Simultaneous detection of uric acid and glucose on a dual-enzyme chip using scanning electrochemical microscopy/scanning chemiluminescence microscopy

Scanning electrochemical microscopy (SECM) and scanning chemiluminescence microscopy (SCLM) were used for imaging an enzyme chip with spatially-addressed spots for glucose oxidase (GOD) and uricase microspots. For the SECM imaging, hydrogen peroxide generated from the GOD and/or uricase spots was directly oxidized at the tip microelectrode in a solution containing glucose and/or uric acid (electrochemical (EC) detection). For the SCLM imaging, a tapered glass capillary (i.d. of 1∼2 μm) filled with luminol and horseradish peroxidase (HRP) was used as the scanning probe for generating the chemiluminescence (CL). The inner solution was injected from the capillary tip at 78 pl s⁻¹ while scanning above the enzyme-immobilized chip. The CL generated when the capillary tip was scanned above the enzyme spots was detected using a photon-counter (CL detection). Two-dimensional mapping of the oxidation current and photon-counting intensity against the tip position affords images of which their contrast reflects the activity of the immobilized GOD and uricase. For both the EC and CL detections, the signal responses were plotted as a function of the glucose and uric acid concentrations in solution. The sensitivities for the EC and CL detection were found to be comparable.     

吡嗪衍生物在石墨表面上的自组装单层膜结构

利用扫描隧道显微镜研究了荧光液晶分子2, 5-二-[2-(3, 4-二-十二烷氧基-苯基)-乙烯基]-3, 6-二甲基吡嗪(BPDP12)在石墨表面上自组装单层膜的结构. 实验结果表明, 该化合物在石墨表面形成两种自组装结构：一种是稳定的, 分子的共轭中心相互平行, 烷基链相互交错的密排结构；另一种是不稳定的, 分子的共轭中心彼此为烷基链所分隔的非密排结构. 分子之间较强的π-π作用和分子烷基链之间的范德华作用力对分子组装的取向形成竞争, 是产生两种不同组装结构的根本原因.     

甘露醇纯度的差示扫描量热法测定

使用差示扫描量热法(DSC)对甘露醇纯度进行测定。密封式铝坩埚封装样品,最佳实验条件为升温速率约0.7℃·min-1,样品量约2.5mg,氮气流速为20～40mL·min-1;纯度测定的RSD为0.016,纯度准确测定的下限为98%,通过F检验及t检验,该方法与药典法无显著差异。该方法简便、快速、准确,适合甘露醇等高纯度药品的纯度测定。     

Investigation of Active and Inactivated Yeast Cells by Scanning Electrochemical Impedance Microscopy

Scanning electrochemical microscopy (SECM), electrochemical impedance spectroscopy (EIS) and scanning electrochemical impedance microscopy (SEIM) were used to investigate electrochemical activity of active and inactivated yeast Saccharomyces cerevisiae cells. SEIM experiment was performed using a unique electrochemical impedance spectrometer with a fast Fourier transform (FFT‐EIS) function, which enabled simultaneously perturb/evaluate electrochemical system at 50 frequencies. This allowed very quick observing the differences between impedance spectra, which were taken every few seconds. Therefore, we were able to apply SEIM for relatively fast determination of electrochemical impedance dependence on the distance between ultramicroelectrode (UME) and surface modified by immobilized yeast cells. It was determined that electrochemical activity and ‘breathing’ (a consumption of dissolved oxygen) of yeast can be electrochemically observed when the distance between UME and surface of yeast cells is in the range from 0 μm to 25 μm. Therefore, 25 μm is the maximum distance suitable for efficient investigation of yeast cell activity when experiments are performed in FFT‐SEIM mode. Charge transfer resistance of active and inactivated yeast cells was determined using EIS. It was calculated that charge transfer resistance of active yeast cells is 1.5 times lower than that of inactivated yeast cells. Lipophilic vitamin K₃ (Vit‐K₃) and hydrophilic vitamin K₁ (Vit‐K₁) were mixtured and used as redox mediators for charge transfer from yeast cells.     

对DSC单峰纯度测定法的评述

指出了当前流行的差示扫描量热法DSC单峰法测样品纯度所基于的假定有一些不确切的地方,并用计算机动态摸拟了DSC实验过程,结果证实了本文的论断。     

取代烷基侧链长度对二维纳米结构的影响

合成了一系列烷基取代的间苯三酚衍生物,并在大气条件下用扫描隧道显微镜研究了它们在高定向裂解石墨表面的吸附和组装行为.实验结果表明,这些自组装分子具有条状结构特征.在链长较短的分子图像中,两条平行的烷氧基链肩并肩地排列在苯环的一侧,另一条烷氧基链则排列在苯环的另一侧,链与链之间彼此相互交错排列形成均一的烷基条带.当链长增加时,这种高稳定性和密排结构遭到破坏,出现单个分子和分子对共存的组装结构.这是由于烷基链与烷基链之间以及烷基链与基底之间的作用力共同决定的.通过调控分子烷基链的长度可以得到不同的表面二维纳米结构.     

Morphology assessment of chemically modified cryostructured poly(vinyl alcohol) hydrogel

The morphology of hydrogels based on poly(vinyl alcohol) (PVA) in their frozen hydrated state, modified with biologically active di- and multifunctional molecules was studied by scanning electron microscopy (SEM) with cryo-attachment. The porosity of samples was found to be more regular and ordered in the case of samples containing difunctional, and especially multifunctional carboxylic acids as compared to the neat PVA hydrogel. The morphology is dependent not only from the hydrogel composition but also the number of freezing-thawing cycles. Resulted highly porous and oriented structure has significant influence on materials properties, such as compressive stress and crosslinking density.     

钯纳米线电极的制备及其应用于乙醇的电化学氧化研究

纳米线作为纳米科学领域中的重要一员,因其优异的光学、电学及磁学等特性引起了凝聚态物理学界、化学界以及材料科学界科学家们的极大关注,并己成为当今纳米科技研究的热点领域[1].纳米线的制备方法有多种,本文提及的模板法制备纳米线结构技术是20世纪90年代初发展起来的一种既经济又简便实用的新工艺[2].     

Vapour liquid equilibria of monocaprylin plus palmitic acid or methyl stearate at P = (1.20 and 2.50) kPa by using DSC technique

The Differential Scanning Calorimetry (DSC) technique is used for measuring isobaric (vapour + liquid) equilibria for two binary mixtures: {monocaprylin + palmitic acid (system 1) or methyl stearate (system 2)} at two different pressures P = (1.20 and 2.50) kPa. The obtained PTx data are correlated by Wilson, NRTL and UNIQUAC models. The original UNIFAC group contribution method is also considered and new binary interaction parameters for the main groups CH₂, CCOO, OH and COOH are regressed, to account for the non-idealities found in these lipid systems. Established thermodynamic consistency tests are applied and attest the quality of the measured data. In terms of relevance of the selected components, system 1 can be found in the purification and deodorization steps during the production of edible oils, while, system 2 can be found in the purification steps of biodiesel. It should be noted that no such data could be found in the open literature, not only for the specific components selected but also for the combination of the classes of components considered; that is, acylglycerol plus fatty acid or fatty ester.     

Organic semi-conducting architectures for supramolecular electronics

The properties of organic electronic materials in the solid-state are determined not only by those of individual molecules but also by those of ensembles of molecules. The ability to control the architectures of these ensembles is thus essential for optimizing the properties of conjugated materials for use in electronic devices (light emitting diodes, field effect transistors, solar cells, …) and is primordial for potential technological applications in nanoelectronics.Here, we report on the observation by atomic force microscopy (AFM) of 1D and 2D nanoscale architectures obtained in the solid-state from solutions of molecularly-dissolved conjugated block copolymers or oligomers, and demonstrate that the conjugated molecules can organize onto a surface over lengthscales from nanometers to several microns, forming semiconducting fibrils or bi-dimensional organizations (monolayers) by π-stacking processes (by changing the sample preparation conditions).     

Scanning Tunneling Microscopy and Atomic Force Microscopy in Organic Chemistry

When Kekulé awoke from dreams of snakes biting their own tails, he didn't have the benefit of a scanning tunneling microscope (STM) image to confirm that his vision of benzene as a cyclic molecule was accurate. References to STM in the chemical literature increase steadily, although the technique was perhaps oversold in its early days of the 1980s, with such promises as DNA sequencing and tailored bi-molecular chemical reactions (literally, two molecules). Publications alternate between attempting to explain the process by which images of traditional insulators are obtained and simply presenting the end images themselves as stunning views of atoms and molecules. While imaging mechanisms are still being debated, these instruments' ability to “see” single molecules has been established, albeit at the fringes of our expectations. For example, whereas STM studies at present might not be able to answer the question of why adsorption of CO doubles the density of platinum atoms on the surface of a single crystal of the metal, the images go far in illustrating that this is a process which platinum undergoes. As with any emerging analytical tool, these scanning, very localized microscopic methods are undergoing the growing pains of irreproducible results and mis-marketed artifacts. Nonetheless, we assemble here, primarily for the uninitiated, a collection of careful and credible studies to mark the progress of scanning tunneling microscopy and atomic force microscopy into chemistry, and to encourage a healthy blend of idealism and skepticism toward future work.     

Investigation of negative differential resistance properties of self-assembled dipyridinium using STM

Recently, research on conducting molecules containing thiol functional groups such as benzenethiol has been progressing [X. Xiao, B. Xu, N.J. Tao, Nano Lett. 4 (2004) 267]. This conducting molecule is applicable to the study of the negative differential resistance (NDR) and switching properties of logic device. The 4-{4[4-(4-{1-[4-(4-acetylsulfanyl-phenylethynyl)-phenyl]-2,6-diphenyl-pyridinium-4-yl}-phenyl)-2,6-diphenyl-pyridinium-1-yl]-phenylethynyl}-phenylthioacetate (dipyridinium) molecule contains thiol functional groups such as benzenethiol. Thus, we have studied an NDR property of a dipyridinium molecule using the self-assembly method in scanning tunneling microscopy (STM). The Au substrate was exposed to a 1 mM solution of 1-dodecanethiol in ethanol for 24 h to form a monolayer. After thorough rinsing of the sample, it was exposed to a 0.1 μM solution of dipyridinium in dimethylformamide (DMF) for 30 min. After the assembly, we measured the electrical properties of the self-assembly monolayers (SAMs) using ultra high vacuum scanning tunneling microscopy (UHV-STM) and scanning tunneling spectroscopy (STS). As a result, we confirmed the properties of NDR in a negative region at −1.67 V and a positive region at 1.78 V. The energy gap (E_g) was found to be 3.12 eV [C. Arena, B. Kleinsorge, J. Robertson, W.I. Milne, M.E. Welland, J. Appl. Phys. 85 (1999) 1609]. This molecule is applicable to the fabrication of molecular junctions.     

4-甲氟基香豆素衍生物的热力学特性研究

This paper describes the DSC study of 4-trifluorocoumarin derivatives, C_(481), C_(485), C_(500) and C_(480), providing their DSC thermograms and thermodynamic parameters during the phase transitions of these compounds. Singlemelting peaks were observed on DSC thermogram respectively.Experimental results show the existence of certain correlations between the melting point, heat of fusion and molecular structure for this series of compounds.     

有机涂层失效过程的电化学阻抗和电位分布响应特征

结合使用电化学阻抗谱(EIS)和扫描Kelvin探针(SKP)技术研究了在质量分数为3.5%的NaCl溶液中的铁基有机涂层劣化过程特征. 结果表明, 根据EIS和SKP的响应特征, 可将涂层劣化过程分为3个主要阶段: (Ⅰ) 涂层渗水阶段. 此时, 涂层渗水阶段的EIS阻抗持续减小, 但保持单容抗弧特征, SKP特征是电位持续降低, 但分布保持均匀; (Ⅱ) 基底金属腐蚀发生阶段. 此时, EIS阻抗快速下降, 并产生第二时间常数; SKP特征为表面电位差增大; (Ⅲ) 基底金属腐蚀发展与涂层失效阶段. 此时, EIS出现扩散尾, SKP电位差保持较大数值. 实验结果表明, 在研究有机涂层劣化过程中, EIS和SKP的结合使用能够互相补充完善, 获得涂层劣化过程中更为准确\, 可靠的变化信息.     

仿生生物膜上多巴胺的电子转移过程研究

利用薄层法(TLCV)研究了硝基苯(NB)/水(W)界面上二茂铁(Fc)-多巴胺(DA)体系的电子迁移(ET)过程,得到该体系界面电子转移速率常数为1.012cm.s^-1.mol^-1.L,界面电子转移反应为单电子过程(n=0.89).采用扫描电化学显微镜(SECM)对同一体系进行研究,得到电子迁移速率常数为(1.10±0.2)cm.s^-1.mol^-1.L,两种方法所得结果吻合,证明了薄层法的可行性.同时,低的反应物浓度比又一次验证了Barker理论.     

Effect of methanolic plant extract on copper electro-polishing in ortho-phosphoric acid

The behavior of copper electro-polishing in ortho-phosphoric acid using the galvanostatic polarization method was ascertained. This was examined via measuring and comparing anode potential –limiting current relationship in solution of regularly mounting concentrations (from 50 to 1800 ppm of methanolic Allium sativum (garlic extract), Tilia cordata (Tilia leafs), Foeniculum vulgare (fennel seeds), and Lablab purpureus (Dolichos lablab extract) and weight loss method. Influence of temperature on the dissolution kinetics were investigated. First order kinetic is applicable to the copper dissolution in solution containing plant extracts. Surface morphologies, brightness and roughness of polished specimens were examined with a scanning electron microscope (SEM), reflectance and atomic force microscope (AFM). Addition of methanolic plant extract to electro-polishing solution produce a lesser limiting current. According to SEM, UV–VIS-NIR spectra and surface roughness measurements, addition of high concentration (1800 ppm) of methanolic plant extract to the electrolytic solution is highly effective to enhance surface quality. High reflection property is obtained when the different type of methanolic plant extract is added to the electro-polishing electrolyte. The minimum Ra and PV values are achieved by garlic extract, which records the highest reflectance value and inhibition efficiency. Weight loss data obtained is excellent conformity with the result obtained by electrochemical measurements.     

Construction of two-dimensional (2D) H-bonded supramolecular nanostructures studied by STM

In this review,a group of two-dimensional（2D） hydrogen-bonded supramolecular networks developed in our laboratory are discussed.Our attention is mainly focused on:（1） recognition of Fe³⁺ through twocomponent molecular networks;（2） site-selective fabrication of 2D fullerene arrays;and（3） fabrication of the nanoporous structure regulated by photoisomerization reaction process.It is envisioned that special supramolecular nanostructures,through H-bonding interactions,can be constructed or reconstructed to be further investigated toward the research of multi-component systems,molecule recognition,single molecular switches,and host-guest supramolecular chemistry.     

Recent advances in scanning electrochemical microscopic analysis and visualization on lithium-ion battery electrodes

Scanning electrochemical microscopy is a family of techniques that probes the local electrochemical surface environments with micrometer- and nanometer-scale space resolution and sub-picoampere chemical sensitivity. A recent growing trend uses these probes to investigate surface systems related to lithium-ion batteries, yielding a prodigious amount of new information. In this review, we give an overview of the recent progress on the scanning electrochemical microscopy and related techniques’ breakthroughs on lithium-ion battery electrodes research.     

异代酯基枝状分子表面组装及结构转化机理的STM研究

利用扫描隧道显微技术(STM)研究了3种异代酯基Janus枝状分子(G₁G₂COOCH₃, G₀G₃COOCH₃, G₁G₃COOCH₃)在高定向裂解石墨(HOPG)表面的组装结构. 室温下, G₁G₂COOCH₃, G₀G₃COOCH₃和G₁G₃COOCH₃分别在表面形成有序、局部有序及无序结构. 将样品加热至60~80 ℃后, 表面无序结构可以转化为有序的二聚体密堆积结构. 实验结果表明, 随着枝状分子代数的增加, 分子之间及分子与基底之间作用力增强, 室温下分子组装行为更依赖于分子吸附动力学过程, 组装结构趋于无序化, 而加热可以增强枝状分子在表面的活动性, 调整分子的位置关系, 使表面无序结构转化为热力学稳定的有序二聚体密堆积组装结构.     

A study of the surface morphology of poly(p-phenylene terephthalamide) chars using scanning probe microscopy

The objective of this work was to investigate the changes in surface morphology associated with thermal degradation of poly(p-phenylene terephthalamide) (PPTA) into chars. To this end, PPTA samples decomposed at several temperatures up to 800 °C were studied on a local scale using atomic force microscopy (AFM) and scanning tunnelling microscopy (STM). Domains with a diameter of 40-50 nm started appearing among PPTA nanofibrils at about 500 °C. At this temperature and above, a film coating the fibre developed. This layer was much less rigid than PPTA, and remained deposited on the fibres, even at high temperatures. At 800 °C, the STM images showed a surface distribution typical of a carbonaceous material, isotropic although somewhat heterogeneous. When an intermediate isothermal step (500 °C, 200 min) was introduced along with heat treatment of PPTA under a constant rate, the material obtained at the end of this step was conductive enough to be studied by STM. Although the coating over the fibres also remained after the isothermal step, it was less homogeneous than in the absence of isothermal treatment. On further heating, the residue exhibited a surface morphology typical of a carbonaceous material, but much more homogeneous and isotropic than in the absence of the isothermal step.