A General and Highly Selective Palladium‐Catalyzed Hydroamidation of 1,3‐Diynes

A chemo‐, regio‐, and stereoselective mono‐hydroamidation of (un)symmetrical 1,3‐diynes is described. Key for the success of this novel transformation is the utilization of an advanced palladium catalyst system with the specific ligand Neolephos. The synthetic value of this general approach to synthetically useful α‐alkynyl‐α, β‐unsaturated amides is showcased by diversification of several structurally complex molecules and marketed drugs. Control experiments and density‐functional theory (M06L‐SMD) computations also suggest the crucial role of the substrate in controlling the regioselectivity of unsymmetrical 1,3‐diynes.     

Dynamic Effects in Intramolecular Schmidt Reactions: Entropy,Electrostatic Drag,and Selectivity Prediction

Electrostatic drag in the intramolecular Schmidt reactions of azidopropylcyclohexanones is characterized using density functional theory (DFT) calculations and direct dynamics simulations. Despite resulting from enthalpically favorable interactions, electrostatic drag slows down N₂ loss during formation of bridged lactam products, an effect with implications for controlling product selectivity.     

An insight into the electrocatalytic properties of porous La0.3Sr0.7Fe0.7Cr0.3O3−δ electrodes towards oxygen reduction reaction

Journal of Solid State Electrochemistry - The electrocatalytic properties of porous La0.3Sr0.7Fe0.7Cr0.3O3−δ electrodes towards oxygen reduction reaction were investigated as a function...     

Redox targeting of energy materials

The redox-mediated electrochemical–chemical process, when it involves the redox-targeting reaction with energy materials, has shown intriguing potential for various energy-related applications. This review starts with a brief discussion on the evolution of redox-targeting reactions for high-energy redox-flow batteries and the critical future studies for large-scale energy storage. Then, with spatially decoupled water electrolysis as an example, the merits of redox-targeting reaction by liberating the catalyst from electrode surface are highlighted, followed by an introduction of redox targeting–based thermal-to-electrical conversion. We have also featured various redox-targeting processes in other fields of study, such as electrochromic window, redox catalysis, and spent battery material recycling. Overall, this review attempts to demonstrate the incredible versatility and prospects of redox-targeting process for energy-related applications.     

Preparation and properties of ZnMoO4 anode materials with polymer network gel method

Polymer network gel method combines the advantages of solid-phase method and liquid phase method, triggering acrylamide (AM) radical polymerization in aqueous solution and N, N′- methylene bis acrylamide (MBAM) active double bond cross-linking reaction, forming polymer chains to form a three-dimensional network. The polymer network space formed by the gel is bound and evenly distributed to the ions in the solution, thereby reducing the contact and aggregation of molecules and achieving the purpose of uniform particle size and small particle size. The principle diagram of network gel is shown in Figure. Using cubic zinc acetate and ammonium molybdate tetrahydrate as raw materials, cubic ZnMoO₄ negative electrode materials were prepared with polymer network gel method. The polymer network gel method has various effects on the structure, morphology and electrochemical properties of materials. Besides, the calcination temperature and calcination time were also the key factors to the electrochemical properties of the materials. In this paper, the effects of the ratio of monomer and crosslinker, calcination temperature and calcination time on ZnMoO₄ materials were studied by single variable method, the preparation process was optimized, and its characterization and electrochemical tests were carried out. After 100 cycles, the optimized ZnMoO₄ electrode has a discharge capacity of 374.0 mAh· g^?1, 332.5, 263.5 and 177.1 mAh · g^?1 at current densities of 0.1, 0.5, 1.0 and 2.0 A g^?1, respectively. The electrochemical results show that the optimized ZnMoO₄ has high capacity, large rate capability and excellent cycle stability.     

Three-dimensional roselike α-Ni(OH)2 assembled from nanosheet building blocks for non-enzymatic glucose detection

Glucose detection plays very important roles in diagnostics and management of diabetes. The search for novel catalytic materials with appropriate architectures is the key step in the fabrication of highly sensitive glucose sensors. In this work, α-Ni(OH)₂ roselike structures (Ni(OH)₂-RS) assembled from nanosheet building blocks were successfully synthesized by a hydrothermal method through the hydrolysis of nickel chloride in the mixed solvents of water and ethanol with the assistance of polyethylene glycol (PEG). The structure and morphology of the roselike α-Ni(OH)₂ were characterized by transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and N₂ adsorption–desorption isotherm measurement. TEM and FE-SEM images showed that the synthesized Ni(OH)₂ was roselike and the size of the leaf-shaped nanosheet was about 5 nm in thickness, which leads to larger active surface areas and faster electron transfer for the detection of glucose. Compared with the bare GCE and bulk Ni(OH)₂/GCE, the Ni(OH)₂-RS/GCE had higher catalytic activity toward the oxidation of glucose. Under the optimal conditions, the Ni(OH)₂-RS/GCE offers a variety of merits, such as a wide linear response window for glucose concentrations ranging from 0.87 μM to 10.53 mM, short response time (3 s), a lower detection limit of 0.08 μM (S/N = 3), as well as long term stability and repeatability.     

Determination of Acetylcysteine in Pharmaceutical Samples by Silicomolybdenum Blue Spectrophotometry

An accurate and fast spectrophotometric method for the determination of acetylcysteine by silicomolybdenum blue has been established. The various effect factors on the determination of acetylcysteine by silicomolybdenum blue spectrophotometry are investigated in detail. The results show that under the optimum reaction conditions, SiO₃^2‐ reacts with Mo₇O₂₄^6‐ to form silicon molybdenum heteropoly acid (H₄Si(Mo₃O₁₀)₄). Then H₄Si(Mo₃O₁₀)₄ is reduced by hydrosulfuryl (‐SH) in acetylcysteine to form silicomolybdenum blue (H₄Si(Mo₃O₁₀)₂(Mo₃O₉)₂). The absorbance of silicomolybdenum blue is measured at the maximal absorption wavelength of 735 nm, and the content of acetylcysteine can be calculated based on this absorbance. A good linear relationship is obtained between the absorbance of silicomolybdenum blue and the concentration of acetylcysteine in the range of 5.040∼25.20 μg⋅mL^‐1. The linear regression equation is A = 0.0272 + 21.484C (mg⋅mL^‐1), with a linear correlation coefficient of 0.9995. This proposed method has been successfully applied to the determination of acetylcysteine in pharmaceutical samples, and the results agree well with those obtained by pharmacopoeial method.     

Separation and Characterization of Unknown Impurities in Amikacin Sulfate by HPLC–MS n

Nine impurities in amikacin sulfate made in China were separated and identified by HPLC–MSⁿ for the further improvement of official monographs in pharmacopoeias. The mass fragmentation patterns and structural assignment of these impurities were studied. The column was Acchrom Click XIon (250 × 4.6 mm, 5 μm). The mobile phase was 250 m mol L⁻¹ ammonium formate and 1.4 % formic acid aqueous solution–acetonitrile–water (30:48:22). In positive mode, full scan LC–MS was first performed in order to obtain the m/z value of the protonated molecules, LC–MS–MS was then carried out on the compounds of interest on AB SCIEX 4000 Q TRAP™ composite triple quadrupole/linear ion trap tandem mass spectrometer. The complete fragmentation patterns of nine impurities were studied and used to obtain information about the structure of these impurities. The structures of nine impurities in amikacin sulfate were deduced based on the HPLC–MSⁿ data, in which three impurities were novel impurities. Three novel impurities were 1-N-(l-4-amino-2-hydroxybutyryl) derivative of 4-O-(6-AG)DS, 1-N-(l-4-amino-2-hydroxybutyryl) derivative of 6-O-(3-AG)DS and 1-N-(l-4-amino-2-hydroxybutyryl) derivative of kanamycin D.

     

Facile Synthesis of the Pentasaccharide Repeating Unit of the Exopolysaccharide from Cryptococcus neoformans Serotype D

β‐D ‐GlcpA‐(1→2)‐[β‐D ‐Xylp‐(1→2)‐α‐D ‐Manp‐(1→3)]‐α‐D ‐Manp‐(1→3)‐α‐D ‐Manp, the repeating unit of the exopolysaccharide from Cryptococcus neoformans serotype D, was synthesized as its 4‐methoxyphenyl glycoside. The approach presented here also provides a route to the synthesis of more complex repeating units of glucuconoxylomannan (GXM) of C. neoformans serotypes A–C.     

Steroidal Alkaloids from Veratrum maackii Regel with Genotoxicity on Brain‐Cell DNA in Mice

Two new steroidal alkaloids, 23‐methoxycyclopamine 3‐O‐β‐D ‐glucopyranoside ( 1 ) and isoecliptalbine ( 2 ), were isolated from the root and rhizoma of Veratrum maackii Regel , together with five known compounds, i.e., verussurine ( 3 ), verabenzoamine ( 4 ), verazine ( 5 ), isoverazine ( 6 ), and verazinine ( 7 ). Their structures were established by extensive analysis of spectroscopic data, as well as by comparison with literature data. Compounds 1 – 7 could cause DNA damage in the cerebellum and cerebral cortex of mice in a dose‐dependent manner by using single‐cell gel electrophoresis (comet assay).