Immobilisation of cobaltferritin onto gold electrode based on self-assembled monolayers

The iron storage protein, ferritin, has a cavity of ～7?nm in diameter in which iron is oxidised and stored as a hydrated oxide core. Electron transfer is known to be an important step in the sequestering of iron by cellular ferritin. The cavity was used as a nanocontainer to grow cobalt nanoparticles. The immobilisation of ferritin on the electrode surface is essential for various bioelectronic applications. A cobaltferritin-immobilised electrode based on self-assembled monolayer (SAM)-modified gold electrode was developed. The cobaltferritin-immobilised SAM-modified electrode was characterised by electrochemical and atomic force microscopy (AFM) techniques. The results indicated that cobaltferritin was selectively immobilised onto succinimidyl alkanedisulfide-modified Au electrode by the covalent interaction between cobaltferritin and the terminal functional groups of the SAMs. The cobaltferritin immobilised modified electrode showed a direct electron transfer reaction between cobaltferritin and the electrode. The electrochemically regulated uptake and release of cobalts for cobaltferritin immobilised on the SAMs were demonstrated. The results obtained in this study indicate that cobaltferritin has potential for a biomaterial in nanoscale synthesis for potential magnetic, catalytic and biomedical-sensing applications.     

Electrochemical protection of thin film electrodes in solid state nanopores

Solid state nanopores are a core element of next-generation single molecule tools in the field of nano-biotechnology. Thin film electrodes integrated into a pore can interact with charges and fields within the pore. In order to keep the nanopore open and thus functional electrochemically induced surface alteration of electrode surfaces and bubble formation inside the pore have to be eliminated. This paper provides electrochemical analyses of nanopores drilled into TiN membranes which in turn were employed as thin film electrodes. We studied physical pore integrity and the occurrence of water decomposition yielding bubble formation inside pores by applying voltages between -4.5 and +4.5 V to membranes in various protection stages continuously for up to 24 h. During potential application pores were exposed to selected electrolyte-solvent systems. We have investigated and successfully eliminated electrochemical pore oxidation and reduction as well as water decomposition inside nanopores of various diameters ranging from 3.5 to 25 nm in 50 nm thick TiN membranes by passivating the nanopores with a plasma-oxidized layer and using a 90% solution of glycerol in water as KCl solvent. Nanopore ionic conductances were measured before and after voltage application in order to test for changes in pore diameter due to electrochemical oxidation or reduction. TEM imaging was used to confirm these observations. While non-passivated pores were electrochemically oxidized, neither electrochemical oxidation nor reduction was observed for passivated pores. Bubble formation through water decomposition could be detected in non-passivated pores in KCl/water solutions but was not observed in 90% glycerol solutions. The use of a protective self-assembled monolayer of hexadecylphosphonic acid (HDPA) was also investigated.     

Controlled nucleation and growth of surface-confined gold nanoparticles on a (3-aminopropyl)trimethoxysilane-modified glass slide: a strategy for SPR substrates

The thickness of the gold film and its morphology, including the surface roughness, are very important for getting a good, reproducible response in the SPR technique. Here, we report a novel alternative approach for preparing SPR-active substrates that is completely solution-based. Our strategy is based on self-assembly of the gold colloid monolayer on a (3-aminopropyl)trimethoxysilane-modified glass slide, followed by electroless gold plating. Using this method, the thickness of films can be easily controlled at the nanometer scale by setting the plating time in the same conditions. Surface roughness and morphology of gold films can be modified by both tuning the size of gold nanoparticles and agitation during the plating. Surface evolution of the Au film was followed in real time by UV-vis spectroscopy and in situ SPRS. To assess the surface roughness and electrochemical stability of the Au films, atomic force microscopy and cyclic voltammetry were used. In addition, the stability of the gold adhesion is demonstrated by three methods. The as-prepared Au films on substrates are reproducible and stable, which allows them to be used as electrodes for electrochemical experiments and as platforms for studying SAMs.     

铜表面硅烷-稀土掺杂膜的制备及缓蚀性能

运用分子自组装技术在铜片表面组装γ-巯丙基三甲氧基硅烷(MPTS)与稀土的掺杂膜。用原子力显微镜(AFM)观察了铜表面成膜过程,用金相显微镜观察铜片在0.5mol/L盐酸溶液中腐蚀72h后的表面形貌,运用电化学测量法对其防腐蚀性能进行评价。结果表明,硅烷-稀土掺杂膜对铜的缓蚀效率较单一的硅烷膜有明显提高,稀土浓度及组装时间对掺杂膜抗腐蚀性能有一定影响。经过极化曲线和交流阻抗的测定,确定硅烷-稀土掺杂膜的最佳组装条件为:LaCl3质量浓度为10g/L,组装30min,缓蚀率达93%。     

Electrochemical Growth of Nanosized Conducting Polymer Wires on Gold Using Molecular Templates

Conducting polymer nanowires and nanorings (see Figure) can be synthesized using the strategy described here—electrochemical growth on gold electrodes modified with self‐assembled monolayers (SAMs) of well‐separated thiolated cyclodextrins in an alkanethiol “forest”. Thiolated aniline monomer is anchored to the surface within the cyclodextrin cavity and forms an initiation point for polymer wire growth.     

Application of disorganized monolayer films on gold electrodes to the prevention of surfactant inhibition of the voltammetric detection of trace metals via anodic stripping of underpotential deposits: detection of copper

Development of an approach to prevention of electrode surface fouling by surfactants in samples is demonstrated. Spontaneously adsorbed monolayer systems employing short alkyl chains and bulky end groups are used to form porous disorganized monolayers on gold electrodes. Detection of copper by stripping of underpotential deposits formed at electrodes modified with disorganized films of mercaptoethanesulfonate (MES), mercaptopropanesulfonate, mercaptoacetic acid, and mercaptopropanoic acid was possible, and to a much lesser extent at aminoethanethiol and L-cysteine films. Use of short deposition times in conjunction with linear sweep anodic stripping voltammetry allowed detection of Cu2+ ions down to 1 x 10(-6) M in sulfuric acid solution, using underpotential deposition as the deposition step of the procedure. Calibration graphs were linear in the concentration range (1-80) x 10(-6) M Cu2+ using 15-s deposition at 0.00 V versus Ag/AgCl. The surfactants Tween 20, Tween 80, and Triton X-100 were found to have no affect on detection of Cu2+ ions in the calibration curve concentration range using MES-modified gold electrodes, whereas at unmodified gold electrodes very severe attenuation of the detection capability was manifested. The average slope for all calibration curves at the MES-modified electrode in the absence and presence of the surfactants at two different concentration levels was 0.0710 +/- 0.0024 microA microM(-1); in contrast, the slope of the calibration line at uncoated gold electrodes in the presence of surfactant was 0.0268 microA microM(-1). These results indicate the excellent ability of a disorganized, porous monolayer for prevention of fouling of the electrode surface by the surfactants.     

Porphyrin Monolayer‐Modified Gold Clusters as Photoactive Materials

Porphyrin monolayer‐modified gold clusters (three‐dimensional system) have been prepared successfully. Their electrochemical and photophysical properties have been compared to those of the corresponding two‐dimensional system of self‐assembled monolayers (SAMs) of the porphyrin as well as the bis(porphyrin) disulfide reference in solutions. In particular, the time‐resolved single‐photon counting fluorescence studies have indicated that the undesirable quenching of the porphyrin excited singlet state via energy transfer to the gold surface of the three‐dimensional system is much suppressed, as compared to the quenching of the porphyrin SAMs on the two‐dimensional flat gold surface. Thus, the present systems have a variety of potential utility for development of the artificial photosynthetic materials, photocatalysts, and chemical and biochemical sensors using fluorescent chromophore‐monolayer modified gold clusters.     

Synthesis and electrografting of dendron anchored OEGylated surfaces and their protein adsorption resistance

In this study, a series of electrochemically active oligo(ethylene glycol) (OEG) linear-dendrons have been synthesized and grafted onto electrode surfaces by cyclic voltammetry (CV) to improve protein resistance. Dendronized molecules with peripheral carbazole functionality and branching architecture enabled tethering of the poly(ethylene glycol) (PEG) or OEG group with a predictable number of electrochemical reactive groups affecting OEG distribution and orientation. It is possible that ample spacing between the OEG chains affects the intrinsic hydration of these layers and thus surface protein resistance. The films were characterized by CV, surface plasmon resonance (SPR), static contact angle measurements, and atomic force microscopy (AFM). This approach should enable improved nonbiofouling properties on biorelevant electrode surfaces (metal or metal oxides) by potentiostatic or potentiodynamic electrochemical methods, providing an alternative to the self-assembled monolayer (SAM) approach for anchoring PEG layers.     

Nanofabrication of bio-self assembled monolayer and its electrochemical property for toxicant detection

Cyclic voltammetry (CV) has been used to investigate the electrochemical behavior of a glutathione (GSH) self assembled monolayer on modified gold electrodes (Bio-SAM). The GSH monolayer exhibits an influence on electrode surface activity. Electrochemically immobilized dsDNA onto a Cyt c/GSH-SAM/Au electrode, which is useful for the fabrication of a nanobiosensing device. The immobilized Cyt c followed by dsDNA immobilized films maintained its surface activity and finally dsDNA/Cyt c/GSH-SAM/Au electrode, targeted for the detection of toxicants. The films were characterized by CV, DPV, and AFM. The differential pulse voltammetry (DPV) technique was applied to detect three kinds of common toxins, 2-aminoanthracene (2-AA), 3-bromobenzanthrone (3-BBA) and bisphenol A (BPhA). The electrochemical signals showed good inverse relationship with the increase of concentrations of toxicants. Our proposed system based on electrochemical method with nanoscale film technology can be applied at highly sensitive biosensor for detecting various toxic chemicals.     

Microstructure formation in electrochemically deposited Copper thin films

The influence of the electrochemical potential and deposition mode on the preferred orientation, morphology and microstructure of crystallites in electrochemically deposited (ECD) copper thin films was investigated using X‐ray diffraction (XRD), scanning electron microscopy (SEM) and the diffraction of back‐scattered electrons (EBSD). As a working electrode for the ECD process, thin gold layers were employed that were deposited on floating‐glass substrates in a vacuum evaporation process. With increasing negative electrochemical potential in the ECD process, the deposition mode changed from the charge transfer controlled one to the diffusion controlled one. At the highest electrochemical potentials, the copper deposition and the hydrogen release were running concurrently. The change of the deposition mode was accompanied by a change of the surface roughness of the thin films and by a change of the direction and degree of the preferred orientation of crystallites. The surface roughness of the deposited copper thin films increased with increasing electrochemical potential. Compact plate‐like crystallites with the preferred orientation {111} grew in the transport controlled deposition mode. Development of the {111} texture was supported by the {111} preferred orientation of the gold layers and by surface energy of copper, which is the lowest in the (111) plane. The diffusion controlled deposition mode was characterized by the growth of globular {110}‐oriented crystallites. The {110} texture resulted from the minimization of the anisotropic strain energy of copper via reduction of the structure defects in this deposition modus. For highest electrochemical potentials, the copper deposition run simultaneously with the development of hydrogen that resulted in growth of needle‐like crystallites with the {100} texture.     

Cell chip with nano-scale peptide layer to detect dopamine secretion from neuronal cells

A cell chip with a nano-scaled thin film of cysteine modified synthetic oligopeptide C(RGD)4 was fabricated to detect dopamine secretion from neuronal cells. Thin C(RGD)4 peptide layer was fabricated on chip surface for increasing the binding affinity of cells to gold electrode surface, which is essential for the electrochemical detection of dopamine released from PC12 cells. The structural formation of the peptide thin film was confirmed by both atomic force microscopy (AFM) and scanning electron microscopy (SEM). Redox characteristics of chemical dopamine were firstly characterized by voltammetric tool to compare the dopamine released from PC12 cells. Cells grown on the chip were then subjected to cyclic voltammetric (CV) analysis after 48 hours of incubation. The intensities of reduction peaks were found to be increased with increasing the concentrations of PC12 cells. In addition, the electrochemical redox signal increased more in the cells treated with glucose and potassium compared to the control group. Hence, the developed cell chip can be used to determine the effects of drugs on living cells electrochemically.     

Initial epitaxial growth of (111) Au/(111) Cu and (111) Cu/(111) Au

The room temperature modes of growth of Au/(111) Cu and Cu/(111) Au are described. For the former growth mode initial deposits (2.4 Å) of gold on copper form smooth flat islands delineated by coincidence lattice misfit dislocations. For 6.0 Å of gold deposit, both thick and thin gold areas were observed with almost complete substrate coverage. For a 10 Å deposit, surface coverage was complete. Strain measurements and dislocation densities obtained on the (111) Au/(111) Cu films suggest the presence of two separate misfit dislocation networks at the interface. The coincidence lattice networks were large enough for transmission electron microscopy observation but contributed little to total overlayer strain. The (van der Merwe) natural lattice misfit dislocations were too closely spaced for direct observation but their presence was inferred because of the strain measurements. The initial epitaxy of Cu/(111) Au was similar to the Stranski-Krastanov model: the initial monolayer of copper (also delineated by coincidence misfit dislocations) grew smoothly on the gold; additional copper formed essentially stress-free “nuclei” on top of the initial copper layer.     

Fabrication of cone-shaped boron doped diamond and gold nanoelectrodes for AFM-SECM

We demonstrate a reliable microfabrication process for a combined atomic force microscopy (AFM) and scanning electrochemical microscopy (SECM) measurement tool. Integrated cone-shaped sensors with boron doped diamond (BDD) or gold (Au) electrodes were fabricated from commercially available AFM probes. The sensor formation process is based on mature semiconductor processing techniques, including focused ion beam (FIB) machining, and highly selective reactive ion etching (RIE). The fabrication approach preserves the geometry of the original AFM tips resulting in well reproducible nanoscaled sensors. The feasibility and functionality of the fully featured tips are demonstrated by cyclic voltammetry, showing good agreement between the measured and calculated currents of the cone-shaped AFM-SECM electrodes.     

Feedback-independent Pt nanoelectrodes for shear force-based constant-distance mode scanning electrochemical microscopy

A new generation of platinum nanoelectrodes for constant-distance mode scanning electrochemical microscopy (CD-SECM) has been prepared, characterized, and used for high spatial resolution electrochemical measurements and visualization of electrochemically induced concentration gradients in microcavities. The probes have long (1-2 cm), narrow quartz tips that were conically polished and have a Pt nanoelectrode that is slightly offset from center. Because of the size and location of the electrode on the probe, it does not exhibit SECM feedback while approaching the analyzed sample surfaces even to distances within a few hundred nanometers. The probe was positioned near the surface while scanning and performing electrochemical measurements through use of nonoptical shear force control of the tip-to-sample distance. Test structures consisted of cylindrically shaped microcavities that are 50 microm in diameter with three individually addressable electrodes: a gold disk at 8-microm depth, a crescent-shaped gold ring at 4-microm depth along the wall, and a top gold electrode at the rim. Different electrodes within the microcavity were used to reduce and oxidize redox species in 250 microL of a solution of 5 mM hexaamineruthenium(III) chloride and 0.1 M potassium chloride, protected from evaporation by mineral oil, while the SECM tip followed the topography of the structures and monitored the current from the oxidation of [Ru(NH3)6]2+. Electrochemically generated concentration profiles were obtained from these complex test structures that are not possible with any other SECM technology at this time.     

图案化金属铜纳米线阵列的制备与表征

采用紫外线光刻技术与电化学沉积相结合的方法,成功制备了不同图案的铜纳米线阵列:一种是圆形图案;另一种是QDU图案.首先利用紫外线光刻技术在多孔阳极氧化铝模板(AAO)生成预设图案,以此作为"二次模板";再利用电化学方法将铜纳米线沉积到"二次模板"的开孔中.扫描电镜(SEM)测试结果表明,大面积、高规整的铜纳米线图案阵列各自独立地立在基底上, 同时,用电子能谱(EDS)分析了铜纳米线的化学成分.透射电镜(TEM)也探测到了铜纳米线的微结构.     

Covalent deposition of ferritin nanoparticles onto gold surfaces

Ferritin nanoparticles have been deposited immobilized onto a properly modified gold surface by specific covalent bonding through lysine rests at the ferritin external surface. Atomic force microscopy (AFM) images confirmed the existence of a single ferritin monolayer. This is an easy and flexible route to form stable ferritin networks, which are covalently fixed to a gold substrate.     

Forming microstructured alkanethiol self-assembled monolayers on gold by laser ablation

A process to form microstructured alkanethiol self-assembled monolayers (SAMs) on gold is described. It is well known that alkanethiols spontaneously form homogenous SAMs on gold surfaces. By means of laser ablation, the exposed areas of alkanethiol monolayers can be removed from the gold surface. Free gold is obtained which can react further with second and third thiols. By this technique, structured alkanethiol SAMs are obtained reliably and easily. In a rather narrow window of pulse intensities, in our example 120$hboxMW/cm^2pm hbox10%$from a frequency-doubled Nd : YVO$_4$laser with 6-ns pulsewidth operating at a repetition rate of 20 kHz, ablation of alkanethiol monolayers is obtained without causing any damage to the gold substrate. Examples are presented where lines down to 10$muhbox m$in width were laser ablated into an SAM formed either from a hydrophilic or a hydrophobic alkanethiol and filled with a monolayer of a second alkanethiol of opposite hydrophilicity. The patterned structures were examined by optical and fluorescence microscopy as well as by lateral force microscopy. The presented method enables the preparation of microstructured SAMs on gold and probably on a wide variety of other substrates.     

Label-free electrochemical detection for aptamer-based array electrodes

An electrochemical impedance spectroscopy method of detection for aptamer-based array electrodes is reported in which the binding of aptamers immobilized on gold electrodes leads to impedance changes associated with target protein binding events. Human IgE was used as a model target protein and incubated with the aptamer-based array consisting of single-stranded DNA containing a hairpin loop. To increase the binding efficiency for proteins, a hybrid modified layer containing aptamers and cysteamine was fabricated on the photolithographic gold surface through molecular self-assembly. Atomic force microscopy analysis demonstrated that human IgE could be specifically captured by the aptamer and stand well above the self-assembled monolayer (SAM) surface. Compared to immunosensing methods using anti-human IgE antibody as the recognition element, impedance spectroscopy detection could provide higher sensitivity and better selectivity for aptamer-modified electrodes. The results of this method show good correlation for human IgE in the range of 2.5-100 nM. A detection limit of 0.1 nM (5 fmol in a 50-microL sample) was obtained, and an average of the relative standard deviation was <10%. The method herein describes the first label-free detection for arrayed electrodes utilizing electrochemical impedance spectroscopy.     

磁头表面含氟三氯硅烷自组装膜的生长机理

在磁头表面制备了1H,1H,2H,2H-四氢全氟辛烷基三氯硅烷（FOTS）自组装膜,采用X射线光电子能谱仪（XPS）、时间飞行二次离子质谱仪（TOF-SIMS）、接触角测量仪和原子力显微镜（AFM）对FOTS自组装膜进行表征,研究了自组装膜的生长机理．结果表明,FOTS自组装膜的生长经过了亚单层膜的低等覆盖,亚单层膜的中等覆盖、团聚和聚结四个阶段．其中第一层和第二层自组装膜的亚单层膜形态和生长方式不同,第一层的亚单层膜呈岛状,岛的生长是自身向外扩展;第二层的亚单层膜呈簇状,簇通过效量增加来实现生长．超薄完整的单层FOTS自组装膜（膜厚为0．8nm、Ra为0．125nm）能使磁头表面的接触角值增加,疏水性能提高．     

Construction of multilayers of bare and Pd modified gold nanoclusters and their electrocatalytic properties for oxygen reduction

Abstract

Multilayers of gold nanoclusters (GNCs) coated with a thin Pd layer were constructed using GNCs modified with self-assembled monolayers (SAMs) of mercaptoundecanoic acid and a polyallylamine hydrochloride (PAH) multilayer assembly, which has been reported to act as a three-dimensional electrode. SAMs were removed from GNCs by electrochemical anodic decomposition and then a small amount of Pd was electrochemically deposited on the GNCs. The kinetics of the oxygen reduction reaction (ORR) on the Pd modified GNC/PAH multilayer assembly was studied using a rotating disk electrode, and a significant increase in the ORR rate was observed after Pd deposition. Electrocatalytic activities in alkaline and acidic solutions were compared both for the GNC multilayer electrode and Pd modified GNC electrode.