表面增强拉曼光谱研究正己硫醇分子在银基底表面自组装过程的时间和浓度因素影响

表面增强拉曼光谱(SERS)是一种具有超灵敏检测能力的谱学技术,可以在单分子水平上检测分子结构的动态变化过程。烷基硫醇的自组装膜是一类典型的类晶态有序结构薄膜,在仿生、材料、电子和化学等领域有着重要的应用,越来越受到人们的关注。本文利用SERS对正己硫醇(hexanethiol,HT)分子在银基底上的吸附和组装过程进行研究,对HT的拉曼和自组装膜SERS光谱进行了指认。根据C-S,C-C和CH₃键结构的反式和旁式的特征光谱信息,研究HT吸附在银纳米粒子表面的构象,以及自组装膜结构的有序性。研究了吸附时间和浓度两个因素对成膜规律产生的影响。实验结果表明,当HT溶液浓度较高时,HT单层膜成膜速率较快,且有序性较好;当HT溶液浓度较低时,HT单层膜成膜速率较慢,且有序性较差。这一研究结果对成膜动力学以及烷基硫醇的有序单层膜的制备具有重要的指导意义,为基于烷基硫醇的自组装单层膜在防腐、器件和生物方面的应用奠定了基础。     

Adsorption of purpald SAMs on silver and gold electrodes: a Raman mapping study

The adsorption modes of 4‐amino‐3‐hydrazino‐5‐mercapto‐1,2,4‐trizole (purpald) self‐assembled monolayers (SAMs) formed on SERS‐active silver and gold electrodes were comparatively studied using surface‐enhanced Raman scattering (SERS), and the self‐assembling procedures were investigated by the Raman mapping technique. Purpald SAMs adopted a titled orientation with S, N2 atoms anchoring to the silver electrode and the  N7H₂ close to the surface, whereas purpald stood up on the gold electrode through S, N5 atoms and with  N8H₂ adjacent to the surface. The density functional theory (DFT) at the level of B3LYP was performed to help explain their different adsorption behaviors on the silver and gold electrodes. Copyright © 2006 John Wiley & Sons, Ltd.     

Electrochemical and in situ SERS spectroelectrochemical investigations of 4‐methyl‐4H‐1, 2, 4‐triazole‐3‐thiol monolayers at a silver electrode

Electrochemically anticorrosive behavior of 4‐methyl‐4H‐1, 2, 4‐triazole‐3‐thiol (MTTL) self‐assembled monolayers (SAMs) on the silver electrode was studied by means of electrochemical impedance spectroscopy (EIS) and polarization measurements. The promising inhibition effect of the MTTL for silver had been affirmed. Results of surface‐enhanced Raman scattering (SERS) experiments indicated that the MTTL molecule in a tilted orientation was self‐assembled on the silver surface through S⁶ and N² atoms to form monolayers. An in situ electrochemical SERS experiment implied the changes of adsorption fashion of MTTL momolayers on the silver surface with the potential shifted to more negative direction. Copyright © 2009 John Wiley & Sons, Ltd.     

2-氨基乙硫醇自组装单分子膜表面电离常数的FT-SERS方法测定(英文)

本文报道了采用原位傅立叶变换-表面增强拉曼散射(Fouriertransform-surfaceenhancedRamanscattering,FT-SERS)光谱技术测定在缓冲溶液和金电极界面上自组装单分子膜(self-assembledmonolayers,SAMs)的表面电离常数及其随电极电位改变的研究之初步结果。该方法通过应用FT-SERS原位光谱技术测定SAMs中质子化端基氨基的对离子ClO4特征峰强度随溶液pH值改变而变化的数值,获得相应的FT-SERS滴定曲线,进而可以确定一定条件下该SAMs功能化端基的表面电离常数。实验测定了2-氨基乙硫醇(2-aminoethanethiol,2AT)SAMs在三个不同电位下,在含有NaClO4支持电解质的Britton＆Robinson缓总溶液中的表面电离常数。实验结果揭示了在所研究的电位范围内,2ATSAMs端基氨基基团的表面pKa值随电极电位的正向增加而减小的变化规律。     

溶液酸碱性对金纳米粒子在端基功能化单分子膜表面组装影响的SERS光谱研究

在4,4’-二硫联吡啶在Au表面形成自组装单分子层膜的基础上,采用表面增强拉曼散射光谱(SERS)研究了在不同pH值条件下金纳米粒子在4,4’-二硫联吡啶自组装单分子膜/Au体系表面的组装。研究结果表明,由于处于单分子膜表面的吡啶环中氮原子的质子化程度随溶液环境中pH值的变化而变化,使得金纳米粒子与单分子膜表面间的结合作用程度不同,由此会引起金纳米粒子在单分子膜表面的覆盖度存在差异,并最终导致所观测到的4-巯基吡啶自组装单分子膜的SERS光谱强度存在明显的差异。而且,令人感兴趣的是,所观测到的SERS谱峰强度随金纳米粒子组装时pH值的变化呈现出明显的规律性。结合分子结构特征的分析,初步阐明了SERS谱峰强度随pH值这一组装条件的改变而发生规律性变化的内在原因。     

Thermal stability of thiol and silane monolayers: A comparative study

The stability of self-assembled monolayers (SAMs) at elevated temperatures is of considerable technological importance. The thermal stability of 1-octadecanethiol (ODT), 16-mercaptohexadecanoic acid (MHDA) and 1H,1H,2H,2H-perfluorodecanethiol (PFDT) SAMs on gold surfaces, and of 4-aminobutyltriethoxysilane (ABTES) and 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (PFDS) assembled on hydroxylated silicon surfaces, was studied by X-ray photoelectron spectroscopy (XPS). The samples were heated in ultrahigh vacuum to temperatures in excess of that required for SAM degradation. ODT monolayers were stable to ca. 110 °C, while MHDA and PFDT SAMs were stable to ca. 145 °C. ABTES SAMs were found to be indefinitely stable to 250 °C, while PFDS SAMs were stable to 350 °C. These studies demonstrate the advantages of using silane monolayers for moderate to high temperature applications and illustrate differences that arise due to the nature of the tail group. To demonstrate the feasibility of silanes for template-directed patterning, a hydroxylated silicon oxide surface containing microcontact-printed PFDS patterns was spin-coated with a mainly hydrophilic block copolymer. Annealing the surface at 90 °C for 2 h caused the block copolymer to dewet the hydrophobic PFDS-patterned regions and adsorb exclusively on the unpatterned regions of the surface.     

Self-assembled monolayers of octadecanoic acid on indium arsenide

Self-assembled monolayers (SAMs) of octadecanoic acid (ODA) on oxidized InAs were prepared and characterized, and their stability in ambient, solvents and against heating was investigated. Results confirm the formation of densely packed, well-ordered monolayers. Storage of ODA SAMs in ambient does not lead to any noticeable degradation for months. ODA can be rinsed off the surface by some organic solvents, but SAMs are stable in water. ODA SAMs are stable up to 120 °C in ambient, above which temperature ODA starts to desorb. Above 200 °C, oxidation of the InAs substrate occurs.     

硒杂环化合物(4,5-苯并苤硒脑)在金表面上的自组装

为了寻求新的自组装单分子膜体系 ,构建新的功能膜 ,研究了具备平面型的大环共轭硒杂环化合物——— 4,5 苯并苤硒脑 (苯并 [c]硒二唑 ,简称苤硒脑 )在金表面的自组装单分子膜 .通过X射线光电子能谱 (XPS)和电化学手段对其进行表征 .XPS研究结果表明 ,自组装形成单分子膜后 ,苤硒脑分子中Se3d结合能从 5 7.4eV下降到 5 7.1eV ;表明硒杂环化合物是通过金硒键固定在金表面上的 ;电化学循环伏安法实验表明 ,金电极表面上自组装该有机硒后 ,Fe(CN) 63 -/ 4 -的氧化还原峰几乎完全消失 ;以四硼酸钠为底液 ,测得该化合物自组装在金表面上时 ,其还原电位在 - 0 .6 6V ,与在溶液中用裸金电极测得的还原峰电位基本一致 .     

溶液酸碱性对异构体氨基酸单分子膜影响的表面增强拉曼光谱研究

利用表面增强拉曼(SERS)光谱技术研究比较了在粗糙化银电极表面吸附的亮氨酸与异亮氨酸自组装单层膜结构以及溶液酸碱性对分子吸附作用的影响。研究表明在粗糙化银电极表面两种氨基酸分子主要是以COO-为作用位点进行吸附的。进一步的研究也揭示溶液pH值的变化没有显著改变两种氨基酸分子在银电极表面以去质子化羧基吸附为主的特征,但对于羧基吸附作用的影响程度及其变化规律是迥异的,对氨基的影响也有一定的差异。     

烷基硫醇/金自组装单分子膜表面上金属沉积特性研究进展

本文介绍了金属原子在烷基硫醇自组装单分子膜表面的再沉积行为,从理论上分析了其作用机理,归纳出了金属在自组装单层膜表面的再沉积规律。     

烷基硫醇/金自组装单分子膜表面上金属沉积特性研究进展

本文介绍了金属原子在烷基硫醇自组装单分子膜表面的再沉积行为,从理论上分析了其作用机理,归纳出了金属在自组装单层膜表面的再沉积规律。     

Ordered self-assembled monolayers of Peptide nucleic acids with DNA recognition capability

We report on the formation of ordered self-assembled monolayers (SAMs) of single-stranded peptide nucleic acids (ssPNA). In spite of their remarkable length (7 nm) thiolated PNAs assemble standing up on gold surfaces similarly to the SAMs of short alkanethiols. SAMs of ssPNA recognize complementary nucleic acids, acting as specific biosensors that discriminate even a point mutation in target ssDNA. These results are obtained by surface characterization techniques that avoid labeling of the target molecule: x-ray photoemission, x-ray absorption and atomic force microscopy.     

TiO2-based superhydrophobic-superhydrophilic patterns: Fabrication via an ink-jet technique and application in offset printing

A superhydrophobic-superhydrophilic pattern was prepared on an anodized Al plate by a new fabrication process. The process consists of five key steps: (1) TiO₂ coating of the plate, (2) surface modification with self-assembled monolayers (SAMs), (3) formation of aqueous UV light-resistant ink patterns by an ink-jet technique, (4) photocatalytic decomposition of SAMs and surface conversion to the superhydrophilic state and (5) removal of the aqueous ink patterns by water washing. It is particularly noteworthy that the wettability pattern can be quickly formed on the plate, without the use of a photomask. The fabricated superhydrophobic-superhydrophilic pattern is shown to be applicable to offset printing.     

单晶硅表面有机硅烷/Ag2O纳米微粒复合自组装膜的制备和表征

利用分子自组装成膜技术 ,在单晶硅表面制备了有机硅烷 /Ag2 O纳米微粒复合膜 .应用接触角测定仪、原子力显微镜和X射线光电子能谱仪分析表征了薄膜的组成和结构 .结果表明 ,通过硅烷偶联剂 3 氨丙基 三乙氧基硅烷在单晶硅基底表面的成功组装 ,获得了较为均匀的硅烷化表面 ,而Ag2 O纳米微粒可在硅烷化表面成功地进行组装 ,并呈亚单层排布     

Self-assembled monolayers on magnesium alloy surfaces from carboxylate ions

Self-assembled monolayers (SAMs) of carboxylate salts (C_n−1H_2n−1COONa, n = 12, 16, 18) were successfully formed on Mg alloy substrate in ethanol solution and characterized by the contact angle measurement, ATR-FTIR, ellipsometry and XPS. The SAMs were regularly and densely anchored to the Mg alloy substrate via monodentate bonding with the tilting angles of about 40°, 33° and 27° for C12, C16 and C18 monolayers, respectively. Electrochemical impedance spectroscopy (EIS) proved the corrosion protection of SAMs for Mg alloy substrate with protective efficiency (PE) of even up to 98.5%.     

Characterization and protonation behavior of bipyridine thiol self-assembled monolayer on Au(1 1 1) studied using X-ray photoelectron spectroscopy and scanning tunneling microscopy

The adsorption process, molecular arrangement and protonation behavior of self-assembled monolayers (SAMs) of bipyridine thiol on Au(1 1 1) were investigated using X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM), with a view towards constructing a molecular ion sensor. When the bipyridine SAMs were immersed in a strong CF₃SO₃H solution for protonation of the bipyridine group, additional N(1s) XPS peaks were generated at higher binding peak positions where the origin of the peak was considered to be the N-H species. We further investigated the relationship between the immersion time for the SAMs and the probability of protonation. We observed a decrease in the probability of protonation with a longer immersion time for the SAMs. We consider that both the bipyridine molecular arrangements and the molecular density on the Au surface are crucial for controlling the probability of protonation based on the STM and XPS data.     

Interfacial kinetic enhancement of metal ion adsorption on binary mixed self-assembled monolayers

The adsorption of metal ions, a type of surface reaction on binary mixed self-assembled monolayers (SAMs) on a gold surface composed of 1,6-hexanedithiol (HDT) with 11-mercaptoundecanoic acid (MUA), was monitored by in situ surface plasmon resonance (SPR) measurements. The differential SPR reflectance (ΔR) enables the kinetics of adsorption of Pt²⁺ on the mixed SAMs to be investigated. Unlike single HDT SAM, kinetic analyses of the mixed SAMs showed that the rate of adsorption of Pt²⁺ was enhanced and that it was highly dependent on the fraction of MUA present. These SPR measurements suggest that the adsorption rate of metal ions can be readily manipulated simply by using mixed SAMs.     

Characterization of self-assembled monolayers (SAMs) on silicon substrate comparative with polymer substrate for Escherichia coli O157:H7 detection

This article presents the characterization of two substrates, silicon and polymer coated with gold, that are functionalized by mixed self-assembled monolayers (SAMs) in order to efficiently immobilize the anti-Escherichia coli O157:H7 polyclonal purified antibody.A biosurface functionalized by SAMs (self-assembled monolayers) technique has been developed. Immobilization of goat anti-E. coli O157:H7 antibody was performed by covalently bonding of thiolate mixed self-assembled monolayers (SAMs) realized on two substrates: polymer coated with gold and silicon coated with gold. The F(ab′)₂ fragments of the antibodies have been used for eliminating nonspecific bindings between the Fc portions of antibodies and the Fc receptor on cells. The properties of the monolayers and the biofilm formatted with attached antibody molecules were analyzed at each step using infrared spectroscopy (FTIR-ATR), atomic force microscopy (AFM), scanning electron microscopy (SEM) and cyclic voltammetry (CV). In our study the gold-coated silicon substrates approach yielded the best results.These experimental results revealed the necessity to investigate each stage of the immobilization process taking into account in the same time the factors that influence the chemistry of the surface and the further interactions as well and also provide a solid basis for further studies aiming at elaborating sensitive and specific immunosensor or a microarray for the detection of E. coli O157:H7.     

Device applications of self-assembled monolayers and monolayer-protected nanoclusters

The present status of self-assembled monolayers (SAMs) on different surfaces (2D systems) as well as monolayer formation on metallic and semiconducting cluster surfaces (3D SAM) to form monolayer-protected nanoclusters (MPCs) and their assemblies is reviewed briefly. Attention is focused mainly on the potential electronic and photonic applications of SAMs, MPCs and their 2D and 3D structures fabricated using covalent and hydrophobic interactions in contrast to the usual electrostatic assemblies. These examples illustrate the rational use of organic molecules and nanoclusters using the concept of self-assembly, where subtle systems of double tunnel junctions, hetero junctions and single-electron transition devices could be developed based on the structure and chemistry of multifunctional molecules. The tailoring of cluster size and cluster–cluster spacing to reveal interesting transitions in electronic properties is also demonstrated using the low temperature behavior of the 3D network of nanoclusters as an example. These devices are believed to play an important role in the coming years as the chip functions and clock frequencies reach orders of magnitude beyond those extrapolated from Moore’s law.     

Adsorption properties of decyl thiocyanate and decanethiol on platinum substrates studied by sum-frequency generation spectroscopy

Recently, thiocyanate groups were successfully used as precursors for thiolate assemblies. Indeed, they provide a useful alternative to thiol groups for self-assembly on metallic substrates. In order to check the adsorption properties and the quality of the thiocyanate-based self-assembled monolayers (SAMs), we use sum-frequency generation spectroscopy (SFG) and apply it to characterize the ad-layers of two similar molecules: decanethiol (DT) and decyl thiocyanate (DTCN) adsorbed on platinum surfaces. By comparing the SFG signals of the methyl and methylene vibration modes, we show that DTCN SAMs are less ordered than DT ones. These effects are related to the SAMs quality which depends on the molecular packing as highlighted by scanning tunnelling microscopy and X-ray photoelectron spectroscopy.