Underpotential Deposition‐Induced Synthesis of Composition‐Tunable Pt?Cu Nanocrystals and Their Catalytic Properties

Pt? Cu alloy octahedral nanocrystals (NCs) have been synthesized successfully by using N,N‐dimethylformamide as both the solvent and the reducing agent in the presence of cetyltrimethylammonium chloride. Cu underpotential deposition (UPD) is found to play a key role in the formation of the Pt? Cu alloy NCs. The composition in the Pt? Cu alloy can be tuned by adjusting the ratio of metal precursors in solution. However, the Cu content in the Pt? Cu alloy NCs cannot exceed 50 %. Due to the fact that Cu precursor cannot be reduced to metallic copper and the Cu content cannot exceed 50 %, we achieved the formation of the Pt? Cu alloy by using Cu UPD on the Pt surface. In addition, the catalytic activities of Pt? Cu alloy NCs with different composition were investigated in electrocatalytic oxidation of formic acid. The results reveal that the catalytic performance is strongly dependent on Pt? Cu alloy composition. The sample of Pt₅₀Cu₅₀ exhibits excellent activity in electrocatalytic oxidation of formic acid.     

Plasmonic Scissors for Molecular Design

Heterogeneous catalysts play an important role in surface catalytic reactions, but selective bond breaking and control of reaction products in catalytic processes remain significant challenges. High‐vacuum tip‐enhanced Raman spectroscopy (HV‐TERS) is one of the best candidates to realize surface catalytic reactions. Herein, HV‐TERS was employed in a new method to control dissociation by using hot electrons, generated from plasmon decay, as plasmonic scissors. In this method, the N?N bond in 4,4′‐dimercaptoazobenzene was selectively dissociated by plasmonic scissors, and the reaction products formed from the radical fragment (SC₆H₅N) were controlled by varying the pH value. Under acidic conditions, p‐aminothiophenol was produced from the radical fragment by attachment of hydrogen ions, whereas under alkaline conditions, 4‐nitrobenzenethiol was obtained by attachment of oxygen ions to the substrate.     

Structural and Dynamic Basis of Human Cytochrome P450 7B1: A Survey of Substrate Selectivity and Major Active Site Access Channels

Cytochrome P450 (CYP) 7B1 is a steroid cytochrome P450 7α‐hydroxylase that has been linked directly with bile salt synthesis and hereditary spastic paraplegia type 5 (SPG5). The enzyme provides the primary metabolic route for neurosteroids dehydroepiandrosterone (DHEA), cholesterol derivatives 25‐hydroxycholesterol (25‐HOChol), and other steroids such as 5α‐androstane‐3β,17β‐diol (anediol), and 5α‐androstene‐3β,17β‐diol (enediol). A series of investigations including homology modeling, molecular dynamics (MD), and automatic docking, combined with the results of previous experimental site‐directed mutagenesis studies and access channels analysis, have identified the structural features relevant to the substrate selectivity of CYP7B1. The results clearly identify the dominant access channels and critical residues responsible for ligand binding. Both binding free energy analysis and total interaction energy analysis are consistent with the experimental conclusion that 25‐HOChol is the best substrate. According to 20 ns MD simulations, the Phe cluster residues that lie above the active site, particularly Phe489, are proposed to merge the active site with the adjacent channel to the surface and accommodate substrate binding in a reasonable orientation. The investigation of CYP7B1–substrate binding modes provides detailed insights into the poorly understood structural features of human CYP7B1 at the atomic level, and will be valuable information for drug development and protein engineering.     

A PEGylated Fluorescent Turn‐On Sensor for Detecting Fluoride Ions in Totally Aqueous Media and Its Imaging in Live Cells

Owing to the considerable significance of fluoride anions for health and environmental issues, it is of great importance to develop methods that can rapidly, sensitively and selectively detect the fluoride anion in aqueous media and biological samples. Herein, we demonstrate a robust fluorescent turn‐on sensor for detecting the fluoride ion in a totally aqueous solution. In this study, a biocompatible hydrophilic polymer poly(ethylene glycol) (PEG) is incorporated into the sensing system to ensure water solubility and to enhance biocompatibility. tert‐Butyldiphenylsilyl (TBDPS) groups were then covalently introduced onto the fluorescein moiety, which effectively quenched the fluorescence of the sensor. Upon addition of fluoride ion, the selective fluoride‐mediated cleavage of the Si? O bond leads to the recovery of the fluorescein moiety, resulting in a dramatic increase in fluorescence intensity under visible light excitation. The sensor is responsive and highly selective for the fluoride anion over other common anions; it also exhibits a very low detection limit of 19 ppb. In addition, this sensor is operative in some real samples such as running water, urine, and serum and can accurately detect fluoride ions in these samples. The cytotoxicity of the sensor was determined to be Grade I toxicity according to United States Pharmacopoeia and ISO 10993‐5, suggesting the very low cytotoxicity of the sensor. Moreover, it was found that the senor could be readily internalized by both HeLa and L929 cells and the sensor could be utilized to track fluoride level changes inside the cells.     

Catalytic Asymmetric Construction of Quaternary α‐Amino Acid Containing Pyrrolidines through 1,3‐Dipolar Cycloaddition of Azomethine Ylides to α‐Aminoacrylates

The first catalytic enantioselective 1,3‐dipolar cycloaddition of azomethine ylides to α‐aminoacrylate catalyzed by a AgOAc/ferrocenyl oxazolinylphosphine (FOXAP) system was developed, which exhibits excellent exo‐ and enantioselectivity (92–99 % ee). This process provides efficient access to useful 4‐aminopyrrolidine‐2,4‐dicarboxylic acid (APDC)‐like compounds containing a unique quaternary α‐amino acid unit.     

A New Series of C‐6 Unsubstituted Tetrahydropyrimidines: Convenient One‐Pot Chemoselective Synthesis,Aggregation‐Induced and Size‐Independent Emission Characteristics

A new series of C‐6 unsubstituted tetrahydropyrimidines 6 have been directly synthesized via a convenient urea‐catalyzed chemoselective five‐component reaction (5CR) under mild conditions. Compounds 6 show typical aggregation‐induced emission enhancement (AIEE) characteristics because they are practically no emissive in solution but emit blue or green fluorescence in aggregates with fluorescence yield up to 93 %. One of the 5CR products, 6 aa , exhibits blue‐ and green‐fluorescence aggregates (bf‐ and gf‐aggregates). The bf‐ and gf‐aggregates are prepared under different conditions and proved to result from different J‐aggregations by single‐crystal X‐ray analysis. In addition, the bf‐ and gf‐aggregates of 6 aa show unusual size‐independent emission (SIE) characteristics because their maximum emission wavelengths in different sizes (suspension particles, film, powder and crystals) are the same, 434 and 484 nm, respectively. Based on the obtained experimental results, the 5CR mechanism, the origins of AIEE and SIE characteristics are discussed.     

RP-HPLC法检测发酵液中赤霉素GA4,GA7的含量

建立了反相高效液相色谱法(RP-HPLC)测定发酵液中赤霉素GA4,GA7的方法。探讨了流动相缓冲盐与甲醇的比例、缓冲盐pH、温度、流速等对两种赤霉素分离的影响,结果表明在Kromasil C18(250 mm×4.6 mm,5μm)色谱柱下,以V(甲醇):V(pH3.0,0.05 mol/L KH2PO4)=60:40为流动相,柱温35℃,流速1.0 mL/min,检测波长228nm,进样量20μL,分离度良好。GA4,GA7标准品质量浓度分别在0.1~8.0 mg/mL,0.1~3.0 mg/mL范围内线性关系良好,线性回归方程为Y4=1.58878+7.06978X4,Y7=0.48281+7.12931X7;GA4,GA7检出限分别为19.6,14.3μg/mL,平均加标回收率分别为98.8%,99.9%,相对标准偏差RSD分别为1.5%,0.34%。     

纳米层状双金属氢氧化物改性PU/PMMA的制备及其弛豫行为

采用原位聚合法,制备了聚氨酯(PU)/聚甲基丙烯酸甲酯(PMMA)/层状双金属氢氧化物(LDH)纳米复合体系(PU/PMMA/LDH).通过广角X射线衍射(WXRD)、透射电子显微镜(TEM)对其结构和形貌进行了表征,并通过热失重(TGA)、动态力学分析(DMA)和宽频介电谱(BDRS)研究了LDH含量(φ)对PU/PMMA体系热稳定性和弛豫行为的影响.结果表明,当φ<1 wt%时,LDH在聚合物基体中以剥离结构为主,PU/PMMA/LDH体系的玻璃化温度(Tg)降低,最大损耗因子(tanδmax)增大;而当φ>1 wt%时,LDH在聚合物基体中以插层结构为主,插层结构对聚合物分子链的限制使复合体系的Tg升高、tanδmax降低.LDH表面与PU硬段间的氢键作用,使复合体系的α介电弛豫转变随φ增加而向高温方向移动,弛豫过程激活参数增大.     

镁电解槽中制备镁稀土合金的电解工艺及机制研究

在模拟镁电解槽中,采用电解法制备出稀土含量<10%的镁稀土合金;研究了熔盐中RECl3和CaCl2的含量、电解温度和阴极电流密度对合金中RE含量和电流效率的影响。并采用循环伏安实验和还原实验研究电解制备镁稀土合金的机制。研究结果表明,电解制备镁稀土合金最佳的工艺条件为:熔盐中RECl3和CaCl2的含量分别为3%和10%(质量分数),电解温度为948 K,阴极电流密度约为8 A.cm-2。其电解过程机制为:阴极上只电解出金属镁,而后金属镁把稀土元素还原出来,形成镁稀土合金。     

碳纳米管上原位沉积钯-钴-镍纳米颗粒及其对乙醇氧化的电活性

以水合肼为还原剂,在水和乙醇的混合溶液中制备多壁碳纳米管(MWCNT)负载的纳米镍(Ni/MWCNT)和纳米镍钴(Ni-Co/MWCNT)颗粒,然后将它们分别与氯化钯溶液反应,形成的钯纳米颗粒原位沉积在MWCNT表面,从而得到MWCNT负载的Pd-Ni/MWCNT和Pd-Ni-Co/MWCNT催化剂。SEM和TEM图像显示,MWCNT上的催化剂颗粒是由5~10 nm的小颗粒团聚而成的30~100 nm的大颗粒,三金属催化剂的粒径比双金属的粒径小,在MWCNT上的分散度更高。ICP和EDS分析显示,Pd直接还原并包覆在纳米镍和纳米镍钴表面;采用循环伏安和计时电流技术,研究了催化剂在碱性溶液中对乙醇氧化的电催化活性,结果表明,Pd-Ni-Co/MWCNT催化剂对乙醇氧化具有强的电催化活性,乙醇氧化对应的峰电流密度达101.8 mA·cm^-2,并且催化剂催化活性稳定。