吡咯烷二硫代氨基甲酸铵自组装膜对铜的缓蚀作用

吡咯烷二硫代氨基甲酸铵(APDTC)是一种环境友好型金属缓蚀剂, 以其在铜表面制备了自组装单分子膜(SAMs), 用电化学方法研究在0.5 mol·L-1 HCl介质中APDTC SAMs对铜的缓蚀作用及其吸附行为. 结果表明, APDTC分子易在铜表面形成稳定的APDTC SAMs, 改变了电极表面的双电层结构, SAMs同时抑制了铜的阳极氧化过程和阴极还原过程, 铜电极的电荷转移电阻明显提高, 双电层电容明显降低. 电化学阻抗和极化曲线测试结果显示, 在0.5 mol·L-1 HCl介质中, 铜表面APDTC SAMs表现出良好的缓蚀效果. 研究结果还表明, APDTC的吸附行为符合Langmuir吸附等温式, 吸附机理是介于化学吸附和物理吸附之间的一种吸附.     

Structural effects on the barrier properties of self-assembled monolayers formed from long-chain omega-alkoxy-n-alkanethiols on copper

The adsorption of long-chain omega-alkoxy-n-alkanethiols [CH(3)(CH(2))(p-1)O(CH(2))(m)SH; m = 11, 19, 22; p = 18, 22] onto copper produces self-assembled monolayers (SAMs) that can provide protection against corrosion of the underlying metal substrate. The resulting films are 40-60 A in thickness and are isostructural with SAMs formed on copper from unsubstituted n-alkanethiols. As evidenced by electrochemical impedance spectroscopy (EIS), the barrier properties of these ether-containing SAMs depend on the chain length of the adsorbate and the position of the ethereal unit along the hydrocarbon chain. For SAMs where the ether substitution is farther from the copper surface, the initial coating resistances are similar to those projected for unsubstituted n-alkanethiolate SAMs of similar thickness. For SAMs where the ether substitution is nearer to the copper surface (m = 11), the resistances are significantly less than those for unsubstituted n-alkanethiolate SAMs of similar thickness, reflecting the effect of the molecular structure on the barrier properties of the film. Upon exposure to 1 atm of O(2) at 100% RH, the SAMs become less densely packed as observed by infrared (IR) spectroscopy, and their barrier properties deteriorate as observed by EIS. The rate that the SAMs lose their barrier properties upon exposure to oxidizing conditions is correlated to the strength of intermolecular interactions within the bulk state of the adsorbate.     

铜表面二硫代氨基甲酸改性葡萄糖自组装膜的缓蚀作用

合成了一种环境友好型的缓蚀剂--二硫代氨基甲酸改性葡萄糖（DTCG）。 采用该缓蚀剂在铜表面制备了自组装膜,并运用电化学阻抗谱、极化曲线方法研究了该膜在3%NaCl溶液中对铜的缓蚀性能。 研究结果表明,DTCG自组装膜对铜有良好的缓蚀效果,在自组装时间为4 h、自组装浓度为120 mg/L的缓蚀效率接近于97%。 量子化学计算结果也证明了DTCG具有优异的缓蚀性能。     

Electrochemical characterization of cationic surfactants’ adsorption on a disturbed n-alkanethiolate self-assembled monolayer-modified polycrystalline gold electrode

The adsorption of cetyltrimethylammonium bromide (CTAB) on disturbed n-alkanethiolate self-assembled monolayers (SAMs) was investigated by electrochemical methods with potassium ferricyanide [K₃Fe(CN)₆] as a probe. Compared with the completely restrained signal at ordinary compact n-alkanethiolate SAMs, the electrochemical response of K₃Fe(CN)₆ at the disturbed n-alkanethiolate SAMs was partly restored and became progressively reversible in the presence of increasing concentrations of CTAB, which was employed to characterize the adsorption of cationic surfactants on hydrophobic SAMs. The effect of CTAB concentration on electrochemical impedance spectroscopy (EIS) plots indicated that CTAB experienced two different types of adsorptive behavior at the disturbed n-alkanethiolate SAMs: monomer adsorption at low concentrations below 1×10^–6 M and monolayer adsorption at CTAB concentrations above 1×10^–5 M. The adsorption of a series of cationic surfactants with similar structures to CTAB on disturbed n-alkanethiolate SAMs was also explored. These surfactants had similar adsorptive behavior and showed nearly linear adsorption characteristics with the length of their hydrophobic tails.     

若干多氮硒杂环化合物在金表面的自组装及其电化学性质

研究了1,2,5-硒二唑并[3,4-b]吡啶（SPb）,1,2,5-硒二唑并[3,4-d]嘧啶-7-（5H,6H）酮（SPO）,1,2,5．硒二唑并[3,4．d]嘧啶-5,7-（4H,6H）二酮（SPDO）等多氮硒杂环化合物在溶液中及其在金表面的自组装单分子膜的电化学性质。以Fe（CN）6^3-/4-为离子探针,利用CV法观察了Fe（CN）6^3-/4-氧化还原峰的变化。结果表明,在溶液中,电极过程主受吸附控制;自组装膜的电化学信号与其溶液相似,在-600mV左右都有一还原峰,表明该类化合物有相似的组装模式,其中SPO和SPDO在金表面形成了致密的单分子膜,有效地封闭了表面与溶液之间的电子交换和传递。     

Interference from Trace Copper in Electrochemical Investigations Employing Carboxylic Acid Terminated Thiol Modified Gold Electrodes

Unexpectedly, electrochemistry at variable chain length carboxylic acid terminated alkylthiol self‐assembled monolayers (SAMs) on gold electrodes gives rise to a Faradaic process in buffered aqueous electrolyte solution. In particular, the three‐carbon chain length, 3‐mercaptopropionic acid (MPA), exhibits a chemically reversible process with a mid‐point potential of 175 mV vs. Ag/AgCl under conditions of cyclic voltammetry. This process is associated with the presence of trace (parts per billion) amounts of copper(II) ions present in the chemical reagents used to prepare the aqueous electrolyte and also from the gold electrode itself. The carboxylic acid moiety on the SAM concentrates Cu²⁺ ions by coordination and this surface confined layer is then reduced. Methods to minimize the interference of Cu²⁺ ions at carboxylic acid terminated SAM are discussed and caution with respect to the interpretation of protein electrochemistry is recommended when using carboxylic acid functionalized SAMs to provide biocompatible electrochemical transduction surfaces, unless a metal free environment can be obtained.     

偶氮苯衍生物自组装膜的表征及组装动力学

报导了4-正辛基-4′-（3－巯基丙氧基）偶氮苯（简称C8AzoC3）自组装膜（Self-AssembledMonolnyersSAMs）的表征及其自组装成膜动力学，接触角滴定、原子力显微镜（AFM）及电化学的实验结果表明，C8AzoC3分子在金表面自组装形成致密有序的流水性单分子膜，并且在电极上没有明显的电化学响应．通过控制组装时间，考察了偶氮苯自组装形成单分子膜的动力学过程，从接触角和电化学数据得到组装过程的速率常数kad为（1.2±0.2）×103mol-1·dm3·s－1；依据不同组装时间形成的自组装膜的特征循环伏安行为，提出了C8AzoC3分子在金表面自组装过程的动态模型．     

Electrochemical Studies of Thiol Self‐Assembled Monolayers at a Heated Gold‐Wire Microelectrode

Mercaptoundecanoic acid (MUA) and glutathione (GSH) self‐assembled monolayers were prepared on gold‐ wire microelectrode. Cyclic voltammetry was used to investigate the influence of temperature on electrochemical behaviors of Fe(CN)₆^3?/4? and Ru(NH₃)₆^3+/2+ at these SAMs modified electrodes in aqueous solution. It is found that temperature shows great influence on electron transfer (ET) and mass transport (MT) for the two SAMs modified electrodes and the influence of temperature depends on the charge properties of the redox couples and terminal groups of SAMs and the structure of the monolayer on gold surface. The temperature can greatly increase MT rate of Fe(CN)₆^3?/4? at both MUA and GSH modified electrodes. However, the increased MT rate doesn't have any effect on the CV's for Fe(CN)₆^3?/4? /MUA system. For Ru(NH₃)₆^3+/2+ , temperature can greatly improve the electrochemical reaction in both MUA and GSH modified electrodes, which is ascribed to temperature‐induced diffusion and convection and the electrostatic interaction between Ru(NH₃)₆^3+/2+ and negatively charged carboxyl groups on the electrode surface.     

3-氨基-1,2,4-三氮唑自组装膜对黄铜的缓蚀作用

3-氨基-1,2,4-三氮唑(ATA)是一种环境友好型金属处理剂, 以其在黄铜表面制备了自组装单分子膜(SAMs), 用电化学方法研究ATA SAMs对黄铜的缓蚀作用及其吸附行为. 结果表明, ATA分子易在黄铜表面形成稳定的ATA SAMs, SAMs抑制了黄铜的阳极氧化过程, 改变了电极表面的双电层结构, 固/液界面双电层电容明显降低, 有良好的缓蚀效果. 研究结果还表明, ATA的吸附行为符合Langmuir吸附等温式, 吸附机理是典型的化学吸附.     

银电极上4-氨基安替比林原位表面增强拉曼光谱电化学

在银电极表面4-氨基安替比林(4-AAP)分子自组装,形成单分子膜层.应用表面增强拉曼散射(SERS)光谱原位考察不同电位下4-AAP在电极表面的吸附机理及其组装液pH值对组装分子与银作用方式的影响.依据密度泛函数(DFT)理论预测4-AAP分子振动模式及其SERS光谱归属.结果表明:在开路电位下,组装层中的4-AAP分子以N15和O3为位点,由苯环倾斜和比林环垂直的方式吸附在银表面;但随着外加电位负移,4-AAP分子的苯环趋于垂直吸附而比林环则逐渐以平行方式靠近银表面.在-0.8V电位下,4-AAP分子从银表面脱附.酸性溶液中组装,形成的4-AAP膜层以N15和O3为位点吸附于银表面,比林环倾斜而苯环直立;碱性条件下,分子的吸附位点不变,比林环呈平行取向,而苯环倾斜于银表面.     

Covalent grafting tyrosinase and its application in phenolic compounds detection

A stepwise strategy is reported for the design of a meditor-free amperometric tyrosinase biosensor. It is based on the azide-alkyne click reaction and carbodiimide coupling. Firstly, azide-terminated alkane thiols monolayers were self-assembled on the Au electrode surface. Then, nitrophenyl groups were covalent attached to the self-assembled monolayers (SAMs) via the click reaction of copper(I)-catalyzed 1,3-dipolar cycloadditions of azide-alkyne. Finally, the nitrophenyl group terminated SAMs were converted to aminophenyl-terminated interface by electrochemical reduction, and tyrosinase was covalent immobilized onto the Au electrode via carbodiimide reaction. Based on the stepwise strategy, a meditor-free amperometric tyrosinase biosensor was farbricated, and it showed good electrocatalytic reduction ability toward phenol, pyrocatechol and m-Cresol. Their linear ranges were over the range of 0.2 to 15.0 μmol·L^?1, 0.2 to 73.0 μmol·L^?1, and 0.2 to 33.0 μmol·L^?1, respectively.     

Nanostructured gold colloid electrode based on in situ functionalized self-assembled monolayers on gold electrode

A novel method for fabricating nanostructured gold colloid electrode based on in situ functionalization of self-assembled monolayers (SAMs) of 4-aminothiophenol (4-ATP) on gold electrode is proposed. The in situ functionalization of 4-ATP SAMs yields a redox active monolayer of 4′-mercapto-N-phenylquinone diimine (NPQD). When the amino-rich surface is exposed to gold colloid, the citrate-stabilized gold nanoparticles (GNPs) can be anchored onto the surface of the in situ functionalized electrode by the electrostatic interactions and a new nanostructured gold colloid surface was obtained. The mixed monolayers of in situ functionalized product, NPQD, and 1,4-benzenedimethanethiol (BDMT) can provide a more compact and order platform to fabricate GNPs on the electrode surface. The film formed by this technique has the advantages of high organization and uniformity, which could provide a desirable microenvironment to assemble GNPs and facilitate the concentration of the analyte from the bulk solution to the electrode surface. The nanostructured gold colloid electrode has favorable effect on the electrochemical oxidation of naphthol isomers.     

Study on the Electrochemical Behavior of Dopamine and Uric Acid at a 2‐Amino‐5‐mercapto‐[1,3,4] Triazole Self‐Assembled Monolayers Electrode

Selected from a series of structurally related heteroaromatic thiols, a newly synthesized reagent 2‐amino‐5‐mercapto‐[1,3,4] triazole (MATZ) was used to fabricate self‐assembled monolayers (SAMs) on gold electrode for the first time. The MATZ/Au SAMs was characterized by electrochemical methods and scanning electronic microscopy (SEM). In 0.04 mol/L Britton–Robinson buffer solution (pH 5), the electrochemical behavior of dopamine showed a quasireversible process at the MATZ/Au SAMs with an electrode kinetic constant 0.1049 cm/s. However, the electrochemical reaction of uric acid at the SAMs electrode showed an irreversible oxidation process, the charge‐transfer kinetics of uric acid was promoted by the SAMs. By Osteryoung square‐wave voltammetry (OSWV), the simultaneous determination of dopamine and uric acid can be accomplished with an oxidation peak separation of 0.24 V, the peak current of dopamine and uric acid were linearly to its concentration in the range of 2.5×10^?6–5.0×10^?4 mol/L for dopamine and 1×10^?6–1×10^?4 mol/L for uric acid with a detection limit of 8.0×10^?7 mol/L for dopamine and 7.0×10^?7 mol/L for uric acid. The MATZ/Au SAMs electrode was used to detect the content of uric acid in real urine and serum sample with satisfactory results.     

Protein interactions with self-assembled monolayers presenting multimodal ligands: a surface plasmon resonance study

This paper describes the use of surface plasmon resonance (SPR) spectroscopy and self-assembled monolayers (SAMs) to understand the characteristics of surfaces that promote the adsorption of proteins at high ionic strengths (high-salt conditions). We synthesized SAMs presenting different multimodal ligands and determined the influence of surface composition, solution composition, and the nature of the protein on the extent of protein adsorption onto the SAMs. Our results confirm that hydrophobic interactions can contribute significantly to protein adsorption under high-salt conditions. In particular, the extent of protein adsorption under high-salt conditions increased with increasing surface hydrophobicity. The extent of protein adsorption was also influenced by the solution composition and decreased with an increase in the chaotropicity of the anion. The combination of SPR and SAMs is well-suited for studying the interaction of proteins with complex surfaces of relevance to chromatography.     

Voltammetry of immobilized cytochrome c on novel binary self-assembled monolayers of thioctic acid and thioctic amide modified gold electrodes

Horse heart cytochrome c (cyt c) was adsorbed on the binary self-assembled monolayers (SAMs) composed of thioctic acid (T-COOH) and thioctic amide (T-NH₂) at gold electrodes via electrostatic interaction. The cyt c adsorbed on the modified gold electrode exhibited well-defined reversible electrochemical behavior in 10 mM phosphate buffer solution (PBS, pH 7.0). The surface concentration (Γ) of electroactive species, cyt c, on the binary SAMs was higher than that in single-component SAMs of T-COOH, and reached a maximum value of 9.2 × 10⁻¹² mol cm⁻² when the ratio of T-COOH to T-NH₂ in adsorption solution was of 3:2, and the formal potential (E^0′=(E_pa+E_pc)/2) of cyt c was −0.032 V (vs. Ag|AgCl (3 M NaCl)) in a 10 mM PBS. The interaction between cyt c and the binary SAMs made the E^0′ shift negatively when compared with that of cyt c in solution (+0.258 V vs. NHE, i.e., +0.058 V vs. Ag|AgCl (3 M NaCl)). The fractional coverage of bound cyt c was a 0.64 theoretical monolayer. The standard electron transfer rate constant of cyt c immobilized on the binary SAMs was also higher than that on single-component SAMs of T-COOH, and the maximum value of 15.8 ± 0.6 s⁻¹ was obtained when the ratio of T-COOH to T-NH₂ in adsorption solution was at 3:2. The results suggest that the electrode modified with the binary SAMs functions better than the electrode modified with single-component SAMs of T-COOH.     

The effect of the surface coverage of the phosphonic acid terminated self-assembled monolayers on the electrochemical behavior of dopamine

The surface coverage of 3-mercaptopropylphosphonic acid (HS-CH₂CH₂CH₂-PO₃H₂, MPPA) self-assembled monolayers (SAMs) on gold surface can be controlled by the dissociation degree of phosphonic acid groups (-PO₃H₂) in the bulk solution and adsorption time of MPPA molecules under the basic condition. Electrochemical measurements show that the low-density MPPA-SAMs modified gold electrode enhances significantly the kinetics of electron transfer of dopamine (DA), and improves the antifouling capability of modified electrode towards DA oxidation. The present results offer crucial information for design and optimization of the electrochemical sensors for DA determination.     

Elucidating the Influence of Electrical Potentials on the Formation of Charged Oligopeptide Self-Assembled Monolayers on Gold

Self-assembled monolayers (SAMs) based on oligopeptides have garnered immense interest for a wide variety of innovative biomedical and electronic applications. However, to exploit their full potential, it is necessary to understand and control the surface chemistry of oligopeptides. Herein, we report on how different electrical potentials affect the adsorption kinetics, stability and surface coverage of charged oligopeptide SAMs on gold surfaces. Kinetic analysis using electrochemical surface plasmon resonance (e-SPR) reveals a slower oligopeptide adsorption rate at more positive or negative electrical potentials. Additional analysis of the potential-assisted formed SAMs by X-ray photoelectron spectroscopy demonstrates that an applied electrical potential has minimal effect on the packing density. These findings not only reveal that charged oligopeptides exhibit a distinct potential-assisted assembly behaviour but that an electrical potential offers another degree of freedom in controlling their adsorption rate.     

Formation of ordered self-assembled monolayers by adsorption of octylthiocyanates on Au(111)

Self-assembled monolayers (SAMs) were formed by the spontaneous adsorption of octythiocyanate (OTC) on Au(111) using both solution and ambient-pressure vapor deposition methods at room temperature and 50 degrees C. The surface structures and adsorption characteristics of the OTC SAMs on Au(111) were characterized by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). The STM observation showed that OTC SAMs formed in solution at room temperature have unique surface structures including the formation of ordered and disordered domains, vacancy islands, and structural defects. Moreover, we revealed for the first time that the adsorption of OTC on Au(111) in solution at 50 degrees C led to the formation of SAMs containing small ordered domains, whereas the SAMs formed by vapor deposition at 50 degrees C had long-range ordered domains, which can be described as (radical3 x 2 radical19)R5 degrees structures. XPS measurements of the peaks in the S 2p and N 1s regions for the OTC SAMs showed that vapor deposition is the more effective method as compared to solution deposition for obtaining high-quality SAMs by adsorption of OTC on gold. The results obtained will be very useful in understanding the SAM formation of organic thiocyanates on gold surfaces.     

Interactions of doxorubicin with self-assembled monolayer-modified electrodes: electrochemical, surface plasmon resonance (SPR), and gravimetric studies

We present the results on the partitioning of doxorubicin (DOX), a potent anticancer drug, through the model membrane system, self-assembled monolayers (SAMs) on gold electrodes. The monolayers were formed from alkanethiols of comparable length with different ω-terminal groups facing the aqueous electrolyte: the hydrophobic -CH(3) groups for the case of dodecanethiol SAMs or hydrophilic -OH groups of mercaptoundecanol SAMs. The electrochemical experiments combined with the surface plasmon resonance (SPR) and gravimetric studies show that doxorubicin is likely adsorbed onto the surface of hydrophilic monolayer, while for the case of the hydrophobic one the drug mostly penetrates the monolayer moiety. The adsorption of the drug hinders further penetration of doxorubicin into the monolayer moiety.     

The Influence of Bromine Adsorption on Copper Electrodeposition on Polycrystalline Gold Electrodes Modified with Self-Assembled Monolayers

The influence of bromine adsorption on copper electrodeposition on a polycrystalline gold electrode modified with self-assembled monolayers (SAMs) has been investigated by chronoamperometry and cyclic voltammetry. It was found that the deposition potential of copper was shifted negatively due to the SAMs. The hydrogen bond interaction between omega-carboxyl thiols decreased the defect density of the SAMs and significantly retarded the deposition of copper. The presence of bromide anions also shifted the potential more negatively through adsorption into the defects of SAMs. Copyright 2001 Academic Press.