Interfacial characteristics of the self-assembly system of poly-L-lysine 3-mercaptopropionic acid gold electrode

The interfacial characteristics of poly-L-lysine (PL) attached on self-assembled monolayers (SAMs) of 3-mercaptopropionic acid (MPA) were studied by an electrochemical method. The results indicated that PL\MPA layer inhibited partly the diffusion process of redox species in solution, and the electrode surface behaved like a microelectrode array. Its permeation effect was also strongly affected by Mg2+. The more Mg2+ ions were added into the electrolyte solution, the greater the difficulty with which the electron transfer of potassium ferricyanide took place. The three different conformations of PL on the electrode surface had different influences on the electron transfer processes of ferricyanide. PL in random coil state hindered most strongly the electron transfer behavior of ferricyanide,while the alpha-helical PL had nearly no effect and the effect of the beta-sheet state PL was intermediate of these. (C) 1997 Elsevier Science S.A.

Electrochemical study of interactions between DNA and viologen-thiol self-assembled monolayers

We investigated the binding characteristics of double-stranded DNA to self-assembled monolayers (SAMs) containing viologen groups formed on the surface of gold electrodes via Au-S bonds. The positive charged and hydrophobic surfaces of the viologen SAMs modified gold electrodes are suitable to bind strongly dth DNA, whose interactions to solution DNA and adsorbed DNA both lead to positive shifts (22.5 mV and 65 mV, respectively) in the first redox potential ci viologen centers, indicating that the main interaction is from a hydrophobic interaction. Meanwhile, the binding of DNA strongly affects the kinetics of electron transfer of the viologen group so that the separation of anodic and cathodic peak potentials becomes larger and the heterogeneous electron transfer constant becomes smaller.

Self-assembled monolayers of thiols on gold electrodes for bioelectrochemistry and biosensors

Monolayers of biological compounds including redox proteins and enzymes, and phospholipids have been immobilized on a gold electrode surface through self-assembling. These proteins and enzymes, such as cytochrome c, cytochrome c oxidase and horseradish peroxidase (HRP), immobilized covalently to the self-assembled monolayers (SAMs) of 3-mercaptopropionic acid on a gold electrode, communicate directly electrons with the electrode surface without mediators and keep their physiological activities. The electron transfer of HRP with the gold electrode can also be mediated by the alkanethiol SAMs with electroactive group viologens on the gold electrode surface. All these direct electrochemistries of proteins and enzymes might offer an opportunity to build a third generation of biosensors without mediators for analytes, such as H2O2, glucose and cholesterol. Monensin and valinomycin have been incorporated into the bilayers on the gold electrode consisting of the SAMs of alkanethiol and a lipid monolayer, which have high selectivity for monovalent ions, and the resulting Na+ or K+ sensor has a wide linear range and high stability. These self-assembly systems provide a good mimetic model for studying the physiological function of a membrane and its associated enzyme. (C) 1997 Elsevier Science S.A.

The crystal structure and drawing-induced polymorphism in poly(aryl ether ketone)s .2. Poly(ether ether ketone ketone), PEEKK

The crystal structure, morphology and polymorphism induced by uniaxial drawing of poly(ether ether ketone ketone) [PEEKK] have been studied by transmission electron microscopy (TEM), electron diffraction (ED) and wide angle X-ray diffraction (WAXD). On the basis of WAXD and ED patterns,the crystal structure of unoriented PEEKK is determined to have two-chain orthorhombic packing with unit cell parameters of a 0.772 nm, b = 0.600 nm, c = 1.004 nm (form I), A stress-induced crystal modification (form II) is identified and found to possess a two-chain orthorhombic lattice with unit cell dimensions of a = 0.461 nm, b = 1.074 nm, c = 1.080 nm. The 7.5% increase in c-axis dimension for form II is attributed to an overextended chain conformation, arising from extensional deformation during uniaxial drawing and fixed ''in-situ'' through strain-induced crystallization. The average ether-ketone bridge bond angles in form II crystal are determined to be 148.9 degrees by using standard bond lengths. The crystal morphology of PEEKK bears a great similarity to that of PEEK. The crystals grow in the form of spherulites and have the b-axis of unit cell radial. The effects of draw rate on strain-induced crystallization and induction of form II structure are also discussed.

Electrochemical study of the interfacial characteristics of redox-active viologen thiol self-assembled monolayers

The electrochemical behavior of the electroactive self-assembled monolayers (SAMs) of thiol-functionalized viologen, CH3(CH2)(9)V2+(CH2)(8)SH, where V2+ is a viologen group, on the gold electrodes is examined by cyclic voltammetry and electrochemical a.c. impedance. A monolayer of viologen is immobilized on the gold electrode surface via the Au-S bond and the normal potentials corresponding to the two successive one-electron transfer processes of the viologen active centers are -310 mV and -652 mV (vs. Ag/AgCl) in 0.1 mol l(-1) phosphate buffer solution (pH 6.96) respectively. These results suggest that the viologen SAMs are stable and well-behaved monolayers. The experimental impedance data corresponding to different forms of viologen group have been fitted to equivalent electrical circuits, and the surface capacitances and resistances have been given. The heterogenous electron transfer rates of the first and the second redox processes are 7.57 s(-1) and 1.49 s(-1) respectively through a.c. impedance.

Viologen-thiol self-assembled monolayers for immobilized horseradish peroxidase at gold electrode surface

A stable, well-behaved self-assembled monolayer (SAM) of viologen-functionalized thiol was used to immobilize and electrically connect horseradish peroxidase (HRP) at gold electrode. Viologen groups in SAMs facilitated the electron transfer from the electrode to the protein active site so that HRP exhibited a quasi-reversible redox behavior. HRP adsorbed in the SAMs is very stable, and close to a monolayer with the surface coverage of 6.5 x 10(-11) mol/cm(2). The normal potential of HRP is -580 mV vs Ag/AgCl corresponding to ferri/ferro active center and the standard electron transfer rate constant is 3.41 s(-1) in 0.1 M phosphate buffer solution (pH 7.1). This approach shows a great promise for designing enzyme electrodes with other redox proteins and practical use in tailoring a variety of amperometric biosensor devices. Copyright (C) 1997 Elsevier Science Ltd.

The crystal structure and drawing-induced polymorphism in poly(aryl ether ketone)s .1. Poly(oxybiphenyl-4-4'-diyloxy-1,4-phenylenecarbonyl-1,3-phenylenecarbonyl-1,4-phenylene)

Crystal structure and polymorphism induced by uniaxial drawing of a poly(aryl ether ketone) [PEDEKmK] prepared from 1,3-bis(4-fluorobenzoyl)benzene and biphenyl-4,4'-diol have been investigated by means of transmission electron microscopy (TEM), electron diffraction (ED), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC) techniques. The melting and recrystallization process in the temperature range of 250-260 degrees C, far below the next melting temperature (306 degrees C), was identified and found to be responsible for the remarkable changes in lamellar morphology. Based on WAXD and ED patterns, it was found that crystal structure of isotropic-crystalline PEDEKmK obtained under different crystallization conditions (melt-crystallization, cold-crystallization, solvent-induced crystallization, melting-recrystallization, and crystallization from solution) keeps the same mode of packing, i.e., a two-chain orthorhombic unit cell with the dimensions a = 0.784 nm, b = 0.600 nm, and c = 4.745 nm (form I). A second crystal modification (form II) can be induced by uniaxial drawing above the glass transition temperature, and always coexists with form I. This form also possesses an orthorhombic unit cell but with different dimensions, i.e., a = 0.470 nm, b = 1.054 nm, c = 5.064 nm. The 0.32 nm longer c-axis of form II as compared with form I is attributed to an overextended chain conformation due to the expansion of ether and ketone bridge bond angles during uniaxial drawing. The temperature dependence of WAXD patterns for the drawn PEDEKmK suggests that form II can be transformed into the more stable form I by relaxation of overextended chains and relief of internal stress at elevated temperature in absence of external tension.

Dynamic spectroelectrochemical measurement for the conformational transition of cytochrome c induced by bromopyrogal red

The conformational transition of horse heart cytochrome c induced by bromopyrogal red (BPR) in very low concentration has been firstly investigated by dynamic spectroelectrochemical technique, both at the BPR adsorbed platinum gauze electrode and at a bare platinum gauze electrode in a solution containing BPR. The effect of BPR on the structure of cytochrome c was studied by UV-visible and Fourier transform IR spectroscopy. The unfolded cytochrome c behaves simply as an electron transfer protein with a formal potential of -142 mV vs. a normal hydrogen electrode. The difference between the formal potentials of the native and unfolded cytochrome c is coupled to a difference in conformational energy of the two states of about 40 kJ mol(-1), which agrees well with the result reported. The stability and slow refolding of the unfolded cytochrome c are discussed.

Ac voltammetric and square wave voltammetric study of the self-assembled monolayers of thiol-functionalized viologen derivative

Electroactive self-assembled monolayers (SAMs) containing viologen group are formed through the adsorption of thiol-functionalized viologen compound CH3(CH2)(9)V2+(CH2)(8)SH, where V2+ is N,N'-dialkylbipyridinium (i.e. a viologen group), onto gold electrodes from methanol/water solution and its electrochemical behavior is investigated ty Ac voltammetry and square wave voltammetry, which have the high sensitivity against background charging. The viologen SAM formed is a sub-monolayer and the normal potentials corresponding to the two successive one-electron transfer processes of the active centers (viologen) are -360 mV and -750 mV (vs. Ag/AgCl) in 0.1 mol/L phosphate buffer solutions (pH 6.96) respectively, and the standard electron transfer rate constant is 9.0 s(-1). The electrochemical behavior of this SAM in various solutions has been preliminarily discussed.

PLASMA-INDUCED GRAFTING OF STYRENE ONTO NASCENT POLYETHYLENE POWDER

In this paper, the graft copolymers of styrene to nascent linear polyethylene reactor powders were prepared through plasma graft polymerization. The grafting reaction was initiated by the alkyl radicals formed on the surface of nascent polyethylene with plasma treatment as indicated by electron spin resonance spectra. In graft copolymerization by alkyl radicals, the grafting yield increased with either the plasma power or the plasma treatment lime. Compared with ordinary polyethylene powders, nascent polyethylene reactor powders were found to be more easily plasma-grafted. This has been attributed to the greater sensitivity to irradiation in producing reactive centres under the same conditions. High density polyethylene showed almost the same grafting yield as linear low density polyethylene at 50 degrees C. The surface morphology of nascent polyethylene observed by scanning electron microscope before and after the grafting showed that the silk-like fibrils were not destroyed by plasma treatment.

GAMMA-RADIATION INDUCED CROSS-LINKED PEO-LICLO4 SOLID-ELECTROLYTE SYSTEM

Aimed at raising the room temperature ionic conductivity of PEO-based solid polymer electrolyte and considered that the ionic conduction preferentially occurs in the amorphous phase, we lightly crosslinked the high MW PEO through gamma-irradiation and further suppressed the residual crystallinity by plasticizing with propylene carbonate. By incorporating LiClO4 salt to the above described polymer host, the ambient (25 degrees C) ionic conductivity of the electrolyte system could reach as high as 6.8 X 10(-4) S/cm. As the electrolyte was a crosslinked system, it was mechanically self-supportable. Based on the preliminary results of the electrochemical performance of the secondary lithium battery, assembled by using this kind of solid electrolyte and polyaniline as positive electrode, it is realized that the electrolyte thus prepared is of high expectancy.

REEVALUATION OF 2,2-BIPYRIDINE AND PYRAZINE AS PROMOTERS FOR DIRECT ELECTRON-TRANSFER BETWEEN CYTOCHROME-C AND METAL-ELECTRODES

Results from previous electrochemical studies have indicated that 2,2'-bipyridine and pyrazine do not function as promoters for heterogeneous electron transfer between cytochrome c and metal electrodes. Their lack of activity was attributed to the improper positioning of the two functional groups in 2,2'-bipyridine and the inefficient length of pyrazine. In the present study it was determined that both 2,2'-bipyridine and pyrazine act as promoters when self-absorbed over a sufficiently long dipping time or at roughened electrodes. The promoter characteristics of these two molecules were studied and compared with those of 4,4'-bipyridine. The difference in their promoter behavior appears to result primarily from their different strengths of adsorption and not because electrodes modified with 2,2'-bipyridine or pyrazine are unsuitable for accelerating direct electron transfer reactions in cytochrome c. These results have implications regarding the mechanism(s) of promoter effects in electrochemical reactions of cytochrome c.

A mechanistic model of algal photoinhibition induced by photodamage to Photosystem-II

Photoinhibition is a central problem for the understanding of plasticity in photosynthesis vs. irradiance response. It effectively reduces the photosynthetic rate. In this contribution, we present a mechanistic model of algal photoinhibition induced by photodamage to photosystem-II. Photosystem-IIs (PSIIs) are assumed to exist in three states: open, closed and inhibited. Photosynthesis is closely associated with the transitions between the three states. The present model is defined by four parameters: effective cross section of PSII, number of PSIIs, turnover time of electron transfer chains and the ratio of rate constant of damage to that of repair of D1 proteins in PSIIs. It gives a photosynthetic response curve of phytoplankton to irradiance (PI-curve). Without photoinhibition, the PI-curve is in hyperbola with the first three parameters. The PI-curve with photoinhibition can be simplified to the same form as the hyperbola by replacing either the number of PSIIs with the number of functional PSIIs or the turnover time of electron transfer chains with the average turnover time.

Covariance analysis of the Coulomb explosion of ammonia induced by intense nanosecond laser at 532 nm

The Coulomb explosion of ammonia clusters induced by nanosecond laser at 532 not with an intensity of similar to 10(12) Wcm(-2) has been studied by time of flight mass spectrometry. The dominant multiply charged ions are N3+ and N2+ with kinetic energies of 110 and 50 eV respectively. The electrons generated from the multiphoton ionization are heated through inverse bremsstrahlung by the laser field when colliding with neutral or ionic particles. When their energies surpass the corresponding ionization potentials of the molecules or ions, the subsequent electron impact ionization may take place thus resulting in multi-charged nitrogen ions. Covariance analysis is made to study the possible pathways of the Coulomb explosion.