An organoantimony nitrate complex with azastibocine framework as water tolerant Lewis acid catalyst for the synthesis of 1,2-disubstitued benzimidazoles

A novel organoantimony complex of 6-cyclohexyl-6,7-dihydrodibenzo[c,f] [1,5]azastibocin-12(5H)-yl nitrate ( 2 ) was synthesized and systematically characterized by techniques such as NMR spectra, TG-DSC, and X-ray diffraction. It was found that the complex 2 exhibits relatively strong Lewis acidity (3.3 < Ho ≤ 4.8) and could be employed as a water tolerant Lewis acid catalyst for the synthesis of synthetically valuable benzimidazole derivatives starting from aldehydes and arylenediamines. This catalytic system shows excellent tolerance toward a wide variety of functional groups, such as methyl, methoxyl, fluoro, chloro, bromo, nitro, cyan, trifluoromethyl, 1-naphthaldehyde, furfural and n-butyl, together with facile reusability in 5 times scale enlarged synthesis.     

Prussian Blue Modified Amperometric Hg2+ Ion Biosensor Based on Glucose Oxidase Inhibition

In this research a Hg²⁺ ion biosensor was developed by combining Prussian blue (PB) with glucose oxidase (GOx) – an enzyme that can be inhibited by Hg²⁺ ions. An application of PB in the design of Hg²⁺ ion biosensor enabled detecting changes in hydrogen peroxide reduction current at low operational potential of 0.2 vs Ag|AgCl,KCl_sat. The described Hg²⁺ ion biosensor exhibited wide linear range from 27 μM to 247 μM of Hg²⁺ and higher maximal detectable concentration of Hg²⁺ than other GOx inhibition-based biosensors, making it convenient for the analysis of samples with high concentration of Hg²⁺ ions.     

Dual Esterase‐ and Steroid‐Responsive Energy Transfer Modulation of Ruthenium(II) and Rhenium(I) Complex Functionalized Gold Nanoparticles

A number of adamantane‐containing ruthenium(II) and rhenium(I) complexes have been synthesized, characterized, and noncovalently functionalized with β‐cyclodextrin‐capped gold nanoparticles (β‐CD–GNPs) through the host–guest interaction between cyclodextrin and adamantane. The resultant nanoconjugates have been characterized by transmission electron microscopy (TEM), energy‐dispersive X‐ray analysis (EDX), and 2D ROESY ¹H NMR experiments. The Förster resonance energy transfer (FRET) properties of the nanoconjugates can be modulated by both esterase‐accelerated hydrolysis and competitive displacement of steroid, by monitoring the emission intensity and luminescence lifetime. The FRET efficiencies are found to vary with the nature of the chromophores and the length of the spacer between the transition metal complexes and the GNPs. This work constitutes a “proof‐of‐principle” assay method for the dual‐functional detection of important classes of biomolecules, such as enzymes and steroids.     

New Methods for β-Lactam Formation from β-Amino Acids Using (C6H5)3P/CC14 and (C6H5)3P/NBS

Triphenylphosphine/carbon tetrachloride and triphenyl-phosphine/N-bromosuccinimide were found to be very effective for β-lactam formation from β-amino acids in acetonitrile.     

光电催化二氧化碳还原研究进展

CO_2是最常见的化合物,作为潜在的碳一资源,可用于制备多种高附加值的化学品,如一氧化碳、甲烷、甲醇、甲酸等。传统的热催化转化CO_2方法能耗高,反应条件苛刻。因此,如何在温和条件下高效地将CO_2转化成高附加值的化学品,一直以来是催化领域的研究热点和难点之一。光催化技术反应条件温和、绿色环保。然而,纯光催化反应普遍存在太阳能利用效率有限,光生载流子分离效率低等问题。针对上述问题,在光催化的基础上引入电催化,可以提高载流子的分离效率,在较低的过电位下,实现多电子、质子向CO_2转移,从而提高催化反应效率。总之,光电催化技术可以结合光催化和电催化的优势,提高CO_2催化还原反应效率,为清洁、绿色利用CO_2提供了一种新方法。本文依据光电催化CO_2还原反应基本过程,从光吸收、载流子分离和界面反应等三个角度综述了光电催化反应的基本强化策略,并对未来可能的研究方向进行了展望。     

Durable Mesenchymal Stem Cell Labelling by Using Polyhedral Superparamagnetic Iron Oxide Nanoparticles

Small polyhedral superparamagnetic iron oxide (SPIO) nanoparticles (<10 nm) coated with a thin layer of silica were prepared (SPIO@SiO₂ and SPIO@SiO₂‐NH₂). Surface modification of the small polyhedral silica‐coated SPIO nanoparticles with amines led to substantially higher mesenchymal stem cell (MSC) labelling efficiency without the use of additional transfecting agents. Therefore, amine surface‐modified nanoparticles (SPIO@ SiO₂‐NH₂) appeared to be the preferred candidate for MSC labelling. In vitro studies demonstrated that controlled labelling of SPIO@SiO₂ and SPIO@SiO₂‐NH₂ did not cause MSC death or proliferation inhibition. MSCs labelled with SPIO@SiO₂‐NH₂ nanoparticles retained differentiation potential and showed osteogenic, adipogenic and chondrogenic differentiations. The noncytotoxic polyhedral SPIO@SiO₂‐NH₂ nanoparticle‐labelled MSCs were successfully implanted in rabbit brain and erector spinae muscle, and demonstrated long‐lasting, durable MRI labelling efficacy after 8–12 weeks.     

Synthesis of Gold Microplates Using Bovine Serum Albumin as a Reductant and a Stabilizer

Gold microplates were synthesized in aqueous solutions by reducing HAuCl₄ with the hydroxyl groups in both serine and threonine of bovine serum albumin (BSA), which is a globular protein in its native state. In this article, we systematically investigated the effects of temperature, pH value, the concentration of BSA, and ionic species on the reduction kinetics and thus the size and morphology of the final product. The optimal experimental conditions for producing uniform Au microplates include the following: an elevated temperature in the range of 55–65 °C, an acidic solution with pH≈3, and the presence of NaCl (0.14 M ). We found that if any one of these parameters was deviated from the optimal condition, Au microplates would not be formed in high yields. We also found that the surfaces of the as‐synthesized Au microplates were covered by a dense array of BSA bumps.     

Cyano-Carbonates (II) -Eficient Iatent Acyl Carbanious in 1,4-Additions

Alkylations of cyano-carbonate anions with ethyl acrylate or methyl vinyl ketone followed by hydrolysis yield 1,4-addition products in excelleat yields.     

Strong Morphological Effect of Mn3O4 Nanocrystallites on the Catalytic Activity of Mn3O4 and Au/Mn3O4 in Benzene Combustion

Gold nanoparticles (3–4 nm) were deposited on Mn₃O₄ nanocrystallites with three distinct morphologies (cubic, hexagonal, and octahedral). The resulting structures were characterized, and their activities for benzene combustion were evaluated. The dominant exposed facets for the three kinds of Mn₃O₄ polyhedrons show the activity order: (103)≈(200)>(101). A similar activity order was derived for the interfaces between the Au and the Mn₃O₄ facet: Au/(200)≈Au/(103)>Au/(101). The metal–support interactions between the Au nanoclusters and specific facets of the Mn₃O₄ polyhedrons lead to a unique interfacial synergism in which the electronic modification of the Au nanoparticles and the morphology of the Mn₃O₄ substrate have a joint effect that is responsible for a significant enhancement in the catalytic activity of the Au/Mn₃O₄ system.