Photocatalytic Enantioselective Radical Cascade Multicomponent Minisci Reaction of ß-Carbolines Using Diazo Compounds as Radical Precursors.

Here, a photocatalytic asymmetric multicomponent cascade Minisci reaction of ß-carbolines with enamides and diazo compounds is reported, enabling an effective enantioselective radical C─H functionalization of ß-carbolines with high yields and enantioselectivity (up to 83% yield and 95% ee). This enantioselective multicomponent Minisci protocol exhibits step economy, high chemo-/enantio-selective control, and good functional group tolerance, allowing access to a variety of valuable chiral ß-carbolines. Notably, diazo compounds are suitable radical precursors in enantioselective cascade radical reactions. Moreover, the efficiency and practicality of this approach are demonstrated by the asymmetric synthesis of bioactive compounds and natural products.

Chiral Cpx Rhodium(III)-Catalyzed Enantioselective Aziridination of Unactivated Terminal Alkenes.

Chiral cyclopentadienyl-rhodium(III) Cpx Rh(III) catalysis has been demonstrated to be competent for catalyzing highly enantioselective aziridination of challenging unactivated terminal alkenes and nitrene sources. The chiral Cpx Rh(III) catalysis system exhibited outstanding catalytic performance and wide functional group tolerance, yielding synthetically important and highly valuable chiral aziridines with good to excellent yields and enantioselectivities (up to 99 % yield, 93 % ee). This protocol presents a novel and effective strategy for synthesizing enantioenriched aziridines from simple alkenes. Various transformations were performed on the aziridine products, illustrating the versatility and synthetic potential of this protocol for constructing highly functionalized compounds.

Significantly improved thermoelectric performance of SnSe originating from collaborative adjustment between valence and conduction bands, mass fluctuations, and local strain.

In this study, environmentally friendly, low cost, and easy to synthesize InSn and VSn co-doped SnSe materials was designed and prepared via vacuum melting and spark plasma sintering technology, which avoids the shortcomings of high-performance Pb, Ge, and Na-doped SnSe samples. InSn and VSn, doping achieved appropriate bandgap (Eg) and energy band degeneracy (NV) from the valence and conduction band, obtaining the highest electrical conductivity of 4726 S m-1 at 773 K. The impurity state controls the carrier transport process below 573 K, while Eg and NV control the process above 573 K. InSn and VSn doping induces quality fluctuation and local strain, which decreases the lattice thermal conductivity. Owing to the higher power factor and low lattice thermal conductivity, the ZT value of the Sn0.985In0.01Se sample was 1.3 at 773 K. Dual regulation of the valence and conduction band provides a new idea for adjusting the transport behavior of semiconductors.

Photocatalytic enantioselective Minisci reaction of ß-carbolines and application to natural product synthesis.

A highly efficient enantioselective direct C-H functionalization of ß-carbolines via a Minisci-type radical process under a photo-redox and chiral phosphoric acid cooperative catalytic system has been disclosed. Through this protocol, a wide range of C1 aminoalkylated ß-carbolines were constructed directly with high levels of enantioselectivities from readily available ß-carbolines and alanine-derived redox-active esters. This transformation allows straightforward access to highly valuable enantioenriched ß-carbolines, which are an intriguing structural motif in valuable natural products and synthetic bio-active compounds. This protocol has been utilized as a highly efficient synthetic strategy for the concise asymmetric total synthesis of marine alkaloids eudistomin X, (+)-eudistomidin B and (+)-eudistomidin I.

Surface-Induced Desolvation of Hydronium Ion Enables Anatase TiO2 as an Efficient Anode for Proton Batteries.

Hydrogen ion is an attractive charge carrier for energy storage due to its smallest radius. However, hydrogen ions usually exist in the form of hydronium ion (H3O+) because of its high dehydration energy; the choice of electrode materials is thus greatly limited to open frameworks and layered structures with large ionic channels. Here, the desolvation of H3O+ is achieved by using anatase TiO2 as anodes, enabling the H+ intercalation with a strain-free characteristic. Density functional theory calculations show that the desolvation effects are dependent on the facets of anatase TiO2. Anatase TiO2 (001) surface, a highly reactive surface, impels the desolvation of H3O+ into H+. When coupled with a MnO2 cathode, the proton battery delivers a high specific energy of 143.2 Wh/kg at an ultrahigh specific power of 47.9 kW/kg. The modulation of the interactions between ions and electrodes opens new perspectives for battery optimizations.

Symmetric and asymmetric overgrowth of a Ag shell onto gold nanorods assisted by Pt pre-deposition.

The plasmonic properties of noble metallic nanoparticles could be tuned by morphology and composition, enabling opportunities for applications in sensors, photocatalysis, biomedicine, and energy conversion. Here, we report a method of the symmetric and asymmetric overgrowth of a Ag shell onto gold nanorods assisted by Pt pre-deposition via a 2-step approach. Firstly, gold nanorods (AuNRs), synthesized via a seed-mediated method, were used as seeds to form a AuNR-Pt structure, by using K2PtCl4 as the precursor. In this step, most of the Pt material was selectively deposited on the tips of the AuNR. Secondly, by using AgNO3 as the precursor, a Ag shell was overgrown on the surface of the AuNRs-Pt nanoparticles, resulting in a (AuNR-Pt)-Ag core-shell tri-metallic nanostructure. Due to the surface energy and lattice matching between Au and Ag, the Ag shell preferred to be epitaxially overgrown on the side of AuNR. The Ag shell thickness and symmetry of the (AuNR-Pt)-Ag could be tuned by changing the amounts of AgNO3 precursor. With the increase of the Ag shell thickness, the (AuNR-Pt)-Ag nanostructures changed from symmetric to asymmetric. The obtained (AuNR-Pt)-Ag nanostructures were studied using UV-vis-NIR spectroscopy, transmission electron microscopy, EDS mapping, DLS, and ICP-MS. The growth mechanism was discussed.

Balsam-pear-like rutile/anatase core/shell titania nanorod arrays for photoelectrochemical water splitting.

In this work, a solution combustion followed by dissolution in hydrogen peroxide is adopted to achieve a precursor for decorating anatase TiO2 nanosheets along single-crystalline rutile TiO2 nanorods, which achieves balsam-pear-like core/shell nanorod arrays with enhanced photoelectrochemical water splitting. The enhanced photoelectrochemical performance is attributed to the novel nanoarchitecture, which can simultaneously offer a high surface area, enhanced light-harvesting, a rutile/anatase junction for charge carrier separation and a conductive pathway for charge carrier collection. The photoanode design can also give hints to other functional materials.