分子印迹电化学发光分析

分子印迹电化学发光兼具分子印迹技术及电化学发光方法两者的优点,即高灵敏度、高选择性、可控性好、易于微型化和操作简单等特点。近几年来在生物仿生传感器、有害农药残留物质及食品安全监测等方面具有广泛的应用。本综述简要介绍分子印迹电化学发光传感器及分子印迹固相萃取电化学发光的概况,并对其今后的研究趋势进行展望。     

分子印迹-电化学发光技术研究进展

分子印迹-电化学发光技术具有分子印迹技术的高选择性及电化学发光技术的高灵敏性,以及发光易于调控、稳定性好、便于微型化和仪器操作简单等优点,已被广泛地应用于重金属检测、免疫传感技术、基因传感技术、酶传感技术、食品安全与药物分析等领域。该文结合本实验室的研究工作介绍了分子印迹电化学发光传感器的原理和构建思路。在此基础上,着重介绍了分子印迹电化学发光技术在食品安全与药物分析中的应用,并对其今后的研究趋势进行了展望。     

基于磁性分子印迹聚合物的电化学传感器的研究进展

分子印迹聚合物与磁性纳米材料结合,制备成磁性分子印迹纳米敏感膜,这样做不仅可以发挥分子印迹聚合材料的优势,而且磁性纳米粒子可有效提高电化学传感器的灵敏度、稳定性以及生物相容性等。近年来将磁性分子印迹纳米敏感膜应用于电化学传感器制备成的磁性分子印迹电化学传感器得到了较快的发展。本文就近5年来磁性分子印迹电化学传感器敏感膜所用的磁性材料、敏感膜制备方法以及磁性分子印迹电化学传感器在环境、食品以及临床方面的应用进行了综述总结。     

分子印迹电化学传感器

分子印迹电化学传感器能够选择性识别并检测特定目标化合物,因其设计简单、灵敏度高、价格低廉、携带方便、易于微型化和自动化等优点,在临床诊断、环境监测、食品分析等方面越来越受到人们的关注.本文作者主要论述分子印迹技术与电化学技术相结合构建分子印迹电化学传感器,包括分子印迹电化学传感器的种类,以及电化学方法制备分子印迹聚合物膜的常用单体等.对分子印迹电化学传感器领域新出现的分子印迹聚合物-纳米材料复合物以及纳米结构分子印迹聚合物也一并做了评述.     

基于分子印迹技术的电化学发光分析

基于分子印迹技术的电化学发光分析是近几年刚刚发展起来的新型分析方法,兼具分子印迹技术与电化学发光方法两者的优点,具有高灵敏度、高选择性、可控性好、易于微型化和操作简单等特点,在生命科学、食品安全及环境监测等领域有着广泛的应用前景。本综述简要介绍了常用的电化学发光体系和基本原理,综述了近年来分子印迹电化学发光分析的主要研究进展,对不同类型分子印迹电化学分析的构建方法、原理及所构建方法的性能(包括灵敏度、选择性、检测范围和稳定性等)进行了评述。基于分子印迹技术的电化学发光分析主要可以分为三类:制备固态发光电极、非固态发光电极构建分子印迹电化学发光传感器和分子印迹固相萃取与电化学发光分析联用,其中制备固态发光电极用于构建分子印迹电化学发光传感器最有发展前景。最后,本综述也对分子印迹电化学发光分析今后的发展趋势和方向进行了展望。     

电化学表面增强拉曼光谱的量子化学研究

对于在分子水平上研究电化学表面吸附和反应过程,表面增强拉曼光谱(SERS)显示出了其独到的优势,提供了有力的技术方法,但对于其表面增强机理仍有待深入研究.本文总结了将量子化学计算应用于电化学表面增强拉曼光谱(EC-SERS)分析的研究,以电化学界面分子吸附、电化学反应以及光电化学反应的研究体系为模型,提取EC-SERS光谱所蕴藏的物理化学信息.通过对吡啶在电化学表面的吸附、水的吸附及其电化学反应、以及对巯基苯胺的电化学表面催化偶联反应等体系的研究,揭示了电化学表面吸附、反应和光电化学过程的本质.     

有序分子组装膜电极非理想伏安图的理论研究

在有序分子组装体系的电化学研究中,电活性物种间的相互作用直接导致其偏离理想的电化学行为,譬如出现双峰或者峰展宽的现象。从这些非理想的电化学数据中提取热力学和动力学数据显得相对困难,因而了解和评价这些非理想的电化学行为显得十分有必要。本文着重就这些非理想电化学现象的理论模型、基本公式和微观认识进行了评述。理解这些非理性电化学的影响因素,不仅加深对表面电化学体系的认识,更对现在的研究热点课题如主客体识别、分子电子器件、生物传感器等具有重要意义。     

生物电化学仪器的发展现状与展望

电荷传递是生命运动的基本过程之一,电化学方法在生命科学中的应用为相关生命现象的研究提供了一个有效而独特的物理化学视角,并带来超出常规生物学检测的丰富信息.随着生物电化学研究的不断扩展和深化,已从早期的生物分子电化学研究深入向活体、活细胞、单活细胞水平甚至活细胞中单分子水平发展.研究者对仪器设备性能如灵敏度、分辨率(时间分辨、空间分辨和能量分辨)和操作性等提出了越来越高的要求.本文综述了生物电化学仪器在应用领域和研究领域的现状,重点介绍单细胞电化学检测系统的构建,并初步探讨国内生物电化学研究仪器的发展趋势.     

生物小分子的电分析化学研究——Ⅳ.维生素K_3的电化学性质和光谱电化学表征

研究了维生素K_3在热解石墨电极上的电化学行为、分子定向和分子间的相互作用,用紫外吸收光谱电化学验证了它的电化学还原机理.实验结果表明维生素K_3在热解石墨电极上的反应是受吸附作用控制的2e、2H~+准可逆过程,维生素K_3分子是以C(6,7)位上的H按垂直方向吸附于热解石墨电极表面的,且吸附分子间存在着相斥的相互作用,其吸附平衡常数约为1.11×10~5,吸附能约为28.8KJ.mol~(-1).吸收光谱电化学实验结果表明维生素K_3电化学还原产物为2-甲基1,4-萘酚.     

植物激素电化学传感技术研究进展

植物激素是植物自身合成的微量小分子有机物,作为信号分子,在极低浓度就能对植物生长发育产生显著调控作用.植物激素的超微量及原位测定技术是该研究领域的重要研究课题.在众多的检测手段中,电化学方法因其高灵敏和可动态监测等特点而备受青睐.本文综述了近年来植物激素电化学传感技术的最新研究进展,内容涵盖植物激素电化学生物传感、植物激素直接电化学传感、植物激素光电化学传感、植物激素分子印迹电化学传感等研究领域,并对植物激素电化学传感技术的发展趋势进行了展望.     

Laser flash photolysis and magnetic field effect studies on the interaction of uracil and its derivatives with menadione and 9,10-anthraquinone

Laser flash photolysis and an external magnetic field have been used to study the interaction of two quinone molecules, namely, 9,10-anthraquinone (AQ) and 2-methyl-1,4-naphthoquinone, commonly known as menadione (MQ), with the RNA base uracil (U) and two of its derivatives, 1,3-dimethyluracil (dmU) and uridine (dU). We have conducted our studies in homogeneous organic and heterogeneous micellar media in order to investigate the effect of media on the molecules and any change in reactivity on account of substitution. In organic homogeneous medium, both the quinones have behaved similarly with the bases. Here U has undergone both electron transfer (ET) and hydrogen (H) transfer, while dU and dmU have failed to exhibit any ET. Failure to support ET has been attributed to keto-enol tautomerism, which has been found to have a significant role in determining the occurrence of ET from these pyrimidine bases. However, in SDS micelles some variations regarding the reactivity of these molecules have been discerned. The variations are 2-fold. Here ET from U has been found to get completely eclipsed by a dominant H abstraction with both the quinones, and AQ reveals a difference in the extent of H abstraction with the bases in SDS. With U and dU, the prevailing H abstraction with AQ has succeeded in formation of only AQH(*), while dmU has produced both AQH(*) and AQH(2), the latter being formed by two successive H abstraction. Explanations of this intriguing behavior with U and its derivatives with quinone molecules have been the main concern in this work.     

Ab initio calculation for inner reorganization energy of gas-phase electron transfer in organic molecule–ion systems

A series of electron transfer (ET) reactions between some organic molecules have been investigated through ab initio calculations. Biphenyl (Bp) and 9,9^′-dimethylfluorene anion radicals are chosen as the donor, whereas several organic molecules with different redox abilities are chosen as the acceptor. The inner reorganization energy and the endothermicity of the ET reactions in those molecule–ion systems have been estimated through the HFSCF and complete active space multiconfiguration SCF calculations. Double-well potentials for the gas-phase ET reactions have been constructed using the linear reaction coordinate, and the results show that the quinone-containing ET reactions are in Marcus' inverted region. It has been found that the inner reorganization energies are different for various donor-acceptor couples, unlike the experimentally fitted ones. The contribution from the inter-ring torsional motion in Bp to the inner reorganization energy has been evaluated from the energy difference of the biphenyl-acceptor and the dimethylfluorine-acceptor systems. Comparisons with the experimentally observed results have been made.     

In situ STM imaging and direct electrochemistry of Pyrococcus furiosus ferredoxin assembled on thiolate-modified Au111 surfaces

We have addressed here electron transfer (ET) of Pyrococcus furiosus ferredoxin (PfFd, 7.5 kDa) in both homogeneous solution using edge plane graphite (EPG) electrodes and in the adsorbed state by electrochemistry on surface-modified single-crystal Au111 electrodes, This has been supported by surface microscopic structures of PfFd monolayers, as revealed by scanning tunneling microscopy under potential control (in situ STM). Direct ET between PfFd in phosphate buffer solution, pH 7.9, and EPG electrodes is observed in the presence of promoters. Neomycin gives rise to a pair of redox peaks with a formal potential of ca -430 mV (vs SCE), corresponding to [3Fe-4S]1+/0. The presence of an additional promoter, which can be propionic acid, alanine, or cysteine, induces a second pair of redox peaks at approximately -900 mV (vs SCE) arising from [3Fe-4S]0/1-. A robust neomycin-PfFd complex was detected by mass spectrometry. The results clearly favor an ET mechanism in which the promoting effect of small organic molecules is through formation of promoter-protein complexes. The interaction of PfFd with small organic molecules in homogeneous solution offers clues to confine the protein on the electrode surface modified by the same functional group monolayer and to address diffusionless direct electrochemistry, as well as surface microstructures of the protein monolayer. PfFd molecules were found to assemble on either mercaptopropionic acid (MPA) or cysteine-modified Au111 surfaces in stable monolayers or submonolayers. Highly ordered (2 radical 3 x 5)R30 degrees cluster structures with six MPA molecules in each cluster were found by in situ STM. Individual PfFd molecules on the MPA layer are well resolved by in situ STM. Under Ar protection reversible cyclic voltammograms were obtained on PfFd-MPA/Au111 and PfFd-cysteine/Au111 electrodes with redox potentials of -220 and -201 mV (vs SCE), respectively, corresponding to the [Fe3S4]1+/0 couple. These values are shifted positively by 200 mV relative to homogeneous solution due to interactions between the promoting layers and the protein molecules. Possible mechanisms for such interactions and their ET patterns are discussed.     

Photochemical electron transfer through [corrected] the interface of hybrid films of titania nano-sheets and mono-dispersed spherical mesoporous silica particles

Photochemical Electron Transfer (ET) between an organic dye, the porphyrin derivative TMPyP, and an electron acceptor, methyl viologen MV2+, have been investigated at the interface of two different inorganic films, i.e., layered titania nano-sheets (TNS) and a monolayer film of spherical and mono-dispersed mesoporous silica (sMPS) particles (ca. 0.5 microm). TMPyP ions were intercalated within the sMPS nano-cavities to form (TMPyP-sMPS) while MV2+ ions were intercalated into the TNS interlayers to form (MV2+-TNS). The (TMPyP-sMPS) and (MV2+-TNS) films were then stacked on a silica substrate in this order to form a (MV2+-TNS)/(TMPyP-sMPS) film and, upon UV light irradiation, ET could be induced. However, when this film was stacked inversely, i.e., for the (TMPyP-sMPS)/(MV2+-TNS) films on a silica substrate, no photoinduced ET were observed. Interestingly, however, even for this photo-inactive inversely stacked film, ET could be generated by inserting a gold vapor-deposited layer between the (MV2+-TNS) and (TMPyP-sMPS) films. The conjugation conditions at the interface of the inversely stacked (TMPyP-sMPS)/(MV2+-TNS) hybrid film were, thus, confirmed to strongly affect the photoinduced electron transfers and their efficiencies.     

Organic mixed-valence compounds: a playground for electrons and holes

Mixed-valence (MV) compounds are excellent model systems for the investigation of basic electron-transfer (ET) or charge-transfer (CT) phenomena. These issues are important in complex biophysical processes such as photosynthesis as well as in artificial electronic devices that are based on organic conjugated materials. Organic MV compounds are effective hole-transporting materials in organic light emitting diodes (OLEDs), solar cells, and photochromic windows. However, the importance of organic mixed-valence chemistry should not be seen in terms of the direct applicability of these species but the wealth of knowledge about ET phenomena that has been gained through their study. The great variety of organic redox centers and spacer moieties that may be combined in MV systems as well as the ongoing refinement of ET theories and methods of investigation prompted enormous interest in organic MV compounds in the last decades and show the huge potential of this class of compounds. The goal of this Review is to give an overview of the last decade in organic mixed valence chemistry and to elucidate its impact on modern functional materials chemistry.     

Gold nanoparticles enhancing dismutation of superoxide radical by its bis(dithiocarbamato)copper(II) shell

In the past few years three topics in nanoscience have received great attention: catalytic activity of gold nanoparticles (AuNPs), their electron transfer properties, and magnetism. Although these properties could have much in common no report on their synergism has been published. Here we present 10-nm gold nanoparticles conveniently capped with a mixed self-assembled monolayer containing bis(dithiocarbamato)copper(II) complexes, which dismutate superoxide radical with extremely high efficiency (IC(50) = 0.074 μM). This behavior is interpreted as the result of an electron transfer (ET) process between AuNP core and the analyte when associated to copper(II). The ET process involving a charged AuNP core was detected by EPR and UV-vis spectroscopy.     

Mechanism of intramolecular electron transfer in the photoexcited Zn-substituted cytochrome c: theoretical and experimental perspective

Photoinduced electron transfer (ET) in zinc-substituted cytochrome c (Zn-cyt c) has been utilized in many studies on the long-range ET in protein. Attempting to understand its ET mechanism in terms of electronic structure of the molecule, we have calculated an all-electron wave function for the ground-state of Zn-cyt c on the basis of density functional theory (DFT). The four molecular orbitals (MOs) responsible for excitation by UV-vis light (Gouterman's 4-orbitals) are assigned on the basis of the excited states of chromophore model for Zn-porphine complex calculated with the time-dependent DFT method. ET rates between each Gouterman's 4-orbitals and other MOs were estimated using Fermi's golden rule. It appeared that the two occupied MOs of the 4-orbitals show exclusively higher ET rate from/to particular MOs that localize on outermost amino acid residues (Lys 7 or Asn 54), respectively, whereas ET rates involving the two unoccupied MOs of the 4-orbitals are much slower. These results imply that the intramolecular ET in photoexcited Zn-cyt c is governed by the hole transfer through occupied MOs. The couplings of MOs between zinc porphyrin core and specific amino acid residues on the protein surface have been demonstrated in Zn-cyt c immobilized on an Au electrode via carboxylic acid group-terminated self-assembled monolayer. The Zn-cyt c-modified electrode showed photocurrents responsible for photoillumination. The action spectrum of the photocurrent was identical with the absorption spectrum of Zn-cyt c, indicating photoinduced electron conduction via occupied MOs. The voltage dependence of the photocurrent appeared to be linear and bidirectional like a photoconductor, which strongly supports the intramolecular ET mechanism in Zn-cyt c proposed on the basis of the theoretical calculations.     

Relevance of electron transfer mechanism in electrocatalysis: the reduction of organic halides at silver electrodes

The mechanism of dissociative electron transfer (ET) to a series of organic chlorides has been investigated both at an inert electrode and at a catalytic surface such as Ag; electrocatalysis is important only when breaking of the carbon-halogen bond is concerted with the ET.     

Monolayer organic field-effect transistors

Monolayer organic field-effect transistors(OFETs) are attracting worldwide interest in device physics and novel applications due to their ultrathin active layer for two-dimensional charge transport. The monolayer films are generally prepared by thermal evaporation, the Langmuir technique or self-assembly process, etc., but their electrical performance is relatively lower than corresponding thick films. From 2011, the performance of monolayer OFETs has been boosted by using the monolayer molecular crystals(MMCs) as active channels, which opened up a new era for monolayer OFETs. In this review, recent progress of monolayer OFETs, including the preparation of monolayer films, their OFET performance and applications are summarized.Finally, perspectives of monolayer OFETs in the near future are also discussed.     

Non-Condon效应对电子转移速率影响的理论模拟及其在有机半导体中的应用

随着Condon近似下各种电子转移理论的不断发展与完善和人们对non-Condon效应在电子转移过程中重要作用认识的逐步深入,已建立了几个理论模型来研究这种效应对电子转移速率的影响.本文主要总结了近两年来我们在non-Condon效应电子转移理论方面的工作,首先阐述了指数型、高斯型以及直线型non-Condon电子转移速率的全量子表达式,然后运用该理论模型以及分子动力学模拟计算了二噻吩四硫富瓦烯（DT-TTF）有机半导体的迁移率.此外,还进一步利用数值模拟详细研究了这三种线型的non-Condon效应在量子尺度上对电子转移速率的影响.