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In this paper, the deposition and characterization of plasma-polymerized polystyrene (pp-PS) using PECVD under atmospheric pressure on a variety of substrates was investigated. An atmospheric RF plasma torch and an HF dielectric-barrier-discharge (DBD) system were used to deposit thin pp-PS coatings on PTFE, HDPE, stainless steel, glass, and silicon wafer. The styrene vapor was carried by Ar or He. The pp-PS films were characterized by Fourier transform infrared spectroscopy (FTIR) (infrared reflection absorption spectroscopy), X-ray photoelectron spectroscopy (XPS), water contact angle (WCA), static secondary ion mass spectroscopy (SSIMS), and optical microscopy, and the plasma phase was studied by optical-emission spectroscopy. The major features that characterize PS are present in the FTIR, SSIMS, and XPS spectra of our films, although some differences are observed between pp-PS and their conventionally polymerized counterparts: oxygenation, branching, degree of cross-linking, and unsaturation. According to the WCA and XPS results, the films deposited by the RF plasma torch (placed in a Plexiglass chamber) are more oxygenated than those deposited by DBD, which is operated under a much more controlled atmosphere. A comparison of the chemical structure of the deposited coatings (branching, cross-linking) as a function of the nature of the carrier gas was established by FTIR: pp-PS synthesized in the presence of Ar (for both processes) exhibit more branching and a higher degree of cross-linking than pp-PS synthesized with He as the main plasma gas. The optical microscopy points out a diversity of structures that depend on the nature of the substrate and the plasma parameters. Index Terms--Plasma CVD, plasma materials-processing applications, plasmas, plastics.

Chronoamperometric experiments with adsorbed electrocatalysts are commonly performed either for analytical purposes or for studying the catalytic mechanism of a redox enzyme. In the context of amperometric sensors, the current may be recorded as a function of time while the analyte concentration is being increased to determine a linearity range. In mechanistic studies of redox enzymes, chronoamperometry proved powerful for untangling the effects of electrode potential and time, which are convoluted in cyclic voltammetric measurements, and for studying the energetics and kinetics of inhibition. In all such experiments, the fact that the catalyst's coverage and/or activity decreases over time distorts the data. This may hide meaningful features, introduce systematic errors, and limit the accuracy of the measurements. We propose a general and surprisingly simple method for correcting for electrocatalyst desorption and inactivation, which greatly increases the precision of chronoamperometric experiments. Rather than subtracting a baseline, this consists in dividing the current, either by a synthetic signal that is proportional to the instant electroactive coverage or by the signal recorded in a control experiment. In the latter, the change in current may result from film loss only or from film loss plus catalyst inactivation. We describe the different strategies for obtaining the control signal by analyzing various data recorded with adsorbed redox enzymes: nitrate reductase, NiFe hydrogenase, and FeFe hydrogenase. In each case we discuss the trustfulness and the benefit of the correction. This method also applies to experiments where electron transfer is mediated, rather than direct, providing the current is proportional to the time-dependent concentration of catalyst.

A model alkane molecule, triacontane, is used to assess the effects of condensed gold and silver nanoparticles on the molecular ion yields upon atomic ([Ga.sup.+] and [In.sup.+]) and polyatomic ([C.sub.60.sup.+] and [Bi.sub.3.sup.+]) ion bombardment in metalassisted secondary ion mass spectrometry (MetA-SIMS). Molecular films spin-coated on silicon were metallized using a sputter-coater system, in order to deposit controlled quantities of gold and silver on the surface (from 0 to 15 nm equivalent thickness). The effects of gold and silver islets condensed on triacontane are also compared to the situation of thin triacontane overlayers on metallic substrates (gold and silver). The results focus primarily on the measured yields of quasi-molecular ions, such as [(M - H).sup.+] and [(2M - 2H).sup.+], and metal-eationized molecules, such as [(M + Au).sup.+] and [(M + Ag).sup.+], as a function of the quantity of metal on the surface. They confirm the absence of a simple rule to explain the secondary ion yield improvement in MetA-SIMS. The behavior is strongly dependent on the specific projectile/metal couple used for the experiment. Under atomic bombardment ([Ga.sup.+], [In.sup.+]), the characteristic ion yields an increase with the gold dose up to ~6 nm equivalent thickness. The yield enhancement factor between gold-metaUized and pristine samples can be as large as ~70 (for [(M - H).sup.+] under [Ga.sup.+] bombardment; 10 nm of Au). In contrast, with cluster projectiles such as [Bi.sub.3.sup.+] and [C.sub.60.sup.+], the presence of gold and silver leads to a dramatic molecular ion yield decrease. Cluster projectiles prove to be beneficial for triacontane overlayers spin-coated on silicon or metal substrates (Au, Ag) but not in the situation of MetA-SIMS. The fundamental difference of behavior between atomic and cluster primary ions is tentatively explained by arguments involving the different energy deposition mechanisms of these projectiles. Our results also show that Au and Ag nanoparticles do not induce the same behavior in MetA-SIMS of triacontane. The microstructures of the metallized layers are also different. While metallic substrates provide higher yields than metal islet overlayers in the case of silver, whatever the projectile used, the situation is reversed with gold.

Quinol/nitrate oxidoreductase (NarGHI) complex in Escherichia coli is known to operate with ubi and menaquinones however the location and the number of quinol binding sites remain indefinable. So a study is conducted to identify its location and function using a combination of mutagenesis, kinetics, EPR and ENDOR spectroscopies.

We show the theoretical and experimental combination of acoustic and optical methods for the in situ quantitative evaluation of the density, the viscosity, and the thickness of soft layers adsorbed on chemically tailored metal surfaces. For the highest sensitivity and an operation in liquids, a Love mode surface acoustic wave (SAW) sensor with a hydrophobized gold-coated sensing area is the acoustic method, while surface plasmon resonance (SPR) on the same gold surface as the optical method is monitored simultaneously in a single setup for the real-time and label-free measurement of the parameters of adsorbed soft layers, which means for layers with a predominant viscous behavior. A general mathematical modeling in equivalent viscoelastic transmission lines is presented to determine the correlation between experimental SAW signal shifts and the wavegnide structure including the presence of the adsorbed layer and the supporting liquid from which it segregates. A methodology is presented to identify from SAW and SPR simulations the parameters representatives of the soft layer. During the absorption of a soft layer, thickness or viscosity changes are observed in the experimental ratio of the SAW signal attenuation to the SAW signal phase and are correlated with the theoretical model. As application example, the simulation method is applied to study the thermal behavior of physisorbed PNIPAAm, a polymer whose conformation is sensitive to temperature, under a cycling variation of temperature between 20 and 40[degrees]C. Under the assumption of the bulk density and the bulk refractive index of PNIPAAm, thickness and viscosity of the film are obtained from simulations; the viscosity is correlated to the solvent content of the physisorbed layer.

An attempt is made to study the function of the histidine that ligates the distal [4Fe4S] cluster in Df NiFe hydrogenase (H184), and so, it was exchanged for a cysteine or a glycine. The results suggest that the short distance between FeS clusters in biological redox chains might not always be sufficient to allow rapid intramolecular electron transfer (ET).

Protein film voltammetry is used to study NiFe hydrogenase from desulfovibrio fructosovorans. This experimental approach could be used to study the reaction of other multicentered metalloenzymes with their gaseous substrates or inhibitors.

Research has been conducted on the xanthine oxidase family molybdoenzymes that contain two clusters. The X-ray crystal structure of the clusters has been investigated.