Supramolecular Approach to Gold Nanoparticle/Triruthenium Cluster Hybrid Materials and Interfaces

A systematic and comprehensive study of the interaction of citrate-stabilized gold nanoparticles with triruthenium cluster complexes of general formula [Ru(3)(CH(3)COO)(6)(L)](+) [L = 4-cyanopyridine (4-CNpy), 4,4`-bipyridine (4,4`-bpy) or 4,4`-bis(pyridyl)ethylene (bpe)] has been carried out. The cluster-nanoparticle interaction in solution and the construction of thin films of the hybrid materials were investigated in detail by electronic and surface plasmon resonance (SPR) spectroscopy, Raman scattering spectroscopy and scanning electron microscopy (SEM). Citrate-stabilized gold nanoparticles readily interacted with [Ru(3)O(CH(3)COO)(6)(L)(3)](+) complexes to generate functionalized nanoparticles that tend to aggregate according to rates and extents that depend on the bond strength defined by the characteristics of the cluster L ligands following the sequence bpe > 4,4`-bpy >> 4-CNpy. The formation of compact thin films of hybrid AuNP/[Ru(3)O(CH(3)COO)(6)(L)(3)](+) derivatives with L = bpe and 4,4`-bpy indicated that the stability/lability of AuNP-cluster bonds as well as their solubility are important parameters that influence the film contruction process. Fluorine-doped tin oxide electrodes modified with thin films of these nanomaterials exhibited similar electrocatalytic activity but much higher sensitivity than a conventional gold electrode in the oxidation of nitrite ion to nitrate depending on the bridging cluster complex, demonstrating the high potential for the development of amperometric sensors.

Ex Situ Scanning Electrochemical Microscopy (SECM) Investigation of Bismuth- and Bismuth/Lead Alloy Film-Modified Gold Electrodes in Alkaline Medium

Scanning electrochemical microscopy (SECM) in feedback mode was employed to characterise the reactivity and microscopic peculiarities of bismuth and bismuth/lead alloys plated onto gold disk substrates in 0.1 molL(-1) NaOH solutions. Methyl viologen was used as redox mediator, while a platinum microelectrode was employed as the SECM tip. The metal films were electrodeposited ex situ from NaOH solutions containing either bismuth ions only or both bismuth and lead ions. Approach curves and SECM images indicated that the metal films were conductive and locally reactive with oxygen to provide Bi(3+) and Pb(2+) ions. The occurrence of the latter chemical reactions was verified by local anodic stripping voltammetry (ASV) at the substrate solution interface by using a mercury-coated platinum SECM tip. The latter types of measurements allowed also verifying that lead was not uniformly distributed onto the bismuth film electrode substrate. These findings were confirmed by scanning electron microscopy images. The surface heterogeneity produced during the metal deposition process, however, did not affect the analytical performance of the bismuth coated gold electrode in anodic stripping voltammetry for the determination of lead in alkaline media, even in aerated aqueous solutions. Under the latter conditions, stripping peak currents proportional to lead concentration with a satisfactory reproducibility (within 5% RSD) were obtained.

Characterisation of gold electrodes modified with self-assembled monolayers of l-cysteine for the adsorptive stripping analysis of copper

Electrochemical sensors for copper ions in environmental samples were prepared by modifying gold electrodes with l-cysteine by self-assembly. The adsorption of l-cysteine on gold electrodes was studied by electrochemical reductive desorption in 0.5 M KOH, and the interaction of l-cysteine with copper ions was investigated by cyclic voltammetry, chronoamperometry and X-ray photoelectron spectroscopy. At low concentrations the ratio of l-cysteine to bound Cu(II) is 2:1. At higher concentrations (0.1 M) copper reacts with adsorbed cysteine forming copper sulfide on the electrode surface. On a modified l-cysteine gold electrode, Osteryoung square wave voltammetric determination of Cu(II) with a detection limit below 5 ppb has been demonstrated.

Redox voltammetry of sub-parts per billion levels of Cu2+ at polyaspartate-modified gold electrodes

An electrochemical sensor for the detection of Cu2+ is reported which incorporates poly-l-aspartic acid (PLAsp) with 32–96 aspartate units as a selective ligand for the metal ion. PLAsp is covalently attached to a gold electrode modified with a monolayer of 3-mercaptopropionic acid using carbodiimide coupling via an N-hydroxysuccinimide (NHS) ester intermediate. The acid side groups and deprotonated peptide nitrogens on two aspartate moieties are thought to be primarily responsible for chelation of Cu2+, which remains bound when reduced to Cu+. A consequence of the multiple binding points that are available with a polypeptide is the low detection limit. The lowest concentration detected was 3 nM (0.2 ppb) achieved with Osteryoung square wave voltammetry. This detection limit compares favourably with that of ICP-OES and previously reported cysteine-modified electrodes. Analysis of tap and lake water samples using the PLAsp-modified electrode agreed well with ICP-OES analysis of the same samples.

Analytical procedure for total mercury determination in fishes and shrimps by chronopotentiometric stripping analysis at gold film electrodes after microwave digestion

A method for the total mercury determination in fish and shrimps employing chronopotentiometric stripping analysis on gold film electrodes is described. Fish and shrimp tissues were digested using a microwave oven equipped with closed vessels. We developed a microwave heating program which decomposed all the samples employing diluted nitric acid and hydrogen peroxide. The proposed method was validated by analyzing a certified reference material and then applied for different fish species from fresh water and seawater acquired in local markets of São Paulo city, Brazil. The Brazilian legislation establishes 0.5 and 1 mg per kilogram of fish as upper limit of mercury for omnivorous and predator species, respectively. Except for blue shark tissues, the mercury content was situated below 0.5 mu g g(-1) for all the analyzed samples. The detection limit of the proposed method was calculated as 5 ng g(-1) of sample utilizing 5 minutes of electrodeposition (+300 mV vs. Ag/AgCl) on the gold electrode. (c) 2006 Elsevier Ltd. All rights reserved.

Compact disks, a new source for gold electrodes. Application to the quantification of copper by PSA

In this work we describe a versatile and very sensitive way for copper quantification by potentiometric stripping analysis using gold electrodes obtained from recordable compact disks (CDs). This new source of electrodes (CDtrodes) shown similar performance to the commercial gold electrodes with superior versatility and lower cost. Recordable CDs contains a highly pure gold film with thickness between 50 and 100 nm and superficial area of ca. 100 cm(2). The working electrode developed was used successfully in stationary cell and many experimental parameters have been optimized. For copper, the detection limit attained was 30 ng L-1 (600 s deposition time) with remarkable precision (standard deviation of 1.8 % for 20 repetitive measurements using 25 mu gL(-1) of copper with 60 s of deposition time). The gold electrode developed was used for analysis of copper in sugar cane spirits and tap water samples. The results were compared with those obtained by atomic absorption spectroscopy.

Fast assembly of non-thiolated DNA on gold surface at lower pH

In a typical protocol for attaching DNA to a gold electrode, thiolated DNA is incubated with the electrode at neutral pH overnight. Here we report fast adsorption of non-thiolated DNA oligomers on gold electrodes at acidic pH (i.e., pH ~3.0). The peak-to-peak potential difference and the redox peak currents in typical cyclic voltammetry of [Fe(CN)6]3- are investigated to monitor the attachment. Compared with incubation at neutral pH, the lower pH can significantly promote the adsorption processes, enabling efficient adsorption even in 30min. The adsorption rate is DNA concentration-dependent, while the ionic strength shows no influence. Moreover, the adsorption is base-discriminative, with a preferred order of A>C≫G, T, which is attributed to the protonation of A and C at low pH and their higher binding affinity to gold surface. The immobilized DNA is functional and can hybridize with its complementary DNA but not a random DNA. This work is promising to provide a useful time-saving strategy for DNA assembly on gold electrodes, allowing fast fabrication of DNA-based biosensors and devices. © 2013 Elsevier Inc.

Graphene nanodots encaged 3-D gold substrate as enzyme loading platform for the fabrication of high performance biosensors

Herein, a uniform three-dimensional (3-D) graphene nanodots-encaged porous gold electrode was prepared via ion beam sputtering deposition (IBSD) and mild corrosion chemistry for efficient enzyme electrode fabrication. Enzymes, like glucose oxidase and catalase, were modified with pyrene functionalities and then loaded into the graphene nanodots encaged porous gold electrode via non-covalent π-π stacking interaction between pyrene and graphene. The fabricated enzyme electrodes showed profound reusability and repeatability, high sensitivity, inherent selectivity and enhanced detection range. As for glucose analysis a broad linear range from 0.05 to 100 mM was obtained and the linear range for hydrogen peroxide was 0.005 to 4 mM. Detection limits of 30 μM for glucose and 1 μM for hydrogen peroxide were achieved (S/N = 3), respectively. These electrodes can be applied to analyze the clinical samples with reliable results. The formation mechanism and 3-D structure of the porous electrode were investigated using high resolution transmission electron microscope (HRTEM), atomic force microscopy (AFM), scanning electron microscope (SEM) and electrochemical impedance spectroscopy (EIS). Most importantly, various other ideal biosensors can be fabricated using the same porous electrode and the same enzyme modification methodology.

AFM study of morphological changes associated with electrochemical solid--solid transformation of three-dimensional crystals of TCNQ to metal derivatives (metal= Cu, Co, Ni; TCNQ= tetracyanoquinodimethane)

In situ atomic force microscopy (AFM) allows images from the upper face and sides of TCNQ crystals to be monitored during the course of the electrochemical solid–solid state conversion of 50 × 50 μm2 three-dimensional drop cast crystals of TCNQ to CuTCNQ or M[TCNQ]2(H2O)2 (M = Co, Ni). Ex situ images obtained by scanning electron microscopy (SEM) also allow the bottom face of the TCNQ crystals, in contact with the indium tin oxide or gold electrode surface and aqueous metal electrolyte solution, to be examined. Results show that by carefully controlling the reaction conditions, nearly mono-dispersed, rod-like phase I CuTCNQ or M[TCNQ]2(H2O)2 can be achieved on all faces. However, CuTCNQ has two different phases, and the transformation of rod-like phase 1 to rhombic-like phase 2 achieved under conditions of cyclic voltammetry was monitored in situ by AFM. The similarity of in situ AFM results with ex situ SEM studies accomplished previously implies that the morphology of the samples remains unchanged when the solvent environment is removed. In the process of crystal transformation, the triple phase solid∣electrode∣electrolyte junction is confirmed to be the initial nucleation site. Raman spectra and AFM images suggest that 100% interconversion is not always achieved, even after extended electrolysis of large 50 × 50 μm2 TCNQ crystals.

Voltammetric, spectroscopic, and microscopic investigations of electrocrystallized forms of semiconducting AgTCNQ (TCNQ=7,7,8,8-tetracyanoquinodimethane) exhibiting different morphologies and colors

Chemically synthesized AgTCNQ exists in two forms that differ in their morphologies (needles and microcrystals) and colors (red and blue). It is now shown that both forms exhibit essentially indistinguishable X-ray diffraction, spectroscopic, and thermochemical data, implying that they are not separate phases, as implied in some literature. Electrochemical reduction of TCNQ((MeCN)) in the presence of Ag+((MeCN)) generates both red and blue AgTCNQ. On glassy carbon, platinum, or indium tin oxide electrodes and at relatively positive deposition potentials, slow growth of high aspect ratio, red needle AgTCNQ crystals occurs. After longer times and at more negative deposition potentials, blue microcrystalline AgTCNQ thin films are favored. Blue AgTCNQ is postulated to be generated via reduction of a Ag+\[(TCNQ(center dot-))(TCNQ)]((MeCN)) intermediate. At even more negative potentials, Ag-(metal) formation inhibits further growth of AgTCNQ. On a gold electrode, Ag-(metal)) deposition occurs at more positive potentials than on the other electrode materials examined. However, surface plasmon resonance data indicate (hat a small potential region is available between the stripping of Ag-(metal)) and the oxidation of TCNQ(center dot-)(MeCN) back to TCNQ(MeCN) where AgTCNQ may form. AgTCNQ in both the red and blue forms also can be prepared electrochemically on a TCNQ((s)) modified electrode in -0.1 M AgNO3(aq) where deposition of Ag(m,,,I) onto the TCNQ((s)) crystals allows a charge transfer process to occur. However, the morphology formed in this solid-solid phase transformation is more difficult to control.

Eletrodeposição de revestimentos funcionais compósitos Cu/partículas de óxidos de alumínio

Revestimentos funcionais compósitos são um atrativo tecnológico crescente, pois possibilitam a combinação de materiais metálicos, poliméricos ou cerâmicos, resultando em propriedades superiores as dos materiais individuais, sendo por este motivo, largamente aplicados na engenharia de materiais. Na presente dissertação, foram produzidos revestimentos compósitos por eletrodeposição através da codeposição de uma matriz metálica de cobre e de partículas de óxidos de alumínio incorporadas (g - Al2O3 ou AlO(OH)), sobre substratos de aço carbono, a partir de diferentes banhos eletrolíticos. Três etapas foram efetuadas, na primeira realizou-se o estudo da influência do modo de agitação e da presença ou não de ligantes (citrato de sódio 1,00 mol/L) nos teores de cobre e alumina nos revestimentos produzidos. Em seguida foi avaliada a ação de complexantes (citrato de sódio 1,00 mol/L e pirofosfato de potássio 0,90 mol/L) usando polarização potenciodinâmica e voltametria cíclica, em conjunto com microbalança eletroquímica de cristal de quartzo (EQCM) e a posterior produção de revestimentos compósitos a partir de banhos contendo CuSO4 0,02 mol/L + pirofosfato de potássio 0,90 mol/L + 20 g/L de alumina, variando a densidade de corrente aplicada (I), a velocidade de agitação do eletrodo rotatório (A) e o do tempo de agitação prévia (t). Por fim, na terceira etapa, fez-se a substituição de alumina por Boehmita e a produção dos revestimentos a partir de banhos contendo CuSO4 0,02 mol/L + pirofosfato de potássio 0,90 mol/L + 20 g/L de Boehmita, empregando um planejamento composto central, em que os parâmetros citados também foram variados. Os resultados mostraram que a presença de um ligante e a agitação prévia e continuada do eletrólito durante o experimento foram fundamentais para a produção dos revestimentos compósitos. Ensaios de EQCM mostraram que o citrato se adsorveu na superfície do eletrodo de ouro, diferentemente do pirofosfato. Os teores de Boehmita e cobre nos revestimentos produzidos, assim como a morfologia, resistência de polarização e densidade de corrente de corrosão dos revestimentos foram influenciados pelos parâmetros avaliados.

Studying adsorbent dynamics on a quartz crystal resonator using its nonlinear electrical response

The quartz crystal resonator has been traditionally employed in studying surface-confined physisorbed films and particles by measuring dissipation and frequency shifts. However, theoretical interpretation of the experimental observations is often challenged due to limited understanding of physical interaction mechanisms at the interfaces involved. Here we model a physisorbed interaction between particles and gold electrode surface of a quartz crystal and demonstrate how the nonlinear modulation of the electric response of the crystal due to the nonlinear interaction forces may be used to study the dynamics of the particles. In particular, we show that the graphs of the deviation in the third Fourier harmonic response versus oscillation amplitude provide important information about the onset, progress and nature of sliding of the particles. The graphs also present a signature of the surface-particle interaction and could be used to estimate the interaction energy profile. Interestingly, the insights gained from the model help to explain some of the experimental observations with physisorbed streptavidin-coated polystyrene microbeads on quartz resonators. © 2012 Elsevier B.V. All rights reserved.

A sensitive impedimetric thrombin aptasensor based on polyamidoamine dendrimer

A label-free and highly sensitive impedimetric aptasensor based on a polyamidoamine dendrimer modified gold electrode was developed for the determination of thrombin. Amino-terminated polyamidoamine dendrimer was firstly covalently attached to the cysteine functionalized gold electrode through glutaraldehyde coupling. Subsequently, the dendrimer was activated with glutaraldehyde, and amino-modified thrombin aptamer probe was immobilized onto the activated dendrimer monolayer film. The layer-by-layer assembly process was traced by surface plasmon resonance and electrochemical impedance spectroscopy.

Methylene blue as an indicator for sensitive electrochemical detection of adenosine based on aptamer switch

In this paper, a simple, label-free and regenerative method was proposed to study the interaction between aptamer and small molecule by using methylene blue (MB+) as an electrochemical indicator. A thiolated capture probe containing twelve bases was firstly self-assembled on gold electrode by gold-sulfur affinity. Aptamer probe containing thirty two bases, which was designed to hybridize with capture DNA sequence and specifically recognize adenosine, was then immobilized on the electrode surface by hybridization reaction. MB+ was abundantly adsorbed on the aptamer probe by the specific interaction between MB+ and guanine base in aptamer probe. MB+-anchored aptamer probe can be forced to dissociate from the sensing interface after adenosine triggered structure switching of the aptamer. The peak current of MB+ linearly decreased with the concentration of adenosine over a range of 2 x 10 (8)- x 10 (6) M with a detection limit of 1 x 10 (8) M. In addition, we examined the selectivity of this electrochemical biosensor for cytidine, uridine and guanosine that belonged to the nucleosides family and possessed 1 similar structure with adenosine.

Interaction between alpha-actinin and negatively charged lipids membrane investigated by surface plasmon resonance and electrochemical methods

alpha-Actinin has been shown to be capable of interacting with some special membrane phospholipids directly, which is important for its function. In this study, hybrid bilayer membranes composed of negatively charged lipids are constructed on the surface plasmon resonance gold substrate and on the gold electrode, respectively, and the interaction between alpha-actinin and negatively charged lipids membrane is investigated by surface plasmon resonance, cyclic voltammetry and electrochemical impedance spectroscopy methods. alpha-Actinin is proved to be able to interact with the negatively charged lipids membrane directly. It can also insert at least partly into the membrane or lead to some defect or lesion in the membrane, which increase the permeability of the membrane. This study would bring some insight on the interaction between the alpha-actinin and the cell membranes in vivo.