UV-induced synthesis,characterization and formation mechanism of silver nanoparticles in alkalic carboxymethylated chitosan solution

The silver nanoparticles (AgNPs) were synthesized in an alkalic aqueous solution of silver nitrate (AgNO₃)/carboxymethylated chitosan (CMCTS) with ultraviolet (UV) light irradiation. CMCTS, a water-soluble and biocompatible chitosan derivative, served simultaneously as a reducing agent for silver cation and a stabilizing agent for AgNPs in this method. UV–vis spectra and transmission electron microscopy (TEM) images analyses showed that the pH of AgNO₃/CMCTS aqueous solutions, the concentrations of AgNO₃ and CMCTS can affect on the size, amount of synthesized AgNPs. Further by polarized optical microscopy it was found that the CMCTS with a high molecular weight leads to a branch-like AgNPs/CMCTS composite morphology. The diameter range of the AgNPs was 2–8 nm and they can be dispersed stably in the alkalic CMCTS solution for more than 6 months. XRD pattern indicated that the AgNPs has cubic crystal structure. The spectra of laser photolysis of AgNO₃/CMCTS aqueous solutions identified the early reduction processes of silver cations (Ag⁺) by hydrated electron formed by photoionization of CMCTS. The rate constant of corresponding reduction reaction was 5.0 × 10⁹ M⁻¹ s⁻¹.     

长波紫外辐射对Ⅰ型胶原损伤的拉曼光谱研究

应用拉曼光谱技术研究了长波紫外(Ultraviolet-A,UV-A)辐射对Ⅰ型胶原的损伤,检测了Ⅰ型胶原及其经过90min的UV-A辐射后的拉曼光谱,得到了一个较完整的Ⅰ型胶原紫外损伤机制。实验结果表明:90min的UV-A辐射导致Ⅰ型胶原分子内氢键断裂、氢键体系发生变化,肽链的螺旋度减少,逐渐解螺旋,无规卷曲等无序构象增加。此外,UV-A辐射使Ⅰ型胶原分子内脯氨酸的羟基化程度降低。这些变化必然会引起Ⅰ型胶原三螺旋结构的损伤,并导致皮肤光老化过程中组织内胶原纤维的破坏。     

Effect of different doped elements on visible light absorption and ultraviolet light emission on Er3+:Y3Al5O12

In this progress report, seven kinds of novel carefully designed and fabricated up-conversion luminescence agents, Er³⁺:Y₃Al₅O₁₂, Er³⁺:Yb_nY_3?nAl₅O₁₂, Er³⁺:Y₃B_aAl_5?aO₁₂, Er³⁺:Y₃Ga_bAl_5?bO₁₂, Er³⁺:Y₃Al₅N_xO_12?x, Er³⁺:Y₃Al₅F_yO_12?y and Er³⁺:Yb_nY_3?nB_aGa_bAl_5?a?bN_xF_yO_12?x?y, are successfully synthesized using sol–gel methods. After that, their corresponding photocatalysts, Er³⁺:Y₃Al₅O₁₂/TiO₂, Er³⁺:Yb_nY_3?nAl₅O₁₂/TiO₂, Er³⁺:Y₃B_aAl_5?aO₁₂/TiO₂, Er³⁺:Y₃Ga_bAl_5?bO₁₂/TiO₂, Er³⁺:Y₃Al₅N_xO_12?x/TiO₂, Er³⁺:Y₃Al₅F_yO_12?y/TiO₂ and Er³⁺:Yb_nY_3?nB_aGa_bAl_5?a?bN_xF_yO_12?x?y/TiO₂, are also prepared by sol–gel coating process. The obtained up-conversion luminescence agents and photocatalysts were characterized by using XRD, XPS, SEM, UV–vis and fluorescence spectrophotometer. Synchronously, several kinds of organic dyes are used to test their photocatalytic degradation using prepared photocatalysts. It indicates that the up-conversion luminescence ability of Er³⁺:Y₃Al₅O₁₂ can be improved obviously through doping of some elements. And then, the photocatalytic activity of TiO₂ is markedly enhanced by modified up-conversion luminescence agents which can transform much visible light into ultraviolet light.     

1999-2016年期刊《绿色化学》载文的计量分析

绿色化学是新兴的学科交叉领域,了解其知识体系的发展及研究态势,有助于讨论当代学科的发展特点。本文选取该领域的权威期刊《绿色化学》(Green Chemistry)作为研究对象,运用Cite Space与VOSviewer等可视化工具对1999~2016年该刊载文进行了计量分析。研究表明,《绿色化学》自创刊以来,其影响因子与载文量快速增长,学术研究进展较快。目前,该领域的核心地区、机构、研究人员集中在美国、中国、英国、德国、荷兰等国家,国际合作十分频繁。绿色化学领域的研究热点包括离子液体、生物质、催化等主题。     

不对称氢化杂环亚胺合成四氢吡咯/吲哚[1,2-a]并吡嗪

报道了一种铱催化3,4-二氢吡咯并吡嗪和3,4-二氢吲哚[1,2-a]并吡嗪的不对称氢化合成相应的1,2,3,4,-四氢吡咯/吲哚[1,2-a]并吡嗪化合物的方法.该催化体系适用于芳基取代的底物和烷基取代的底物,反应收率高达99%,对映选择性过量值最高为95%.该反应操作简单,原子经济性好.     

Design of Photoactive Covalent Organic Frameworks as Heterogeneous Catalyst for Preparation of Thiophosphinates from Phosphine Oxides and Thiols

Two new covalent organic frameworks (COFs) were synthesized from 4,4′,4′′,4′′′-(pyrene-1,3,6,8-tetrayl)tetraaniline and 2,5-dimethoxyterephthalaldehyde (Py-DMTA-COF) or 2′,5′-dimethoxy-[1,1′:4′,1′′-terphenyl]-4,4′′-dicarbaldehyde (Py-DMTPDA-COF) under solvothermal conditions. These two COFs were further facilely developed as efficient photocatalytic platforms for the synthesis of thiophosphinates. Py-DMTA-COF exhibited better photocatalytic activity, broad substrate applicability, and excellent recycling capacity for the preparation of thiophosphinates from P(O)H compounds and thiols compared to Py-DMTPDA-COF. This methodology was further extended to the seamless gram-scale production of target phosphorothioate derivatives. The results demonstrate that COFs can provide a robust platform for developing metal-free, base-free, highly efficient, and reusable heterogeneous photocatalysts for organic transformations.     

A Membrane Tension-Responsive Mechanosensitive DNA Nanomachine

Membrane curvature reflects physical forces operating on the lipid membrane, which plays important roles in cellular processes. Here, we design a mechanosensitive DNA (MSD) nanomachine that mimics natural mechanosensitive PIEZO channels to convert the membrane tension changes of lipid vesicles with different sizes into fluorescence signals in real time. The MSD nanomachine consists of an archetypical six-helix-bundle DNA nanopore, cholesterol-based membrane anchors, and a solvatochromic fluorophore, spiropyran (SP). We find that the DNA nanopore effectively amplifies subtle variations of the membrane tension, which effectively induces the isomerization of weakly emissive SP into highly emissive merocyanine isomers for visualizing membrane tension changes. By measuring the membrane tension via the fluorescence of MSD nanomachine, we establish the correlation between the membrane tension and the curvature that follows the Young-Laplace equation. This DNA nanotechnology-enabled strategy opens new routes to studying membrane mechanics in physiological and pathological settings.     

Oxygen-Bridged Indium-Nickel Atomic Pair as Dual-Metal Active Sites Enabling Synergistic Electrocatalytic CO2 Reduction

Single-atom catalysts offer a promising pathway for electrochemical CO₂ conversion. However, it is still a challenge to optimize the electrochemical performance of dual-atom catalysts. Here, an atomic indium-nickel dual-sites catalyst bridged by an axial oxygen atom (O-In-N₆-Ni moiety) was anchored on nitrogenated carbon (InNi DS/NC). InNi DS/NC exhibits superior CO selectivity with Faradaic efficiency higher than 90 % over a wide potential range from −0.5 to −0.8 V versus reversible hydrogen electrode (vs. RHE). Moreover, an industrial CO partial current density up to 317.2 mA cm⁻² is achieved at −1.0 V vs. RHE in a flow cell. In situ ATR-SEIRAS combined with theory calculations reveal that the synergistic effect of In-Ni dual-sites and O atom bridge not only reduces the reaction barrier for the formation of *COOH, but also retards the undesired hydrogen evolution reaction. This work provides a feasible strategy to construct dual-site catalysts towards energy conversion.     

Enhancement of transport of curcumin to brain in mice by poly(n-butylcyanoacrylate) nanoparticle

Curcumin, a widely used coloring agent and spice in food, has a potential in blocking brain tumor formation and curing Alzheimer’s disease. Due to the specific properties of blood–brain barrier (BBB), only traces of curcumin were transported across BBB. The aim of the present study was to design and characterize curcumin loaded polybutylcyanoacrylate nanoparticles (PBCN) coated with polysorbate 80, and to evaluate the effect of PBCN as a delivery system on carrying curcumin across BBB. Curcumin loaded nanoparticles were prepared by an anionic polymerization method, and they presented in a core–shell spherical shape under transmission electron microscopy, with an average diameter of 152.0 nm. The average drug loading was 21.1%. Physicochemical status of curcumin in the nanoparticles was confirmed with differential scanning colorimetry and Fourier transform infrared spectroscopy. The in vitro release behavior of drug from the nanoparticles was fitted to a double phase kinetics model. The studies of pharmacokinetic and bio-distribution to brain were conducted in mice after intravenous administration of the nanoparticle formulation at the dose of 5 mg/kg and curcumin solution at the dose of 10 mg/kg via the tail vein. The results showed that in plasma, the area under concentration–time curve (AUC_0–∞) for curcumin loaded nanoparticles was greater than that for the control solution, moreover, the mean residence time of curcumin loaded nanoparticles was 14-fold that of the control solution. In brain, AUC_0–∞ for curcumin loaded nanoparticles was 2.53-fold that for the control solution. In conclusion, the present study demonstrated that PBCN could enhance the transport of curcumin to brain and have a potential as a delivery system to cross the BBB.     

四氯化碳-水-十六烷基三甲基溴化铵三元体系凝胶的生成机理初探

自从1921年凝胶首次由小分子制得以来,小分子凝胶研究已经有了一定的进展。特别是近几十年小分子凝胶在医药、化妆品、食品、卫生用品等各个领域应用,被人们广泛关注。但到目前为止,人们对基于表面活性剂的小分子凝胶的结构和生成机理,特别是水、有机溶剂和表面活性剂在形成小分子凝胶过程中的作用仍认识十分有限。可使用水、四氯化碳和三甲基十六烷基溴化铵(CTAB)制出了一种小分子凝胶,并根据滴定和XRD实验结果提出了水和四氯化碳协同增溶表面活性剂CTAB形成凝胶的机理。红外光谱与核磁共振实验结果证明CTAB在凝胶中通过分子堆砌形成准有序结构。