Electrophotocatalytic Tellurosulfonylation of Alkynes for the Synthesis of ß-(Telluro)vinyl Sulfones.

Difunctionalization of alkynes has gained a lot of interest in current organic chemistry. Herein, we developed an electrophotocatalytic multicomponent cascade reaction of alkynes and indoles with sulfinic acid sodium salts using elemental tellurium as the tellurium source. Using synergistic anodic oxidation and visible-light irradiation, various ß-(telluro)vinyl sulfones have been prepared. This strategy features mild reaction conditions, excellent substrate scope, readily available starting materials, and great functional group tolerance.

Application of chiral recyclable catalysts in asymmetric catalysis.

Chiral drugs hold a significant position within the contemporary pharmaceutical market, and the chiral catalysts play a crucial role in their synthesis. However, current chiral catalysts encounter challenges pertaining to their separation from products and the recycling process. The utilization of chiral recyclable catalysts not only reduces production costs but also aligns with the growing emphasis on environmentally-friendly chiral synthetic chemistry. These recyclable catalysts exhibit diverse carriers and distinct characteristics. Chemists employ the distinctive attributes of individual carriers to render them recyclable, thereby yielding time and cost savings. This review examines the asymmetric recyclable catalytic reactions reported between January 2017 and October 2023, categorizing them based on carrier solubility, and elucidates the loading techniques, catalytic impacts, recovery approaches, and recycling processes associated with these carriers.

Spiro-Josiphos Ligands for the Ir-Catalyzed Asymmetric Synthesis of Chiral Amines under Hydrogenation Conditions.

Transition metal-catalyzed asymmetric hydrogenation possesses unparalleled advantages to prepare chiral amines. Here we reported a novel ligand that combined Josiphos and a spirobiindane scaffold and simultaneously investigated its application in Ir-catalyzed asymmetric hydrogenation for the synthesis of chiral amines. Excellent catalytic activity (5000 TON), high enantioselectivity (up to 99% ee), and broad substrate scope (different C═N substrates) make it highly promising for both academic research and industrial applications.

Zero-Dimensional Carbon Nanomaterials for Fluorescent Sensing and Imaging.

Advances in nanotechnology and nanomaterials have attracted considerable interest and play key roles in scientific innovations in diverse fields. In particular, increased attention has been focused on carbon-based nanomaterials exhibiting diverse extended structures and unique properties. Among these materials, zero-dimensional structures, including fullerenes, carbon nano-onions, carbon nanodiamonds, and carbon dots, possess excellent bioaffinities and superior fluorescence properties that make these structures suitable for application to environmental and biological sensing, imaging, and therapeutics. This review provides a systematic overview of the classification and structural properties, design principles and preparation methods, and optical properties and sensing applications of zero-dimensional carbon nanomaterials. Recent interesting breakthroughs in the sensitive and selective sensing and imaging of heavy metal pollutants, hazardous substances, and bioactive molecules as well as applications in information encryption, super-resolution and photoacoustic imaging, and phototherapy and nanomedicine delivery are the main focus of this review. Finally, future challenges and prospects of these materials are highlighted and envisaged. This review presents a comprehensive basis and directions for designing, developing, and applying fascinating fluorescent sensors fabricated based on zero-dimensional carbon nanomaterials for specific requirements in numerous research fields.

Photocatalytic Cascade Reaction Driven by Directed Charge Transfer over VS -Zn0.5 Cd0.5 S/GO for Controllable Benzyl Oxidation.

Photocatalysis is an important technique for synthetic transformations. However, little attention has been paid to light-driven synergistic redox reactions for directed synthesis. Herein, the authors report tunable oxidation of benzyl to phenylcarbinol with the modest yield (47%) in 5 h via singlet oxygen (1 O2 ) and proton-coupled electron transfer (PCET) over the photocatalyst Zn0.5 Cd0.5 S (ZCS)/graphene oxide (GO) under exceptionally mild conditions. Theoretical calculations indicate that the presence of S vacancies on the surface of ZCS/GO photocatalyst is crucial for the adsorption and activation of O2 , successively generating the superoxide radical (• O2 - ) and 1 O2 , attributing to the regulation of local electron density on the surface of ZCS/GO and photogenerated holes (h+ ). Meanwhile, accelerated transfer of photogenerated electrons (e- ) to GO caused by the π-π stacking effect is conducive to the subsequent aldehyde hydrogenation to benzyl alcohol rather than non-selective oxidation of aldehyde to carboxylic acid. Anisotropic charge transport driven by the built-in electric field can further promote the separation of e- and h+ for multistep reactions. Promisingly, one-pot photocatalytic conversion of p-xylene to 4-methylbenzyl alcohol is beneficial for reducing the harmful effects of aromatics on human health. Furthermore, this study provides novel insights into the design of photocatalysts for cascade reactions.

Multisite-Sequential Cyclization To Construct 1,2,4-Triazole-Based N-Fused Heterocyclics.

A feasible protocol that uses atomic groups (KSCN, KSeCN, and NH2CN), o-bromobenzoyl hydrazides, and formyls as reaction factors to synthesize N-fused 1,2,4-triazole with benzothiazides, benzoselenazinones, and quinazolinones was proposed. The method overcomes the lengthy multistep synthesis, narrow substrate scope, and toxicity challenge induced by the use or production of hazardous substances. It also enables the development of fused-heterocyclic selenium and quinazolinone derivatives. Their fluorescent performance further demonstrates the practicability of this methodology.

Research on Multi-Scale Ecological Network Connectivity-Taking the Guangdong-Hong Kong-Macao Greater Bay Area as a Case Study.

The Guangdong-Hong Kong-Macao Greater Bay Area urban agglomeration is an urban agglomeration with some of the most intensive urbanization since 1980s. A large amount of cultivated land, forest land, water bodies and other land types in the region has been occupied by construction land, resulting in fragmented ecological landscapes and biodiversity in the region and causing many other ecological problems. Based on this, this paper takes the Guangdong-Hong Kong-Macao Greater Bay Area as a case study, constructs an ecological network of the dispersion scale of five species from 1990 to 2020 based on a morphological spatial pattern analysis (MSPA) method, identifies the ecological groups in the network and uses the core node-based community evolution path tracking algorithm to analyze the ecological groups in order to explore the changes of ecological network connectivity at different scales in the region and to reveal the overall and local characteristics and changes of the migratory space of terrestrial mammals with different dispersion capabilities. The research results show that: (1) From 1990 to 2020, the area of construction land in the Guangdong-Hong Kong-Macao Greater Bay Area increased sharply, with good connectivity in the northwest, southwest and eastern regions and poor connectivity in the central region. (2) There are obvious differences between the overall and local changes in the connectivity trends of multi-scale regional ecological networks. On the whole, the overall ecological connectivity of the ecological network at each scale showed a gradual upward trend, and the overall connectivity index IIC and the possible connectivity index PC gradually increased with the increase of the maximum dispersal distance of species. From the perspective of local patches, the larger the species dispersion scale, the larger the value of the revised betweenness centrality index and the patch possible connectivity index. (3) The distribution of ecological groups at different species dispersion scales is different, and the smaller the dispersal scale of the species, the greater the distribution of ecological groups. Small-scale species are limited by the maximum dispersal distance, and the range of their ecological groups is generally small. Small-scale (3 km), mesoscale (10 km) and large-scale (30 km) core nodes of ecological groups show a gradual increase trend, and the overall connectivity of ecological groups has improved. However, the core nodes of the extra-large-scale (60 km) and ultra-large-scale (100 km) ecological groups show a trend of decreasing fluctuations, and the overall connectivity within the ecological group has declined. This study is helpful to clarify the structural characteristics of regional ecological space and provide a theoretical basis for regional ecological planning.

Electrochemical Oxidative C-C Bond Cleavage of Ketones for C-N Bond Formation: A Route to Amides.

Herein, we report an efficient electrochemical activation of the C-C bond of aryl ketones for the preparation of amides under catalyst- and external-oxidant-free conditions using aliphatic amines as the N source. Under environmentally benign electrolysis conditions, a series of amides were synthesized in good yield. Our control experiments revealed that electricity plays an important role in this transformation.

Ni(II)-Catalyzed Regio- and Stereoselective O-Alkylation for the Construction of 1,2-cis-Glycosidic Linkages.

A transition-metal-catalyzed O-alkylation for the regio- and stereoselective construction of 1,2-cis-glycosidic linkages is presented. With nonprecious and readily available Ni(II) as a catalyst, 1,2-cis-glycosides were obtained via O-alkylation of 1,2-carbohydrate diols that can be accessed in a small number of steps. The tedious design of protecting groups or anomeric leaving groups could be avoided with this method. The strategy was applied for the efficient preparation of an important commercialized glycosidic compatible solute GG, its derivative MGG, and a branched α-glucan.

Study on Air Quality and Its Annual Fluctuation in China Based on Cluster Analysis.

Exploring the spatial and temporal distribution characteristics of air quality has become an important topic for the harmonious development of human and nature. Based on the hourly data of CO, O3, NO2, SO2, PM2.5 and PM10 of 1427 air quality monitoring stations in China in 2016, this paper calculated the annual mean and annual standard deviation of six air quality indicators at each station to obtain 12 variables. Self-Organizing Maps (SOM) and K-means clustering algorithms were carried out based on MATLAB and SPSS Statistics, respectively. Kriging interpolation was used to get the clustering distribution of air quality and fluctuation in China, and Principal Component Analysis (PCA) was used to analyze the main factors affecting the clustering results. The results show that: (1) Most areas in China are low-value regions, while the high-value region is the smallest and more concentrated. Air quality in northern China is worse, and the annual fluctuations of the indicators are more dramatic. (2) Compared with AQI, AQFI has a strong indication significance for the comprehensive situation of air quality and its fluctuation. (3) The spatial distribution of SOM clustering results is more discriminative, while K-means clustering results have a large proportion of low-mean regions. (4) PM2.5, PM10 and CO are the main pollutants affecting air quality and fluctuation, followed by SO2, NO2 and O3.

Chiral Cyclopropenimine-catalyzed Asymmetric Michael Addition of Bulky Glycine Imine to α,ß-Unsaturated Isoxazoles.

A highly efficient asymmetric Michael addition of bulky glycine imine to α,ß-unsaturated isoxazoles has been achieved by using 5 mol% of chiral cyclopropenimine as a chiral organo-superbase catalyst under mild conditions. Michael adducts were obtained in excellent yields (up to 97%) and stereoselectivities (up to >99 : 1 dr and 98% ee). A significant solvent effect was found in these chiral organosuperbase catalyzed asymmetric Michael reactions. Gram-scale preparation of Michael adducts and their transformations are realized to provide corresponding products without loss of stereoselectivities. The configurations of Michael adduct was determined by single-crystal X-ray diffraction analysis.

Facile access to chiral chromanone-2-carboxylic acids enabled by rhodium-catalyzed chemo- and enantioselective hydrogenation.

Rh-catalyzed highly chemo- and enantioselective hydrogenation of chromone-2-carboxylic acids was successfully established for the first time, providing a wide range of enantiopure chromanone-2-carboxylic acids with excellent results (up to 97% yield and 99% ee) and high efficiency (up to 10 000 TON). The carboxylic group in the substrate was demonstrated to play a vital role and an enantio-induction mode was elucidated by DFT calculation. This hydrogenation protocol provided straightforward access to various bioactive chromanoids.

Selective Thiocyanation and Aromatic Amination To Achieve Organized Annulation of Enaminone with Thiocyanate.

A tandem insertion of thiocyanate to enamine was performed for the regioselective synthesis of multisubstituted benzoimidazo[2,1-b]thiazoles. This method was shown to be effective in addressing the issue of isomerization encountered in common strategies. With a change made to the leading group on the aniline fragment of enamine, the reaction achieved different transformations, thus enabling multisubstituted benzo[4,5]imidazo[2,1-b]thiazoles and thiazoles in satisfactory yields.

Structurally Diverse Synthesis of Five-, Six-, and Seven-Membered Benzosultams through Electrochemical Cyclization.

We have developed a metal- and oxidant-free approach to structurally diverse synthesis of benzosultams from aryl sulfonamides through an electrochemical cyclization. Upon variation of the ortho substituent on aryl sulfonamides, five-, six-, and seven-membered benzosultams were efficiently assembled in an atom- and resource-economic manner. The generality of the process is demonstrated by the formation of five- to seven-membered cyclic products from 42 substrates bearing substituents with different electronic effects and steric hindrance.

Recent Progress in Fluorescent Sensors for Drug-Induced Liver Injury Assessment.

Drug-induced liver injury (DILI) is a persistent concern in drug discovery and clinical medicine. The current clinical methods to assay DILI by analyzing the enzymes in serum are still not optimal. Recent studies showed that fluorescent sensors would be efficient tools for detecting the concentration and distribution of DILI indicators with high sensitivity and specificity, in real-time, in situ, and with low damage to biosamples, as well as diagnosing DILI. This review focuses on the assessment of DILI, introduces the current mechanisms of DILI, and summarizes the design strategies of fluorescent sensors for DILI indicators, including ions, small molecules, and related enzymes. Some challenges for developing DILI diagnostic fluorescent sensors are put forward. We believe that these design strategies and challenges to evaluate DILI will inspire chemists and give them opportunities to further develop other fluorescent sensors for accurate diagnoses and therapies for other diseases.

Iridium-Catalyzed Asymmetric Hydrogenation of Sterically Hindered Cyclic Imines for Enantioselective Synthesis of Tetrahydroisoquinolines.

An efficient enantioselective hydrogenation of sterically hindered cyclic imines catalyzed by the Ir-tBu-ax-Josiphos complex has been described, producing a series of useful chiral bulky tetrahydroisoquinoline analogs in high isolated yields (85-96%) with good to excellent enantioselectivities (74-99% ee). This transformation provided highly straightforward access to the useful derivatives of tetrahydroisoquinolines, which are of great potential value in drug molecule and natural product research.

Imaging and Monitoring the Hydrogen Peroxide Level in Heart Failure by a Fluorescent Probe with a Large Stokes Shift.

Heart failure is the terminal stage of many cardiovascular diseases and is considered to be closely related to oxidative stress. Early understanding of pathogenesis can greatly improve the treatment and reduce the mortality of heart disease. In this work, based on the analysis of coumarin derivates by theoretical calculations, we designed and synthesized a fluorescent probe BCO with a large Stokes shift (107 nm) and excellent selectivity toward H2O2 in a living system. The distribution of H2O2 in the heart and thoracic aorta tissues was imaged with the aid of the probe BCO, which demonstrated that the cellular H2O2 level is upregulated in heart failure. This work provides a useful tool, BCO, for the evaluation of cellular oxidative stress and to further understand the pathophysiology process of heart disease.

An ICT-based fluorescent probe guided by theoretical calculation for selectively mapping endogenous GSH in living cells.

Glutathione (GSH) is one of the most essential bio-thiols to maintain the redox balance of organisms which is strongly associated with many physiological processes. Detecting the concentration and mapping the distribution of GSH in the living system is significant to study many related diseases. In this work, we have successfully constructed an ICT-based model to guide the design and synthesis of GSH specific fluorescent probe CF1. A serials spectroscopy test demonstrated that the response of CF1 towards GSH owned large stokes shift (~167 nm) and an excellent linear relationship (0-120 µM, R2 = 0.9961). Furthermore, CF1 was successfully applied to image endogenous GSH in different cell lines with high sensitivity. This work is instructive for the oriented synthesis of ICT-based functional fluorescent probe and the further visualization of intracellular targets in the living system.

Visible-light driven synthesis of polycyclic benzo[d][1,3]oxazocine from 2-aminochalcone.

Herein, we report a tandem cycloisomerization/nucleophilic addition/cyclization of 2-amino chalcone with bifunctional nucleophiles driven by visible light. This cascade process is realized by the irradiation of a blue LED at room temperature, which provides a concise route to structurally diverse benzo[d][1,3]oxazocine scaffolds. Mechanistic studies show that the reaction is initiated with the E to Z isomerization of a C-C double bond upon the irradiation of visible light, followed by cyclization/rearomatization to generate a transient quinolinium intermediate, which is trapped by the nucleophile and cyclized to produce the polycyclic benzo[d][1,3]oxazocine.

Bioactive constituents from Salacia cochinchinensis.

Two new isopimarane diterpenoids, named 1α-hydroxy-7-oxoisopimara-8, 15-diene (1), 11ß-hydroxy-7-oxoisopimara-8(14), 15-diene (2), together with six known compounds (3-8), were isolated from the medicinal plant Salacia cochinchinensis. All isolates were assayed for their cytotoxicity and α-glucosidase inhibitory activity. Results suggested compounds 1, 3 possessed significant cytotoxic activity against HepG2, HL60, and Hela cell lines with IC50 values ranging from 0.23 to 0.35 µM, and compounds 7, 8 exhibited noticeable α-glucosidase inhibitory ability with IC50 values of 0.25 and 0.31 µM, respectively.