Voltammetric measurement of pH using a mixed self-assembly of macrocyclic nickel(II) complex and diimine on gold electrode

Redox active mixed self-assembled monolayers (SAMs) of a macrocyclic nickel complex, dinickel (II)(2,2^′-bis(1,3,5,8,12-pentaazacyclotetradec-3-yl)-diethyl disulfide (MNC) and a electrochemically derived diimine, 4^′-mercapto-N-phenylquinone diimine (NPQD) on gold electrode is used for the voltammetric measurement of solution pH (pH 6–9.4). The formal potential of MNC is insensitive to the solution pH and it serves as a reference molecule, whereas the redox reaction of NPQD is pH dependent and it serves as an indicator molecule. The formal potential of NPQD shifts −56 mV while changing the solution pH by one unit. The formal potential of the bifunctional self-assembly is insensitive to oxygen in solution and the dissolved oxygen does not interfere with the voltammetric measurement.     

A butadiyne-linked diruthenium molecular wire self-assembled on a gold electrode surface

A 1,3-butadiyne-linked diruthenium complex 4 is successfully brought onto the gold surface in a lying flat mode to form self-assembled monolayers (SAMs) showing reversible multiple redox behaviors on the electrode surface. The diruthenium species with different oxidation states, particularly the Ru(2)(III,III) state which is unstable and impossible to isolate from the solution, can be detected by in situ IR spectroscopy.     

Enhanced catalytic activity of Fe phthalocyanines linked to Au(111) via conjugated self-assembled monolayers of aromatic thiols for O2 reduction

We have obtained and characterized self assembled monolayers (SAMs) of 4-aminothiophenol (4-ATP) and 1-(4-mercaptophenyl)-2,6-diphenyl-4-(4-pyridyl)pyridinium tetrafluoroborate (MDPP) functionalized with iron phthalocyanine (FePc) adsorbed on gold (111) electrodes. The catalytic activity of these SAMs/FePc was examined for the reduction of O₂ in aqueous media (pH = 4) and compared with that of bare gold and of gold coated directly with FePc molecules. Scanning tunneling microscopy (STM) studies confirm the functionalization of the 4-ATP by FePc. The electrocatalytic studies carried out with Au/FePc, Au/4-ATP/FePc and Au/MDPP/FePc electrodes show that the O₂ reduction takes place by a 4-electron transfer to give water in contrast to a 2-electron-transfer process observed on the bare gold. The activity of the electrodes increases as follows: Au < Au/FePc < Au/4-ATP/FePc < Au/MDPP/FePc.     

Raman mapping and in situ SERS spectroelectrochemical studies of 6-mercaptopurine SAMs on the gold electrode

The self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) were formed at the roughened polycrystalline gold surfaces in acid and alkaline media. The time-dependent Raman mapping spectral analysis in conjunction with the quantum calculations for the vibrational modes using ab initio BLYP/6-31G method suggested that both of the resulted 6MP SAMs adopted the same adsorption mode through the S atom of pyrimidine moiety and the N7 atom of the imidazole moiety anchoring the gold surface in a vertical way. The in situ surface-enhanced Raman scattering spectroelectrochemical experiment was conducted to examine the stability of the SAMs at various bias potentials. It was found that the detaching process of the 6MP SAMs from the surface involved one electron reduction as the voltage was applied at ca. 0.7 V vs a standard calomel electrode.     

Blocking behavior of self-assembled monolayers on gold electrodes

Self-assembled monolayers (SAMs) with metal electrodes, especially thiols on gold, are the subject of this investigation because of the unique properties of SAM-modified surfaces. Normal alkanethiols are used to modify the surface of a conventional gold electrode to block certain ions such as Pb(II) and Cu(II) from the surface of the electrode. Normal alkanethiols are also used to study the SAM-gold interfacial adsorption-desorption behavior of the self-assembled monolayer. The effects of varying chain length of SAMs, varying concentration of the alkanethiol solutions, immersion time of the pure gold electrode in the SAM solution, and the stability of a SAM-modified gold electrode in fresh chloroform are investigated using the oxidation-reduction peaks of gold. Conditions that optimize the surface coverage and the uniformity of the SAMs have been determined. Normal alkanethiols proved to be a good insulator on the electrode surface. Received: 16 January 1997 / Accepted: 4 March 1997     

Electroactive gold nanoparticles protected by 4-ferrocene thiophenol monolayer

Numerous reports have focused on ferrocene-terminated electroactive self-assembled monolayers (SAMs) on a flat Au surface but only a few on ferrocene SAMs on Au colloid. In this paper, we employ 4-ferrocene thiophenol as a novel capping agent to produce electroactive gold nanoparticles in consideration of the peculiar pi-conjugated structure. Transmission electron microscopy shows the narrow-dispersed gold core with an average core diameter of ca. 2.5 nm. UV/vis spectra examine the pi-conjugated structure of 4-ferrocene thiophenol and surface plasmon absorbance of the indicated gold nanoparticles. X-ray photoelectron spectroscopy reveals electronic properties of the Au core and thiol ligands. Electrochemical measurement shows that the oxidation peak current is proportional to the scan rate, indicating the electrode process is controlled by adsorbed layer reaction. The formal potential of the Fc-MPCs is compared with that of free ferrocene in MeCN solution and the Fc-SAMs. The shifts are attributed to the phenyl moiety in the 4-ferrocene thiophenol and dielectric constant of the solvation environment.     

Hemoglobin on phosphonic acid terminated self-assembled monolayers at a gold electrode: immobilization, direct electrochemistry, and electrocatalysis

Phosphonic acid (--PO(3)H(2)) terminated self-assembled monolayers (SAMs) on a gold surface were used as a functional interface to immobilize hemoglobin (Hb). In situ surface-enhanced infrared absorption spectroscopy (SEIRAS) measurements show that Hb immobilization is a sluggish process due to formation of multilayer Hb structures on the PO(3)H(2)-terminated SAMs, as revealed by ellipsometry, atomic force microscopy (AFM), and cyclic voltammetry (CV). In the multilayered Hb film, the innermost Hb molecules can directly exchange electrons with the electrode, whereas Hb beyond this layer communicates electronically with the electrode via protein-protein electron exchange. In addition, electrochemical measurements indicate that immobilization of Hb on the PO(3)H(2)-terminated SAMs is not driven by the electrostatic interaction, but likely by hydrogen-bonding interaction. The immobilized Hb molecules show excellent bioelectrocatalytic activity towards hydrogen peroxide, that is, the PO(3)H(2)-terminated SAMs are promising for construction of third-generation biosensors.     

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。     

Bimetallic nano-structured glucose sensing electrode composed of copper atoms deposited on gold nanoparticles

We describe the preparation and sensing capabilities of a bimetallic electrode consisting of copper atoms deposited on gold nanoparticles (GNPs). The electrode was obtained by first constructing a GNP template on the surface of a glassy carbon electrode by exploiting the hydrogen-bonding interactions between pyridine groups on the surface of the GNPs and the carboxy groups of poly(acrylic acid). GNPs (60?nm in diameter) were homogeneously and densely deposited in the template (as revealed by scanning electron microscopy). The electro-deposition of copper ad-atoms on GNPs occurred at an underpotential and was proven by electrochemical techniques. The presence of GNPs in the template accelerated the deposition at low potential due to its beneficial effect on the rate of electron transfer. The new electrode was studied for its response to glucose. Highly stable and reproducible catalytic activity towards glucose oxidation is observed and attributed to the synergistic catalytic effect of the copper atoms on the surface of the GNPs. The detection limit is as low as 50?nM (at a signal-to-noise ratio of 3), and the response is between 200?nM and 10?mM of glucose.

Direct electrochemistry of Phanerochaete chrysosporium cellobiose dehydrogenase covalently attached onto gold nanoparticle modified solid gold electrodes

Achieving efficient electrochemical communication between redox enzymes and various electrode materials is one of the main challenges in bioelectrochemistry and is of great importance for developing electronic applications. Cellobiose dehydrogenase (CDH) is an extracellular flavocytochrome composed of a catalytic FAD containing dehydrogenase domain (DH(CDH)), a heme b containing cytochrome domain (CYT(CDH)), and a flexible linker region connecting the two domains. Efficient direct electron transfer (DET) of CDH from the basidiomycete Phanerochaete chrysosporium (PcCDH) covalently attached to mixed self-assembled monolayer (SAM) modified gold nanoparticle (AuNP) electrode is presented. The thiols used were as follows: 4-aminothiophenol (4-ATP), 4-mercaptobenzoic acid (4-MBA), 4-mercaptophenol (4-MP), 11-mercapto-1-undecanamine (MUNH(2)), 11-mercapto-1-undecanoic acid (MUCOOH), and 11-mercapto-1-undecanol (MUOH). A covalent linkage between PcCDH and 4-ATP or MUNH(2) in the mixed SAMs was formed using glutaraldehyde as cross-linker. The covalent immobilization and the surface coverage of PcCDH were confirmed with surface plasmon resonance (SPR). To improve current density, AuNPs were cast on the top of polycrystalline gold electrodes. For all the immobilized PcCDH modified AuNPs electrodes, cyclic voltammetry exhibited clear electrochemical responses of the CYT(CDH) with fast electron transfer (ET) rates in the absence of substrate (lactose), and the formal potential was evaluated to be +162 mV vs NHE at pH 4.50. The standard ET rate constant (k(s)) was estimated for the first time for CDH and was found to be 52.1, 59.8, 112, and 154 s(-1) for 4-ATP/4-MBA, 4-ATP/4-MP, MUNH(2)/MUCOOH, and MUNH(2)/MUOH modified electrodes, respectively. At all the mixed SAM modified AuNP electrodes, PcCDH showed DET only via the CYT(CDH). No DET communication between the DH(CDH) domain and the electrode was found. The current density for lactose oxidation was remarkably increased by introduction of the AuNPs. The 4-ATP/4-MBA modified AuNPs exhibited a current density up to 30 μA cm(-2), which is ～70 times higher than that obtained for a 4-ATP/4-MBA modified polycrystalline gold electrode. The results provide insight into fundamental electrochemical properties of CDH covalently immobilized on gold electrodes and promote further applications of CDHs for biosensors, biofuel cells, and bioelectrocatalysis.     

金纳米粒子组装体系中偶联单分子层膜结构的SERS光谱表征与分析

通过分子自组装方法制备4,4′-二硫联吡啶(PySSPy)单分子膜修饰的金电极. 利用所形成的对巯基吡啶自组装单分子膜(SAMs)作为偶联层进行金纳米粒子有序膜的组装. 对该纳米粒子组装体系进行Raman光谱测定, 得到了具有良好信噪比的对巯基吡啶单分子膜的表面增强拉曼散射(SERS)光谱. 在此基础上, 进一步采用电化学现场SERS光谱技术研究了该纳米粒子组装体系的SERS光谱随电位变化的规律. 在该体系稳定的电位范围内表征对巯基吡啶单分子膜的特征谱峰1011与1093 cm^-1、1575与1610 cm^-1以及1206与1215 cm^-1这三对谱峰其强度随着所施加电位的改变呈现出明显的规律性. 分析表明, 偶联单分子层中吡啶环芳香性随着所施加电位的改变而有规律地变化是SERS光谱特征改变的内在原因.     

4-氨基苯硫酚在金电极上电化学转变过程的表面增强拉曼光谱及其理论研究

采用循环伏安法和表面增强拉曼散射现场研究了酸性溶液中4-氨基苯硫酚(PATP)在金电极表面的电化学转变过程, 并结合密度泛函理论(DFT)对光谱进行了指认, 由此确定电极表面的最终产物. 研究结果表明, PATP分子在电极表面首先氧化为阳离子自由基, 该自由基与邻近的分子通过头尾相接生成二聚体4'-巯基-N-苯基苯醌二亚胺, 随后发生水解反应生成4'-巯基-N-苯基苯醌单亚胺. 用DFT在B3LYP/6-311＋G** (C, N, S, H)/ LANL2DZ (Au)水平上计算模拟4'-巯基-N-苯基苯醌二亚胺在金表面的拉曼光谱, 结果与所获得的表面拉曼光谱较好吻合, 平均相对偏差约为2.1%.     

Assembled monolayers of Mo3S4(4+) clusters on well-defined surfaces

A class of inorganic monolayers formed by assembling the molybdenum-sulfur cluster, Mo3S4(4+), onto a well-defined Au(111) surface is presented. The monolayers have been comprehensively characterized by electrochemistry, X-ray photoelectron spectroscopy (XPS), and in situ scanning tunneling microscopy (in situ STM). The voltammetric data show strong reductive and oxidative desorption signals from Au-S interactions, supported by the presence of both S and Mo signals in XPS. In situ STM shows many small pits in the dense adlayers uniformly spread over the surface, which is a typical feature of self-assembled monolayers (SAMs) of alkanethiols. The density of the pits is ca. 23 (+/-5)% and is significantly higher than for straight-chain alkanethiol SAMs with a single -SH group. The pit shapes are irregular, suggesting multiple Au-S interactions from Mo3S4(4+). High resolution images disclose bright round spots of ca. 8 A diameter representing individual molecules in the SAM. This is the first example of in situ monolayer formation by a metal-chalcogenide cluster directly anchored onto the gold surface through core ligands and offers a simple way to prepare a new class of functionalized inorganic monolayers.     

Electrochemical assembly and potential-dependent plasmon absorption of au nanoclusters covered with a 4-aminothiophenol self-assembled monolayer

Gold nanoclusters covered with 4-aminothiophenol (4-ATP) self-assembled monolayers (SAMs) were electrochemically assembled on an Au or ITO electrode. The assembly mechanism is discussed on the basis of results of electrochemical, FT-IR, and XPS measurements. The intensity of plasmon absorption of the gold nanocluster assembly was shown to be dependent on applied potential as a result of electrochemical doping/undoping of a counteranion in the polyaniline film.     

Synthesis and self-assembling properties on gold of 2-methyl-1,4-naphthoquinone derivatives containing ω-mercaptoalkylalkanoate groups

The synthesis of a series of 2-methyl-1,4-naphthoquinone (2-MeNQ) derivatives containing surface active ω-mercaptoalkylalkanoate groups with 5-12 atoms in the side-chains is reported. The compounds form stable self-assembled monolayers (SAMs) on gold. The complete reduction of the terminal 2-MeNQ group in the SAMs was confirmed by in situ Fourier-transform surface-enhanced Raman spectroscopy (FT-SERS). The basic electrochemical properties of the monolayers were determined by cyclic voltammetry (CV).     

Examination of incubation time of bare gold electrode inside cysteamine solution for immobilization of multi-walled carbon nanotubes on a gold electrode modified with cysteamine

A cysteamine (CysAm) nanostructure was generated to act as an intermediate layer between gold electrode and carbon nanotubes. A bare gold electrode was placed in a solution of CysAm to create a self-assembled monolayer on its surface. The modified electrode was then incubated with a solution of multi-walled carbon nanotubes. Cyclic voltammetry and atomic force microscopy were used to characterize the modified electrode. The results indicated that the number of functionalized MWCNTs on the surface of the electrodes increased by enhancing incubation time.

Study on self-assembled monolayer of functionalized thiol on gold electrode forming capacitive sensor for chromium(VI) determination

A capacitive sensor based on S-{12-[1-(pyridin-4-ylmethyl)-1H-1,2,3-triazol-4-yl]dodecyl} ethanethioate (FT), a compound with a functional group exhibiting selective affinity towards Cr(VI) ions, was developed. FT was mixed with shorter-chain thiol-decanethiol (DT), to obtain an Au electrode surface well covered by a thiol monolayer. The composition and high quality of self-assembled monolayers (SAMs) were crucial factors influencing the performance of the capacitive sensor. In this work, SAMs formed from FT and DT mixtures with different compositions were studied. For physicochemical characterization of SAMs X-ray photoelectron spectroscopy (XPS), contact angle measurements as well as atomic force microscopy (AFM) were used. Cyclic voltammetry was employed to estimate an electrode surface coverage. Based on the obtained results, the composition of thiol layer providing the best parameters for capacitive sensing of chromium(VI) was chosen. Moreover, the analytical performance of sensor was verified.

     

Modification of gold electrode by self-assembled 2-mercapto benzothiazole for the determination of Hg2+

An electrochemical method was developed for the determination of mercury using polycrystalline gold electrode modified by self-assembled monolayers (SAMs) of 2-mercaptobenzothiazole (MBTH). Morphological and electrochemical characterisation of the self-assembled structure of MBTH was performed using atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS) measurements. The monolayer of MBTH has shown high affinity for Hg²⁺. The limit of detection for the determination of Hg²⁺ using the MBTH SAMs modified gold electrode was obtained as 0.421 μg L^?1. The pre-concentration of Hg²⁺ at open circuit potential is beneficial for the onsite monitoring of mercury concentration in water samples.     

Immobilization of peroxidase glycoprotein on gold electrodes modified with mixed epoxy-boronic Acid monolayers

The development of bioelectronic enzyme applications requires the immobilization of active proteins onto solid or colloidal substrates such as gold. Coverage of the gold surface with alkanethiol self-assembled monolayers (SAMs) reduces nonspecific adsorption of proteins and also allows the incorporation onto the surface of ligands with affinity for complementary binding sites on native proteins. We present in this work a strategy for the covalent immobilization of glycosylated proteins previously adsorbed through weak, reversible interactions, on tailored SAMs. Boronic acids, which form cyclic esters with saccharides, are incorporated into SAMs to weakly adsorb the glycoprotein onto the electrode surface through their carbohydrate moiety. To prevent protein release from the electrode surface, we combine the affinity motif of boronates with the reactivity of epoxy groups to covalently link the protein to heterofunctional boronate-epoxy SAMs. The principle underlying our strategy is the increased immobilization rate achieved by the weak interaction-induced proximity effect between slow reacting oxyrane groups in the SAM and nucleophilic residues from adsorbed proteins, which allows the formation of very stable covalent bonds. This approach is exemplified by the use of phenylboronates-oxyrane mixed monolayers as a reactive support and redox-enzyme horseradish peroxidase as glycoprotein for the preparation of peroxidase electrodes. Quartz crystal microbalance, atomic force microscopy, and electrochemical measurements are used to characterize these enzymatic electrodes. These epoxy-boronate functional monolayers are versatile, stable interfaces, ready to incorporate glycoproteins by incubation under mild conditions.     

A Reagentless Tyrosinase Biosensor Based on 1,6‐Hexanedithiol and Nano‐Au Self‐Assembled Monolayers

An amperometric tyrosinase biosensor was developed via a simple and effective immobilization method using the self‐assembled monolayers (SAMs) technique. The organic monolayer film was first formed by the spontaneous assembly of thiolor sulfur compound (1,6‐hexanedithiol, HDT) from solution onto gold electrode. When these thiol‐rich surfaces were exposed to Au colloid, the sulfurs form strong bonds to gold nanoparticles, anchoring the clusters to the electrode substrate. After the assembly of gold nanoparticles layer, a new nano‐Au surface was obtained. Thus, the tyrosinase could be immobilized onto the electrode. The tyrosinase retained its activity well in such an immobilization matrix. The various experimental variables for the enzyme electrode were optimized. The resulting biosensor can reach 95% of steady‐state current within 10 s, and the trend in the sensitivity of different phenolic compounds was as follows: catechol>phenol>p‐cresol. In addition, the apparent Michaelis–Menten constant (K and the stability of the enzyme electrode were estimated.