闭合式无线纳米孔电极的一步法制备及单颗粒检测研究

以锥形石英固体纳米孔为模板, 通过化学法制备具有金纳米结构的纳米孔尖端, 从而实现一步法简单、 快速地制备直径为30 nm的闭合式无线纳米孔电极(CWNE); 探讨了制备过程中反应物浓度对制备过程的影响, 制备成功率高达85.7%, RMS噪音低至4.2 pA. 以金纳米颗粒碰撞电极实验为电化学测量模型, 获得了单个颗粒与纳米孔电极相互作用的信号, 验证了闭合式无线纳米孔电极对微秒级电信号的皮安级电流分辨能力, 为进一步探索纳米界面上的电子传递过程提供了稳定的测量界面.     

结合光学成像技术研究单颗粒碰撞电化学

近年来,单颗粒碰撞技术在纳米电化学领域受到广泛关注. 该技术通常控制超微电极处于某一电位,检测单个纳米颗粒随机碰撞到电极表面后产生的瞬时电流. 通过分析电流信号,可以研究单个纳米颗粒的性质. 尽管该技术可以检测单个纳米颗粒的电化学或电催化电流,但是传统的单颗粒碰撞技术缺乏空间分辨率,难以识别和表征特定的纳米颗粒. 因此,结合光学成像技术研究单颗粒碰撞电化学来补充电化学技术缺失的空间信息已成为一种趋势. 本文首先简要综述了单颗粒碰撞技术的三种检测原理,主要介绍了近年来单颗粒碰撞技术与荧光显微镜、表面等离激元共振显微镜、全息显微镜和电致化学发光相结合的研究进展,最后展望了单颗粒碰撞技术未来的发展趋势.     

单纳米颗粒在超微电极上的碰撞电化学分析：微电极和纳米管电极

纳米颗粒的功能与其尺寸、电荷密度和表面化学性质等密切相关,因此研究其内在关系至关重要。近年来,基于纳米颗粒碰撞的电化学方法可以实现对单个纳米颗粒的尺寸、浓度和聚集状态快速检测,进而有效区分纳米颗粒的个体差异和探索单个颗粒活性-结构之间的关系。鉴于电极的尺寸、形状对单颗粒碰撞结果存在显著影响,本文将重点介绍不同颗粒（金属、半导体和绝缘体）与传统超微电极和纳米管电极之间的碰撞行为,并基于目前纳米电化学碰撞技术的不足,展望未来纳米电化学碰撞技术的发展方向。     

双极纳米电极阵列实现单个铂纳米颗粒上氢气析出反应的电致化学发光成像（英文）

本文制备了嵌于多孔阳极氧化铝(AAO)膜中直径为200 nm,间距为450 nm的高密度(5.7×10~8 cm~(-2))的金纳米电极阵列,纳米电极分布规则,尺寸高度均一。我们将该金纳米电极阵列作为双极电极阵列,可将电极一侧的电化学法拉第信号在另一侧电极上转化成电致化学发光(ECL)信号,从而实现对单个铂纳米颗粒上氢气析出反应(HER)进行亚微米空间分辨率的电化学成像。本文介绍的方法为高空间分辨率成像电催化材料、能源材料以及细胞过程的局部电化学活性提供了一个良好的平台。     

双极纳米电极阵列实现单个铂纳米颗粒上氢气析出反应的电致化学发光成像

本文制备了嵌于多孔阳极氧化铝（AAO）膜中直径为200 nm,间距为450 nm的高密度（5.7 × 10⁸ cm^-2）的金纳米电极阵列,纳米电极分布规则,尺寸高度均一。我们将该金纳米电极阵列作为双极电极阵列,可将电极一侧的电化学法拉第信号在另一侧电极上转化成电致化学发光（ECL）信号,从而实现对单个铂纳米颗粒上氢气析出反应（HER）进行亚微米空间分辨率的电化学成像。本文介绍的方法为高空间分辨率成像电催化材料、能源材料以及细胞过程的局部电化学活性提供了一个良好的平台。     

纳米孔道单分子电化学测量仪器的稳定性研究

纳米孔道分析技术是一种基于电化学空间限域效应的单分子检测技术。测量纳米孔道产生的单分子皮安级微弱电流信号对电化学测量仪器的电流分辨、时间分辨和抗噪音能力提出了挑战。Cube纳米孔道电化学测量仪器通过设计频率补偿电路、前置电流放大器测量系统和基于现场可编程逻辑门阵列(FPGA)的高速数字处理电路,实现了便携式超灵敏电化学测量仪器对微弱电流信号的高时间分辨、高电流分辨,以及低噪音的放大、采集和快速处理。稳定性是仪器能够应用于实际单分子测量分析的重要衡量指标之一。该文通过高阻值电阻对该仪器进行稳定性测试,在截止滤波频率为5、10、100 kHz条件下,Cube纳米孔道仪器获取的电流基线的噪音均方根(RMS)值分别比商品化仪器减小了80.0%、87.5%、48.2%,证明Cube纳米孔道仪器抑制噪音能力更强,电流分辨能力更好,仪器测量稳定性更佳。进一步通过统计比较施加电压值的实际值和标准偏差,结果显示该仪器施加电压误差小,其仪器施加电压标准偏差仅为施加电压变化量(10 mV)的0.14%。同时,通过Aerolysin纳米孔道检测Poly(dA)4的实验,对比Cube仪器和商品化仪器在不同施加电压下获取的单分子信号残余电流程度,得到两者误差均小于0.01,结果具有可重复性。因此,Cube纳米孔道仪器具有稳定性好、灵敏度高、便携性强的特点,可应用于纳米孔道单分子分析。     

单分子电泳:纳米孔道电化学的新认识

该文旨在从电泳分离技术的角度认识纳米孔道电化学单分子分析技术,这种技术可以作为"单分子电泳"来理解和研究。纳米孔道电化学单分子分析技术与电泳的本质都是采用外加电场使待测分子产生电迁移。待测分子性质不同,且与介质材料孔道外露基团相互作用不同,使得分子移动速度具有差异,据此实现分离识别。气单胞菌溶素（Aerolysin）纳米孔道,由于其孔径与待测分子尺寸相匹配,其孔道内壁可以看作是由氨基酸组成的具有调控单个分子电迁移能力的特异性孔道界面。每一个氨基酸残基都相当于一个探测单元,在电场力的作用下,待测分子逐一进入孔道时与每一个探测单元相互作用方式、程度与时长不同,从而形成了单个待测分子特征的迁移速度和迁移运动轨迹。在纳米孔道实验中,每秒可以有上千个待测分子穿过孔道,产生特征阻断电流信号。通过对这些信号的阻断电流、阻断时间、阻断频率、信号特征等进行统计分析,可以从"单分子电泳"水平对单个待测物实现高通量的分辨和识别。该文以Aerolysin纳米孔道分辨仅有一个核苷酸差异的寡聚核苷酸（5'-CAA-3'、5'-CAAA-3'、5'-CAAAA-3'）为例,详细阐述了纳米孔道"单分子电泳"的单核苷酸分辨能力,展现了电化学限域空间在电泳单分子水平分离技术上的应用。     

氧化锌纳米簇-金纳米颗粒-壳聚糖复合膜修饰电极用于示差脉冲伏安法测定吗啡

将制备的氧化锌纳米簇和金纳米颗粒分散在壳聚糖中并滴涂在玻碳电极表面,制备了氧化锌纳米簇-金纳米颗粒-壳聚糖复合膜修饰电极(Au-ZnO-CHIT/GCE)。采用循环伏安法研究了吗啡在修饰电极上的电化学行为。结果表明:吗啡在该修饰电极上出现了一个氧化峰,提出了用示差脉冲伏安法测定吗啡的方法。吗啡浓度在5.3×10-6~6.5×10-4mol.L-1范围内与氧化峰电流呈线性关系,检出限(3S/N)为1.8×10-6mol.L-1。修饰电极用于尿液中吗啡的测定,回收率在80.0%~99.6%之间。     

纳米电极稳态电流表征的探讨

稳态循环伏安法具有简单、快速判别电极性能和估算电极尺寸的特性,因而被广泛应用于超微电极的表征.但纳米电极由于尺寸极小,其表面形貌的细微变化对电化学行为有明显的扰动,从而影响纳米电极表征的准确性.结合电化学实验和有限元模拟,探讨了纳米电极尺寸、绝缘层半径和电极半径之和与电极半径之比（RG）和尖端孔道对稳态电流的影响.研究表明尺寸较小（r ≤ 80 nm）的纳米圆盘电极,由于反应速率相对扩散较慢,电极反应过程受动力学效应控制,使稳态电流曲线偏离半球形扩散控制的标准"S"型.此外RG值较小的纳米圆盘电极,物质到电极的传递被增强,使极限电流值增大.我们对内嵌式纳米电极进行了进一步研究,并发现电极尖端孔道阻碍了电活性物质的扩散,削弱了动力学的限制,使极限电流值低于同尺度的纳米圆盘电极,伏安电流曲线呈现标准的"S"型.本研究系统地探讨了电极尖端形貌与稳态电流的相互关系,加深了对纳米电极电化学行为的理解.     

脉冲电沉积Pd-Ni合金纳米颗粒及其甲酸电催化氧化

采用方波脉冲方法,在钯镍合金电解液中成功地电化学沉积出镍原子含量分别为12.0%、16.4%和22.6%的钯镍合金纳米颗粒. 钯镍合金纳米颗粒为球状,粒径50 ~ 80 nm. 随钯镍合金生长电位负移,合金的镍含量提高,其纳米颗粒大小基本相似但纳米颗粒数目增多,交联度提高和真实活性面积增大. 钯镍合金纳米颗粒镍含量提高,在硫酸溶液中其氢弱吸附峰电流增大. 钯镍合金纳米颗粒电极的甲酸电催化氧化活性较好,随合金纳米颗粒的镍含量提高和交联度增加,合金纳米颗粒电极的甲酸电催化氧化稳定性更高.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.