacterial activity of different facets for replacing antibiotics to solve seriously drug-resistant bacteria were further measured. Experimental and theoretical computation results unveiled that CuS with (224) exposed facet exhibited excellent antibacterial activity through synergetic photodynamic and photothermal therapy against Gram-positive Bacillus subtilis, Gram-negative Escherichia coli and drug-resistant Pseudomonas aeruginosa under near-infrared light (808 nm) irradiation.

Electronic Structure Modulation of Ag S by Vacancy Engineering for Efficient Bacterial Infection.

Vacancy engineering can modulate the electronic structure of the material and thus contribute to the formation of coordination unsaturated sites, which makes it easier to act on the substrate. Herein, Ag S and Ag S-100, which mainly have vacancy associates V and V , respectively, are prepared and characterized by positron annihilation spectroscopy. Both experimental and theoretical calculation results indicate that Ag S-100 exhibits excellent antibacterial activity due to its appropriate bandgap and stronger bacteria-binding ability, which endow it with a superior antibacterial activity compared to Ag S in the absence of light.

Nucleophilic Substitution of P-Stereogenic Chlorophosphines: Mechanism, Stereochemistry, and Stereoselective Conversions of Diastereomeric Secondary Phosphine Oxides to Tertiary Phosphines.

A diastereomeric mixture of secondary phosphine oxide is stereospecifically converted to chlorophosphine salt by treatment with oxalyl chloride, which stereoselectively affords P-inverted or retained tertiary phosphines, depending on the substitution with aliphatic or aromatic Grignard reagents, respectively, in high to 99% yield and 99:1 dr. The repulsion of π-electron on aryl to lone electron pair on phosphorus is proposed for the P-retained substitution.

Nonepimerizing Alkylation of H-P Species to Stereospecifically Generate P-Stereogenic Phosphine Oxides: A Shortcut to Bidentate Tertiary Phosphine Ligands.

The secondary R-(-)-menthyl alkylphosphine oxide was confirmed as configurationally stable toward base and was used in base-promoted alkylation, stereospecifically affording P-retained bis or functional tertiary phosphine oxides in excellent yields. The alkylated products were deoxygenated using oxalyl chloride followed by ZnCl-NaBH to form P-inversed bidentate phosphine boranes in high stereoselectivities.

Preparation of Optically Pure Tertiary Phosphine Oxides via the Addition of P-Stereogenic Secondary Phosphine Oxide to Activated Alkenes.

Functionalized P,C-stereogenic tertiary phosphine oxides were prepared by the addition of (RP)-menthyl phenylphosphine oxide to activated olefins, in high drP and drC, and were isolated in excellent yields. The reaction was readily catalyzed by Ca(OH)2 or occurred with gentle heating. A wide range of substrates, including vinyl ketones, esters, nitriles, and nitro alkenes, can be used in the reaction.

Double Asymmetric Induction During the Addition of (RP)-Menthyl Phenyl Phosphine Oxide to Chiral Aldimines.

P,C-Stereogenic α-amino phosphine oxides were prepared from the addition of (RP )-menthyl phenyl phosphine oxide to chiral aldimines under neat condition at 80 °C in up to 91:9 drC and 99% yields. The diastereoselectivity was mainly induced by chiral phosphorus that showed matched or mismatched induction with (S)- or (R)-aldimines, respectively.