Fast synthesis of core-shell LiCoPO4/C nanocomposite via microwave heating and its electrochemical Li intercalation performances

A very simple and rapid method for synthesizing LiCoPO₄/C nanocomposite has been developed via microwave heating. X-ray diffraction confirmed that nanosized olivine LiCoPO₄ was successfully synthesized. Scanning electron microscopy and transmission electron microscopy verified that LiCoPO₄ displays small powders with an average size of ～150 nm and is also coated with uniform amorphous carbon film of ～10 nm in thickness. Compared with pure LiCoPO₄, LiCoPO₄/C composite presented enhanced electrochemical Li-ion intercalation performances. Cyclic voltammetric and electrical tests disclosed that the Li-ion diffusion, the reversibility of lithium extraction/insertion and electrical conductivity were significantly improved in LiCoPO₄/C composite.     

Copper oxide nanoarray based on the substrate of Cu applied for the chemical sensor of hydrazine detection

This communication reports on a novel amperometric hydrazine sensor of CuO nanoarray based on a Cu substrate. Copper oxide nanoarray was directly grown on Cu substrates using a one-step facile hydrothermal method and was characterized using scanning electron microscopy and X-ray powder diffraction. The electrochemical study has shown that the CuO nanoarray exhibits higher catalytic effect on the hydrazine than the normal CuO nanoparticles. This may be attributed to the special structure of the nanomaterials esp. the substrate of the electric Cu. And the amperometric response showed that the CuO nanoarray modified glassy carbon electrode has a low detection and a high sensitivity for hydrazine.     

X-ray induced photocatalysis on TiO2 and TiO2 nanotubes: Degradation of organics and drug release

The photocatalytic activity of titanium dioxide under X-ray radiation is of great interest for biomedical applications. In the present work we explore the use of compact TiO₂ layers and TiO₂ nanotubes for X-ray induced photocatalysis, in particular the degradation of organics and monolayer chain scission for drug release. The radiation was done with a conventional X-ray source and doses up to 50 × 10^?3 J/kg. The results show the feasibility of X-ray catalysis on TiO₂ and X-ray induced monolayer chain scission by the release of surface attached Zn–porphyrin molecules. Furthermore, a higher efficiency for anatase films and nanotubes is obtained than for amorphous morphologies.     

A three‐dimensional homochiral metal–organic framework constructed from manganese(II) with S‐carboxymethyl‐N‐(p‐tosyl)‐l‐cysteine and 4,4′‐bipyridine

In the chiral polymeric title compound, poly[aqua(4,4′‐bipyridine)[μ₃‐S‐carboxylatomethyl‐N‐(p‐tosyl)‐l ‐cysteinato]manganese(II)], [Mn(C₁₂H₁₃NO₆S₂)(C₁₀H₈N₂)(H₂O)]_n, the Mn^II ion is coordinated in a distorted octahedral geometry by one water molecule, three carboxylate O atoms from three S‐carboxyatomethyl‐N‐(p‐tosyl)‐l ‐cysteinate (Ts‐cmc) ligands and two N atoms from two 4,4′‐bipyridine molecules. Each Ts‐cmc ligand behaves as a chiral μ₃‐linker connecting three Mn^II ions. The two‐dimensional frameworks thus formed are further connected by 4,4′‐bipyridine ligands into a three‐dimensional homochiral metal–organic framework. This is a rare case of a homochiral metal–organic framework with a flexible chiral ligand as linker, and this result demonstrates the important role of noncovalent interactions in stabilizing such assemblies.     

A novel threefold‐interpenetrating primitive cubic network based on a dinuclear Zn2 node

In the mixed‐ligand metal–organic polymeric compound poly[[μ₂‐1,4‐bis(imidazol‐1‐yl)benzene](μ₂‐terephthalato)dizinc(II)], [Zn₂(C₈H₄O₄)₂(C₁₂H₁₀N₄)]_n or [Zn₂(bdc)₂(bib)]_n [H₂bdc is terephthalic acid and bib is 1,4‐bis(imidazol‐1‐yl)benzene], the asymmetric unit contains one Zn^II ion, with two half bdc anions and one half bib molecule lying around inversion centers. The Zn^II ion is in a slightly distorted tetrahedral environment, coordinated by three carboxylate O atoms from three different bdc anions and by one bib N atom. The crystal structure is constructed from the secondary building unit (SBU) [Zn₂(CO₂)₂N₂O₂], in which the two metal centers are held together by two bdc linkers with bis(syn,syn‐bridging bidentate) bonding modes. The SBU is connected by bdc bridges to form a two‐dimensional grid‐like (4,4)‐layer, which is further pillared by the bib ligand. Topologically, the dinuclear SBU can be considered to be a six‐connected node, and the extended structure exhibits an elongated primitive approximately cubic framework. The three‐dimensional framework possesses a large cavity with dimensions of approximately 10 × 13 × 17 Å in cross‐section. The potential porosity is filled with mutual interpenetration of two identical equivalent frameworks, generating a novel threefold interpenetrating network with an α‐polonium topology [Abrahams, Hoskins, Robson & Slizys (2002). CrystEngComm, 4 , 478–482].     

A novel (3,4,10)‐connected three‐dimensional hydrogen‐bonded supramolecular network containing a cyclic water hexamer

The title compound, 4,4′‐(1,1,1,3,3,3‐hexafluoroisopropylidene)diphthalic acid hexahydrate, C₁₉H₁₀F₆O₈·6H₂O, crystallizes in the centrosymmetric space group Pbcn, with half of the diphthalic acid residue and three water molecules in the asymmetric unit. The organic molecule is located on a crystallographic twofold axis. In the solid, cyclic water hexamers in chair conformations have crystallographically imposed inversion symmetry. Strong O—H...O hydrogen bonds between the hexamers and organic molecules result in a unique three‐dimensional supramolecular network [O...O = 2.554 (2)–2.913 (2) Å]. This compound represents the first example of a (3,4,4,10)‐connected four‐nodal supramolecular topology with the Schläfli symbol (4³.5.6.7)₂(4³.5².7)₂(4³)₂(4⁶.5⁶.6².7⁸.8¹⁴.9⁹).     

Enhanced photocatalytic Cr(VI) reduction and diclofenac sodium degradation under simulated sunlight irradiation over MIL-100(Fe)/g-C3N4 heterojunctions

Metal-organic framework MIL-100(Fe) and g-C₃N₄ heterojunctions (MG-x, x = 5%, 10%, 20%, and 30%, x is the mass fraction of MIL-100(Fe) in the hybrids) were facilely fabricated through ball-milling and annealing, and characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, transmission electron microscopy, UV-visible diffuse-reflectance spectrometry, and photoluminescence emission spectrometry. The photocatalytic activities of the series of MG-x heterojunctions toward Cr(VI) reduction and diclofenac sodium degradation were tested upon irradiation with simulated sunlight. The influence of different organic compounds (ethanol, citric acid, oxalic acid, and diclofenac sodium) as hole scavengers and the pH values (2, 3, 4, 6, and 8) on the photocatalytic activities of the series of MG-x heterojunctions was investigated. MG-20% showed superior photocatalytic Cr(VI) reduction and diclofenac sodium degradation performance than did the individual MIL-100(Fe) and g-C₃N₄ because of the improved separation of photoinduced electron-hole charges, which was clarified via photoluminescence emission and electrochemical data. Moreover, the MG-x exhibited good reusability and stability after several runs.     

Efficient glycosylation with glycosyl ortho-allylbenzoates as donors

Glycosylation reactions are significant as they provide access to model compounds that are useful for elucidating biochemical pathways. Herein, we describe the development of glycosyl ortho-alkynylbenzoates as novel, bench-top stable, and readily available glycosyl donors. Glycosylation is promoted by inexpensive trimethylsilyl triflate (TMSOTf) in combination with N-iodosuccinimide (NIS) under mild reaction conditions; hence, the novel glycosyl donors are promising reagents for the synthesis of glycosides.     

pH Resistant Ratiometric Measurement of Nicotinamide Adenine Dinucleotide Levels by Time-resolved Fluorescence Spectroscopy

Circular permutation fluorescent protein is a novel method to construct biosensors. The ratio of two excitation channels is employed to quantitatively calibrate the level of analysts. SoNar is one of them, which can be used to monitor cellular NADH/NAD⁺ levels. However, the 490 nm excitation channel of these biosensors is sensitive to pH environments, which is negative in real applications. In this work, we demonstrated that the fractional intensity ratio extracted from time-resolved fluorescence spectroscopy could be used to quantify NADH levels with one excitation (420 nm) and one emission channels. The 420-nm excitation channel was pH resistant. Comparing to average lifetime, the fractional intensity ratio had a 3.2-fold dynamic range, which was much wider than average lifetimes.     

Asymmetric aza-Henry reaction of fluoromethylated imines catalyzed by cinchona-derived bifunctional thiourea

The asymmetric aza-Henry reaction of fluoromethyl imines derived from 4-methoxyaniline with nitromethane was achieved under mild conditions using cinchona-derived bifunctional thiourea as catalyst. A series of chiral fluoromethylated β-nitroamines were synthesized and their transformation to optically pure 4-fluoromethyl-2-imidazolidones was illustrated.