Asymmetry of electron transmission through monolayers of helical polyalanine adsorbed on gold surfaces

Polyalanine derivatives containing cysteamine linker R-(Ala)14NH-(CH2)2-SH, where R is ferrocenecarbonyl or hydrogen, were synthesized and then used to form self-assembled monolayers on gold. The tilt angles and the packing density of the molecules within monolayer assemblies were determined by FTIR spectroscopy and scanning tunneling microscopy, respectively. Electrochemical properties of monolayer-modified electrodes were studied using cyclic voltammetry and impedance spectroscopy. Measurements of electron-transfer rates using electrochemical techniques and scanning tunneling spectroscopy revealed asymmetry dependent on the applied voltage. It is suggested that the observed electron-transfer behavior is connected with the electric field generated by the molecular dipole of the polyalanine helix.     

Functionalization of Electrode Surfaces with Monolayers of Azocompounds and Gold Clusters

Properties of monolayers of azocrown compound self-assembled on gold substrates were studied using voltammetry and scanning tunneling microscopy. The surface concentrations of this compound in monolayers were determined from the area of the voltammetric reduction peaks. The area per one molecule estimated from voltammetry experiments is 0.65 nm². This value was comparable with the limiting molecular area of the compound in the Langmuir–Blodgett film at the air–water interface. We also observed the presence of gold clusters and other gold structures by STM when a gold electrode modified with azocrown compound was dipped into the tetrachloroaurate solution. Even better spectra of clusters were obtained following one voltammetric scan in the range 0.5 to ?0.6 V. After more cycles or if we condition the electrode at 0.4 V the clusters aggregate into wires.     

The determination of traces of thiocyanate and copper(II) ions by cathodic stripping voltammetry

Cathodic stripping methods are described for the determination of traces of thiocyanate ions down to 2 × 10^-8 mol l^-1 and Cu(II) ions down to 1 × 10^-8 mol l^-1. The method involves electrolytic accumulation of copper(I) thiocyanate on the surface of a hanging mercury drop electrode followed by stripping of the deposit during the cathodic scan. For the determination of thiocyanate, a copper amalgam electrode can be used. Examples of application of the method for the determination of traces of thiocyanate in common salts, in saliva and urine as well as for the determination of copper(II) ions in tap water are described.     

Modified electrodes based on lipidic cubic phases

The lipidic cubic phase can be characterized as a curved bilayer forming a three-dimensional, crystallographical, well-ordered structure that is interwoven by aqueous channels. It provides a stable, well-organized environment in which diffusion of both water-soluble and lipid-soluble compounds can take place. Cubic phases based on monoacylglycerols form readily and attract our interest due to their ability to incorporate and stabilize proteins. Their lyotropic and thermotropic phase behaviour has been thoroughly investigated. At hydration over 20%, lipidic cubic phases Ia3d and Pn3m are formed. The latter is stable in the presence of excess water, which is important when the cubic phase is considered as an electrode-modifying material. Due to high viscosity, the cubic phases can be simply smeared over solid substrates such as electrodes and used to host enzymes and synthetic catalysts, leading to new types of catalytically active modified electrodes as shown for the determination of cholesterol, CO(2), or oxygen. The efficiency of transport of small hydrophilic molecules within the film can be determined by voltametry using two types of electrodes: a normal-size electrode working in the linear diffusion regime, and an ultramicroelectrode working under spherical diffusion conditions. This allows determining both the concentration and diffusion coefficient of the electrochemically active probe in the cubic phase. The monoolein-based cubic phase matrices are useful for immobilizing enzymes on the electrode surface (e.g., laccases from Trametes sp. and Rhus vernicifera were employed for monitoring dioxygen). The electronic contact between the electrode and the enzyme was maintained using suitable electroactive probes.     

Electron Transport Through Composite Monolayers

Well-organized thiol monolayers on electrode surfaces are prepared using the Langmuir–Blodgett and self-assembly methods. Planned modification of the molecules building the monolayer allow the electron tunneling efficiency across the monolayer to be controlled. The barrier properties of the monolayers are probed by electrochemical methods. The extent of blocking for all systems under study indicates that contribution of the electroactive molecules that find direct access to the electrode surface can be neglected. These observations permit us to use the monolayers for the determination of the kinetic parameters of Fe(CN)^3– ₆ and IrCl^2– ₆ ion reduction. Such monolayers are employed for the studies of long-range electron transport. We show that insertion of amide bonds in appropriate positions of the alkyl chains of all molecules building the monolayer makes it possible to create a lateral hydrogen-bond network linking the internal amide groups in the monolayer and contributing to the electronic coupling between the redox probe and the electrode. The relation between the location of the amide moiety in the molecule and its importance for the electron tunneling efficiency through the intervening organic medium is discussed.     

Adsorption—Nucleation and growth mechanism of CuSCN monolayer formation on a copper amalgam electrode in thiocyanate solutions

Using voltammetric, galvanostatic and potentiostatic techniques, the electrodeposition of cuprous thiocyanate on a copper amalgam electrode has been studied in acidic solutions containing various thiocyanate ion concentrations. Under the conditions used, the formation of two successive monolayers of CuSCN could be studied before the onset of bulk deposition. It was found that the formation of the first monolayer proceeds according to a complex adsorption-nucleation and growth mechanism. In the first stage, cuprous thiocyanate is adsorbed on the amalgam electrode; in the second, the disordered layer of adsorbate rearranges to form two-dimensional crystalline centres; and in the third stage, these centres grow, completing the formation of the entire monolayer. The second monolayer is formed in a much simpler way, according to a mechanism of two-dimensional, instantaneous nucleation and growth. At high thiocyanate ion concentration, the formation of the CuSCN layer is obscurred by the extensive formation of solution soluble species.     

Properties of monolayers of crown ethers bearing an azo and azoxy group in the macrocycle

Two methods are described for preparing monomolecular layers of crown ethers with an azo or azoxy group in the macrocycle. When the molecules used to build the monolayer are soluble in aqueous solutions, adsorptive preconcentration on mercury electrodes was used to prepare the monolayer coating. The monolayer was electroactive due to the presence of the azo or azoxy unit in the molecules. Monolayers of crown ethers bearing an azo group in the macrocycle were shown to recognize alkali metal cations present in the solution. Changes of the parameters of the voltammetric reduction peaks - peak potential and peak width, served as an indication of specific interactions of the monolayer of 13-membered and 16-membered azocrown ethers with Na⁺ and K⁺ cations, respectively.The monolayers capable of recognizing cations have also been prepared on the aqueous solution-air interface, using the Langmuir technique. In this approach, amphiphilic derivatives of the azocrowns were synthesized and the monolayer has been assembled on the subphase containing metal cations. Binding of the cation by the macrocycle has a stabilizing effect on the monolayer and higher collapse pressures are achieved than on the pure water subphase. The monolayer was transferred from the air-water interface on the solid substrate using the Langmuir-Blodgett technique. Thin mercury film electrodes on the Ag substrate, or An films evaporated on glass slides were employed as the electrode substrates. The former gave monolayer modified electrodes of higher stability.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August, 1995.     

Stability of 47Sc-complexes with acyclic polyamino-polycarboxylate ligands

The aim of this study was to evaluate acyclic ligands which can be applied for labeling proteins such as monoclonal antibodies and their fragments with scandium radionuclides. Recently, scandium isotopes (⁴⁷Sc, ⁴⁴Sc) are more available and their properties are convenient for radiotherapy or PET imaging. They can be used together as “matched pair” in theranostic approach. Because proteins denaturize at temperature above 42 °C, ligands which efficiently form complexes at room temperature, are necessary for labelling such biomolecules. For complexation of scandium radionuclides open chain ligands DTPA, HBED, BAPTA, EGTA, TTHA and deferoxamine have been chosen. We found that the ligands studied (except HBED) form strong complexes within 10 min and that the radiolabelling yield varies between 96 and 99 %. The complexes were stable in isotonic NaCl, but stability of ⁴⁶Sc-TTHA, ⁴⁶Sc-BAPTA and ⁴⁶Sc-HBED in PBS buffer was low, due to formation by Sc³⁺stronger complexes with phosphates than with the studied ligands. From the radiolabelling studies with n.c.a. ⁴⁷Sc we can conclude that the most stable complexes are formed by the 8-dentate DTPA and EGTA ligands.     

Electrochemical wiring of alpha, omega-alkanedithiol molecules into an electrical circuit

The intrinsic electrical conductivity of alpha, omega-alkanedithiol increases if both ends of the molecule are covalently bonded to metallic contacts.     

Enzymatic electrodes nanostructured with functionalized carbon nanotubes for biofuel cell applications

Nanostructured bioelectrodes were designed and assembled into a biofuel cell with no separating membrane. The glassy carbon electrodes were modified with mediator-functionalized carbon nanotubes. Ferrocene (Fc) and 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS) bound chemically to the carbon nanotubes were found useful as mediators of the enzyme catalyzed electrode processes. Glucose oxidase from Aspergillus niger AM-11 and laccase from Cerrena unicolor C-139 were incorporated in a liquid-crystalline matrix-monoolein cubic phase. The carbon nanotubes–nanostructured electrode surface was covered with the cubic phase film containing the enzyme and acted as the catalytic surface for the oxidation of glucose and reduction of oxygen. Thanks to the mediating role of derivatized nanotubes the catalysis was almost ten times more efficient than on the GCE electrodes: catalytic current of glucose oxidation was 1 mA cm⁻² and oxygen reduction current exceeded 0.6 mA cm⁻². The open circuit voltage of the biofuel cell was 0.43 V. Application of carbon nanotubes increased the maximum power output of the constructed biofuel cell to 100 μW cm⁻² without stirring of the solution which was ca. 100 times more efficient than using the same bioelectrodes without nanotubes on the electrode surface.