On the function and mechanism of action of peroxidases

Combustion control and sensors: a review

This review deals with gas sensors combining a metal oxide based sensing layer and a substrate realized by using micromachining. It starts by giving an overview of the design principles and technology involved in the fabrication of micromachined substrates examining thermal and mechanical aspects. Both kinds of micromachined substrates, closed-membrane-type and the suspended-membrane-type, are discussed. The deposition of the sensing layer is complicated by the mechanical fragility of the micromachined substrates. Different approaches used for the formation of the sensing layer such as thin film and thick film deposition techniques are reviewed. Finally, the gas sensing function of the sensitive layer is analyzed and various ways for extracting the information are presented with respect to the improvement of sensor performance brought by this new approach.

Micromachined metal oxide gas sensors: opportunities to improve sensor performance

As a result of the adaptation of life to an aerobic environment, nature has evolved a panoply of metalloproteins for oxidative metabolism and protection against reactive oxygen species. Despite the diverse structures and functions of these proteins, they share common mechanistic grounds. An open-shell transition metal like iron or copper is employed to interact with O2 and its derived intermediates such as hydrogen peroxide to afford a variety of metal–oxygen intermediates. These reactive intermediates, including metal-superoxo, -(hydro)peroxo, and high-valent metal–oxo species, are the basis for the various biological functions of O2-utilizing metalloproteins. Collectively, these processes are called oxygen activation. Much of our understanding of the reactivity of these reactive intermediates has come from the study of heme-containing proteins and related metalloporphyrin compounds. These studies not only have deepened our understanding of various functions of heme proteins, such as O2 storage and trans...

Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins

Infectious pancreatic necrosis virus of fish, infectious bursal disease virus of chickens, Tellina virus and oyster virus of bivalve molluscs, and drosophila X virus of Drosophila melanogaster are naked icosahedral viruses with an electron microscopic diameter of 58 to 60 nm. The genome of each of these viruses consists of two segments of double-stranded RNA (molecular weight range between 2.6 x 10(6) and 2.2 x 10(6), and the virion, capsid proteins fall into three size class categories (large, medium, and small; ranging from 100,000 to 27,000) as determined by polyacrylamide slab gel electrophoresis. The hydrodynamic properties of the five viruses are similar as determined by analytical ultracentrifugation and laser quasi-elastic, light-scattering spectroscopy. The calculated particle weights range between 55 x 10(6) and 81 x 10(6). Tryptic peptide comparisons of 125I-labeled virion proteins showed that five viruses are different from each other, although there was considerable overlap in the peptide maps of the three aquatic viruses, indicting a degree of relatedness. Cross-neutralization tests indicated that drosophila X, infectious pancreatic necrosis, and infectious bursal disease viruses were different from each other and from oyster and Tellina viruses. The same test showed oyster and Tellina viruses to be related. The biochemical and biophysical properties of the five viruses cannt be included in the family Reoviridae or in any of the present virus genera.

Biophysical and biochemical characterization of five animal viruses with bisegmented double-stranded RNA genomes.

The Valence and Spin State of Iron in Oxyhemoglobin as Inferred from Resonance Raman Spectroscopy

The first known broadband single-pulse coherent anti-Stokes Raman scattering (CARS) measurements within the cylinder of a firing internal combustion engine are reported. Postcombustion temperature and carbon monoxide concentration are probed with 1-mm(3) spatial resolution and 10-nsec temporal resolution. Space- and time-resolved measurements, as presented here, are shown to be necessary for the study of fluctuating systems such as engines.

Broadband single-pulse CARS spectra in a fired internal combustion engine

Raman spectra of dilute solutions of some steroisomers of vitamin A type molecules

We report 441.6 nm excitation resonance Raman spectra of oxidized and reduced monomeric heme a-imidazole, cytochrome oxidase-exogenous ligand complexes in various redox states, and alkaline denatured oxidase. These data show that, in reduced oxidase, the cytochrome a3 Raman spectrum has bands at 215, 364, 1230, and 1670 cm-1 not observed in the cytochrome a spectrum. The appearance of these bands in the reduced cytochrome a3 spectrum is due to interactions between the heme a of cytochrome a3 and its protein environment and not to intrinsic properties of heme a. These interactions are pH sensitive and strongly influence the vibrational spectra of both heme a groups. We assign the 1670-cm-1 band to the heme a formyl substituent and propose that the intensity of the 1670 cm-1 is high for reduced cytochrome a3 because the C==O lies in the porphyrin plane and is very weak for oxidized and reduced cytochrome a, oxidized cytochrome a3, and oxidized and reduced heme a-imidazole because the C==O lies out of the plane. We suggest that movement of the C==O in and out of the plane explains the ligand induced spectral shift in the optical absorption spectrum of reduced cytochrome a3. Finally, we confirm the observation of Adar & Yonetani (private communication) that, under laser illumination, resting oxidase is photoreactive.

Raman spectra of heme a, cytochrome oxidase-ligand complexes, and alkaline denatured oxidase.

A differential catalytic microcalorimeter has been fabricated using silicon micromachining techniques. The steady-state device response to different combustible gases was investigated in the laboratory as a function of concentration of the combustible species, oxygen level, and gas flow. The device output was found to be proportional to the concentration of the different combustible gases, while the relative sensitivity to different reactants depends on the specific catalyst used. This paper discusses the design issues and the fabrication process for maximizing the detection limit of the device.

Lajos Rimai

Papers

The Valence and Spin State of Iron in Oxyhemoglobin as Inferred from Resonance Raman Spectroscopy

Broadband single-pulse CARS spectra in a fired internal combustion engine

Raman spectra of dilute solutions of some steroisomers of vitamin A type molecules

Raman spectra of heme a, cytochrome oxidase-ligand complexes, and alkaline denatured oxidase.

Fabrication and properties of a Si-based high-sensitivity microcalorimetric gas sensor