Regulating the assembly and expansion of the silver cluster from the Ag to Ag nanowheel driven by heteroanions.

Precise control over the shape and size of metal nanoclusters through anion template-driven self-assembly is one of the key scientific goals in the nanocluster community, however, it is still not understood comprehensively. In this work, we report the controllable synthesis and atomically precise structures of silver nanowheels Ag37 and Ag46, using homo (Cl ions) and heteroanion (Cl and CrO ions) template strategies, along with macrocyclic -phenyl-thiacalix[4]arene and small PrS ligands. Structural analyses revealed that in Ag37, Cl ions serve as both local and global templates, whereas CrO ions function as local and Cl ions as global templates in Ag46, resulting in a pentagonal nanowheel (Ag37) and a hexagonal (Ag46) nanowheel.

Three-component selective synthesis of phenothiazines and bis-phenothiazines under metal-free conditions.

An iodine-containing reagent promoted three-component method for the selective synthesis of phenothiazines and bis-phenothiazines has been developed. The present protocol starts from simple and easily available cyclohexanones, elemental sulfur, and inorganic ammonium salts, selectively producing phenothiazines and bis-phenothiazines in satisfactory yields under aerobic conditions. This method has the advantages of simple and readily available starting materials and metal-free conditions, affording a facile and practical approach for the preparation of phenothiazines and bis-phenothiazines.

Synthesis of WO@WS core-shell nanostructures solution-based sulfurization for improved performance of water splitting.

High light absorption capacity and excellent charge transportation are significant for superior water-splitting performance. Here, WO/WS core-shell nanowire arrays were fabricated using a two-step hydrothermal method. The crystal phase, morphology, crystal structure, chemical composition, and optical properties were characterized using XRD, SEM, TEM, XPS, and UV-vis spectroscopy.

Comparative analysis of chloroplast genomes of endangered heterostylous species and its closely related species.

, well known for its heterostyly, is the largest genus in the family Primulaceae with more than 500 species. The considerable species number has introduced a huge challenge for taxonomy. The phylogenetic relationships among still maintain unresolved due to frequent hybridization and introgression between closely related species.

Notable Catalytic Activity of Transition Metal Thiolate Complexes against Hydrosilylation and Hydroboration of Carbon-Heteroatom Bonds.

Chemists tend to use transition metal hydride complexes rather than thiolate complexes to catalyse chemical transformations because the hydride complexes possess diverse catalytic reactivity, although most of them are air/moisture-sensitive and difficult to prepare. By comparing the catalytic performances of pincer ligated group 10 metal thiolate and hydride complexes in catalysing the hydroboration and hydrosilylation of C=O and C=N bonds, we demonstrate in this review that transition metal thiolate complexes are much better catalysts than the corresponding hydride complexes in catalysing this type of reactions. Many hydroboration and hydrosilylation reactions catalysed by pincer ligated group 10 metal hydride complexes can also be catalysed by the corresponding thiolate complexes and the thiolate systems are far more active.

Two-dimensional wide-bandgap GeSe vertical ultraviolet photodetectors with high responsivity and ultrafast response speed.

Germanium selenide (GeSe), as a typical member of 2D wide bandgap semiconductors (WBSs), shows great potential in ultraviolet (UV) optoelectronics due to its excellent flexibility, superior environmental stability, competitive UV absorption coefficient, and significant spectral selectivity. However, the GeSe-based UV photodetector suffers from high operation voltages and low photocurrent, which prevents its practical imaging applications. In this work, we report an elevated photocurrent generation in a vertical stacking graphene/GeSe/graphene heterostructure with low operation voltage and low power consumption.

Alkoxysulfonyl radical species: acquisition and transformation towards sulfonate esters through electrochemistry.

Sulfonyl radical mediated processes have been considered as a powerful strategy for the construction of sulfonyl compounds. However, an efficient and high atom-economical radical approach to the synthesis of sulfonate esters is still rare, owing to the limited tactics to achieve alkoxysulfonyl radicals. Herein, an electrochemical anodic oxidation of inorganic sulfites with alcohols is developed to afford alkoxysulfonyl radical species, which are utilized in subsequent alkene difunctionalization to provide various sulfonate esters.

Imaging of hypochlorous acid in mitochondria using an asymmetric near-infrared fluorescent probe with large Stokes shift.

Small-molecule near-infrared (NIR) imaging facilitates deep tissue penetration, low autofluorescence, non-invasive visualization, and a relatively simple operation. As such it has emerged as a popular technique for tracking biological species and events. However, the small Stokes shift of most NIR dyes often results in a low signal-to-noise ratio and self-quenching due to crosstalk between the excitation and emission spectra.

A switchable redox annulation of 2-nitroarylethanols affording -heterocycles: photoexcited nitro as a multifunctional handle.

The efficient transformation of nitroaromatics to functional molecules such as -heterocycles has been an attractive and significant topic in synthesis chemistry. Herein, a photoexcited nitro-induced strategy for switchable annulations of 2-nitroarylethanols was developed to construct -heterocycles including indoles, -hydroxyl oxindoles and -H oxindoles. The metal- and photocatalyst-free reaction proceeds through intramolecular redox C-N coupling of branched hydroxyalkyl and nitro units, which is initiated by a double hydrogen atom abstraction (-HAA) process.

Bicarbonate insertion triggered self-assembly of chiral octa-gold nanoclusters into helical superstructures in the crystalline state.

Constructing atomically precise helical superstructures of high order is an extensively pursued subject for unique aesthetic features and underlying applications. However, the construction of cluster-based helixes of well-defined architectures comes with a huge challenge owing to their intrinsic complexity in geometric structures and synthetic processes. Herein, we report a pair of unique and single stranded helical superstructures spontaneously assembled from - and -Au8c individual nanoclusters, respectively, upon selecting chiral BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthalene) and hydrophilic -HMBA (-mercaptobenzoic acid) as protective ligands to induce chirality and facilitate the formation of helixes.

Simple synthesis of a hierarchical LiMnFePO/C cathode by investigation of iron sources for lithium-ion batteries.

Iron (Fe) substitution is an effective strategy for improving the electrochemical performance of LiMnPO which has poor conductivity. Herein, we focus on investigating the effect of substitution of Mn with different iron sources, on the structure and electrochemical performances of the LiMnPO materials. The Fe-substituted LiMnPO/C composites were synthesized a simple and rational solid-state method, and will be of benefit for engineering applications.

Molecularly engineered AIEgens with enhanced quantum and singlet-oxygen yield for mitochondria-targeted imaging and photodynamic therapy.

Luminogens characteristic of aggregation-induced emission (AIEgens) have been extensively exploited for the development of imaging-guided photodynamic therapeutic (PDT) agents. However, intramolecular rotation of donor-acceptor (D-A) type AIEgens favors non-radiative decay of photonic energy which results in unsatisfactory fluorescence quantum and singlet oxygen yields. To address this issue, we developed several molecularly engineered AIEgens with partially "locked" molecular structures enhancing both fluorescence emission and the production of triplet excitons.

The transient-chelating-group-controlled stereoselective Rh(i)-catalyzed silylative aminocarbonylation of 2-alkynylanilines: access to ()-3-(silylmethylene)indolin-2-ones.

A new method involving mild acryl transient-chelating-group-controlled stereoselective Rh(i)-catalyzed silylative aminocarbonylation of 2-alkynylanilines with CO and silanes is presented for producing ()-3-(silylmethylene)indolin-2-ones. Upon using an acryl transient chelating group, 2-alkynylanilines undergo an unprecedented alkyne -silylrhodation followed by aminocarbonylation to assemble ()-3-(silylmethylene)indolin-2-ones. Mechanistic studies show that acryl transient chelating effects result in the key alkyne -silylrhodation process.

Access to chiral β-sulfonyl carbonyl compounds photoinduced organocatalytic asymmetric radical sulfonylation with sulfur dioxide.

An organocatalytic enantioselective radical reaction of potassium alkyltrifluoroborates, DABCO·(SO) and α,β-unsaturated carbonyl compounds under photoinduced conditions is developed, which provides an efficient pathway for the synthesis of chiral β-sulfonyl carbonyl compounds in good yields with excellent enantioselectivity (up to 96% ee). Aside from α,β-unsaturated carbonyl compounds with auxiliary groups, common chalcone substrates are also well compatible with this organocatalytic system. This method proceeds through an organocatalytic enantioselective radical sulfonylation under photoinduced conditions, and represents a rare example of asymmetric transformation involving sulfur dioxide insertion.

Ecological drivers of avian diversity in a subtropical landscape: Effects of habitat diversity, primary productivity and anthropogenic disturbance.

Understanding the roles of ecological drivers in shaping biodiversity is fundamental for conservation practice. In this study, we explored the effects of elevation, conservation status, primary productivity, habitat diversity and anthropogenic disturbance (represented by human population density and birding history) on taxonomic, phylogenetic and functional avian diversity in a subtropical landscape in southeastern China. We conducted bird surveys using 1-km transects across a total of 30 sites, of which 10 sites were located within a natural reserve.

Rhodium-catalyzed remote difunctionalization of arenes assisted by a relay directing group.

Rhodium-catalyzed diverse tandem twofold C-H bond activation reactions of -olefin-tethered arenes have been realized, with unsaturated reagents such as internal alkynes, dioxazolones, and isocyanates being the coupling partner as well as a relay directing group which triggers cyclization of the -olefin group under oxidative or redox-neutral conditions. The reaction proceeded initial -C-H activation assisted by a built-in directing group in the arene, and the -incorporation of the unsaturated coupling partner simultaneously generated a relay directing group that allows sequential C-H activation at the -position and subsequent cyclization of the -olefins. The overall reaction represents C-C or N-C difunctionalization of the arene with the generation of diverse 2,3-dihydrobenzofuran platforms.

A visible light/heat responsive covalent organic framework for highly efficient and switchable proton conductivity.

In recent years, covalent organic frameworks (COFs) have attracted enormous interest as a new generation of proton-exchange membranes, chemical sensors and electronic devices. However, to design high proton conductivity COFs, especially those with stimulus responsive performance remains a great challenge. Here, the first example of a light/heat switchable COF (COF-HNU9) has been synthesized by grafting a donor-acceptor Stenhouse adduct (DASA) within the channels of a β-ketoenamine-based COF.

A molecular recognition platform for the simultaneous sensing of diverse chemical weapons.

Chemical warfare agents (CWAs) such as phosgene and nerve agents pose serious threats to our lives and public security, but no tools can simultaneously screen multiple CWAs in seconds. Here, we rationally designed a robust sensing platform based on 8-cyclohexanyldiamino-BODIPY (BODIPY-DCH) to monitor diverse CWAs in different emission channels. -cyclohexanyldiamine as the reactive site provides optimal geometry and high reactivity, allowing -BODIPY-DCH to detect CWAs with a quick response and high sensitivity, while -BODIPY-DCH has much weaker reactivity to CWAs due to intramolecular H-bonding.

Correction: Ultrasensitive recognition of AP sites in DNA at the single-cell level: one molecular rotor sequentially self-regulated to form multiple different stable conformations.

[This corrects the article DOI: 10.1039/C9SC04140K.].

Simultaneous tracking of autophagy and oxidative stress during stroke with an ICT-TBET integrated ratiometric two-photon platform.

Over recent years, fluorescent probes exhibiting simultaneous responses to multiple targets have been developed for , real-time monitoring of cellular metabolism using two photon fluorescence sensing techniques due to numerous advantages including ease of operation, rapid reporting, high resolution, long visualization time and being non-invasive. However, due to interference from different fluorescence channels during simultaneous monitoring of multiple targets and the lack of ratiometric capability amongst the available probes, the accuracy in tracing metabolic processes has been restricted. With this research, using a through-bond energy transfer (TBET) mechanism, we designed a viscosity and peroxynitrite (ONOO) mitochondria-targeting two-photon ratiometric fluorescent probe Mito-ONOO.

Copper-catalyzed oxidative-coupling for one-pot synthesis of 5-aryl-1,4-disubstituted 1,2,3-triazoles under mild conditions.

A new reaction system with CuCl as catalyst, TEA as base and O/chloramine-T as oxidant was developed for one-pot oxidative-coupling to synthesize 5-aryl-1,4-disubstituted 1,2,3-triazoles in this paper. A variety of 5-arylated-1,2,3-triazole compounds could be efficiently prepared directly from the readily accessible organic azides, terminal alkynes and arylboronic acids. Advantages of the method include use of low-cost catalyst, clean oxidant, less-toxic additive, and low reaction temperature.

Comparative genomic analysis of provides insights into the evolutionary history of an incomplete denitrification pathway.

Biological denitrification is a crucial process in the nitrogen biogeochemical cycle, and has been reported to be a significant heterotrophic denitrifier in terrestrial geothermal environments. However, neither the denitrification potential nor the evolutionary history of denitrification genes in the genus or phylum is well understood. Here, we performed a comparative analysis of 23 genomes and identified denitrification genes in 15  strains.

Rapid electrochemical detection of MiRNA-21 facilitated by the excellent catalytic ability of Pt@CeO nanospheres.

Pt@CeO nanospheres (NSs) were first synthesized by simply mixing Ce(NO) and KPtCl under the protection of pure argon at 70 °C for 1 h, which exhibited excellent catalytic ability toward hydrogen peroxide (HO). An electrochemical biosensor was successfully developed using Pt@CeO NSs as a capture probe for the ultra-sensitive and fast detection of miRNA-21, a new type of biomarker for disease diagnostics, especially for cancer. During the step-by-step construction process of the RNA sensor, Pt@CeO NSs were functionalized with streptavidin (SA) to obtain SA-Pt@CeO NSs through amide bonds.

Efficient removal of bisphenol pollutants on imine-based covalent organic frameworks: adsorption behavior and mechanism.

The extensive use of bisphenol analogues in industry has aggravated the contamination of the water environment, and how to effectively remove them has become a research hotspot. This study presents two imine-based covalent organic frameworks with different pore sizes (COFs) [TAPB (1,3,5-tris(4-aminophenyl)benzene)-Dva (2,5-divinylterephthaldehyde)-PDA (terephthalaldehyde) (COF-1), and TAPB (1,3,5-tris(4-aminophenyl)benzene)-Dva (2,5-divinylterephthaldehyde)-BPDA (biphenyl dialdehyde) (COF-2)], which have achieved the efficient adsorption of bisphenol S (BPS) and bisphenol A (BPA). The maximum adsorption capacity of COF-2 for BPS and BPA obtained from Langmuir isotherms were calculated as 200.

Unveiling the abnormal capacity rising mechanism of MoS anode during long-term cycling for sodium-ion batteries.

Transition metal sulfides are considered as one of the most potential anode materials in sodium-ion batteries due to their high capacity, low cost, and rich resources. Among plenty of options, molybdenum sulfide (MoS) has been the focus of research due to the graphene-like layered structure and unique electrochemical properties. Importantly, an abnormal capacity increase phenomenon was observed in the MoS anode of sodium-ion batteries, but the mechanisms involved are still unclear.