Interaction between the antibacterial compound,oleuropein, and model membranes

Oleuropein, a secoiridoid glycoside extracted from the olive tree, Olea europaea L., has been described as showing antibacterial properties. However, the exact mechanism of these antimicrobial properties is not yet well understood. In the present study, we have studied the interaction of oleuropein with phosphatidylglycerol (PG) as a model membrane for Staphylococcus aureus (S. aureus) (Gram-positive bacteria) and phosphatidylethanolamine and Escherichia coli (E. coli) lipid extract as a model membrane for E. coli (Gram-negative bacteria). The study has been carried out using monolayers as model membranes and using kinetics at constant area and compression isotherms with Brewster angle microscopy (BAM) observations. The results show that oleuropein interacts in higher extent with PG monolayers, which is related with its stronger antibacterial effect against Gram-positive bacteria. The effects on the membrane are probably produced at the cell surface because oleuropein did not form stable mixed monolayers with the lipids assayed at the air/water interface.     

偶氮苯自组装单分子膜中长程电子转移机理

利用自组装技术在金电极表面构造了具有不同前端健长度偶氮苯功能化的单分子膜体系：Au／S（CH2）nNHCO-N＝N-OCH2CH3（n＝2，3，4，6）．研究结果表明，仍氮苯到金电极的表现电子转移速率随它们之间的距离长度的增加而呈指数性的下降趋势．基于Marcus电子隧穿理论，得到了此自组装膜体系的长程电子隧穿系数ρ＝（1．35±0．2）／CH2在和可逆电活性分子自组装膜体系及理论计算相比较的基础上，从偶氮苯分子自组装膜结构与电子转移过程的关系角度对这一结果进行了分析和说明．     

Molecular dynamics and phase transitions in phospholipid monolayers at liquid-liquid interfaces

Stablen-hexadecane/water andn-tetradecane/water macroemulsions containing monolayers of natural (egg yolk lecithin, EY) and synthetic (dimyristoylphosphatidylcholine, DMPC) phospholipids at liquid-liquid interfaces were prepared. The existence of the monolayers was proved by studying the reduction kinetics of a surface-active spin probe with ascorbate anions. Spin labeled derivatives of stearic acid in which the nitroxide group is locared at different distances from the polar head (5-, 12-, and 16-doxylstearic acids) were used to study the temperature dependences of the molecular ordering, rotational mobility, and local polarity in the monolayers in emulsions and also in bilayers in liposomes obtained from the same lipids. In the EY monolayers, the degree of spin probe solubilization is higher, while the order parameters (S) and rotational correlation times (τ) are lower than those in EY bilayers. The differences between these parameters for mono- and bilayers increase with an increase in the distance of the reporter group from the aqueous phase. In the DMPC monolayers, a first-order phase transition was detected by measuring the temperature dependences ofS and τ. The temperature region of the phase transition in monolayers is shifted to lower temperatures with respect to that for bilayers and depends on the nature of the oil phase. It was concluded that the phospholipid monolayers in emulsions incorporate hydrocarbon molecules, whose concentration in the DMPC monolayers increases on going from the low-temperature (gel) to the high-temperature (liquid crystal) phase. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 418–425, March, 1998.     

Electrochemical Behavior of Epinephrine at a Penicillamine Self-Assembled Gold Electrode,and its Analytical Application

The fabrication and electrochemical characteristics of a penicillamine (PCA) self-assembled monolayer modified gold electrode were investigated. The self-assembled electrode shows obvious electrocatalytic activity for the oxidation of epinephrine (EP). In phosphate buffer (pH 7.73), a sensitive oxidation peak was observed at 0.190V with the PCA modified Au electrode. The peak current is proportional to the concentration of EP in the range of 2.0×10^–56.0×10^–4molL^–1 and 5.0×10^–6 2.0×10^–4molL^–1 for cyclic voltammetry (CV) and differential pulse voltammetry (DPV) with the detection limits of 1.8×10^–7 and 1.3×10^–7molL^–1, respectively. The possible reaction mechanism is also discussed. The PCA self-assembled monolayer modified gold electrode is highly stable and can be applied to the determination of EP in practical injection samples. Application is simple, rapid and produces accurate results.     

席夫碱自组装单分子膜的电化学行为

利用自组装技术将席夫碱硫醇衍生物在金表面形成自组装单分子膜,并初步研究了此自组装单分子膜的电化学行为,发现该席夫碱分子在0.1 mol•L－1的KCl溶液中具有电化学不可逆氧化还原行为，且随着自组装时间的增加表观电极反应速率常数值显著减小,最后减小为0,并对此进行了解释.     

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.     

Monolayer Rectifiers

Molecular-scale electronics has now been enriched by the discovery that molecules, studied singly by scanning tunneling spectroscopy, or a large array of those molecules, studied in parallel as a Langmuir-Blodgett monolayer between metal electrodes, exhibit rectification, i.e., an asymmetric current as a function of applied voltage.This asymmetry can come, first, from work function differences between two dissimilar metals or the metal-molecule interfaces (Schottky barriers), second from an asymmetric placement of the chromophore between the two metal electrodes, and third, from an asymmetry of the molecular orbitals of the molecule.This third, electronic origin of rectification, first proposed by Aviram and Ratner in 1974, and confirmed in the work reported here, gives us hope that, not too many years from now, molecules can form the basis of ultra-small yet ultra-fast electronic devices and integrated circuits.     

On the Structure and Formation of Self-Assembled Lattices of Gold Nanoparticles

The structure and ordering of nanoparticles of gold functionalized with n-alkyl thiol molecules are studied both experimentally and theoretically. Samples where produced using n=6 to n=16 alkyl thiol molecules. High Resolution Electron Microscopy coupled with image processing was used to study the gold particle structure. The details of the particle structure are discussed. We found that when the gold surface is saturated with thiol molecules there is some tendency to produce molecules with a disulphide structure. We also show that ordered arrays of particles can be produced using Langmuir-Blodgett techniques. The crystal structure of the films produced is studied and found to be 3D hcp. We also report that thiol covered gold particles with a size of 5 nm present a rounded shape suggesting that thiol molecules might induce an isotropic surface energy. It is found in the theoretical calculations that a strong bond between gold and sulphur is required to stabilize the complex metal-n-alkyl thiol. It is predicted that otherwise a heavily distorted nanocore will be formed. This is contrary to the observed structure of the particles.     

A peroxidase-tetrathiafulvalene biosensor based on self-assembled monolayer modified Au electrodes for the flow-injection determination of hydrogen peroxide

The construction and performance under flow-injection conditions of an integrated amperometric biosensor for hydrogen peroxide is reported. The design of the bioelectrode is based on a mercaptopropionic acid (MPA) self-assembled monolayer (SAM) modified gold disk electrode on which horseradish peroxidase (HRP, 24.3 U) was immobilized by cross-linking with glutaraldehyde together with the mediator tetrathiafulvalene (TTF, 1 μmol), which was entrapped in the three-dimensional aggregate formed.

The amperometric biosensor allows the obtention of reproducible flow injection amperometric responses at an applied potential of 0.00 V in 0.05 mol L⁻¹ phosphate buffer, pH 7.0 (flow rate: 1.40 mL min⁻¹, injection volume: 150 μL), with a range of linearity for hydrogen peroxide within the 2.0 × 10⁻⁷–1.0 × 10⁻⁴ mol L⁻¹ concentration range (slope: (2.33 ± 0.02) × 10⁻² A mol⁻¹ L, r = 0.999). A detection limit of 6.9 × 10⁻⁸ mol L⁻¹ was obtained together with a R.S.D. (n = 50) of 2.7% for a hydrogen peroxide concentration level of 5.0 × 10⁻⁵ mol L⁻¹. The immobilization method showed a good reproducibility with a R.S.D. of 5.3% for five different electrodes. Moreover, the useful lifetime of one single biosensor was estimated in 13 days.

The SAM-based biosensor was applied for the determination of hydrogen peroxide in rainwater and in a hair dye. The results obtained were validated by comparison with those obtained with a spectrophotometric reference method. In addition, the recovery of hydrogen peroxide in sterilised milk was tested.