Stanislav Miertus

Catalytic Applications in the Production of Biodiesel from Vegetable Oils

The predicted shortage of fossil fuels and related environmental concerns have recently attracted significant attention to scientific and technological issues concerning the conversion of biomass into fuels. First-generation biodiesel, obtained from vegetable oils and animal fats by transesterification, relies on commercial technology and rich scientific background, though continuous progress in this field offers opportunities for improvement. This review focuses on new catalytic systems for the transesterification of oils to the corresponding ethyl/methyl esters of fatty acids. It also addresses some innovative/emerging technologies for the production of biodiesel, such as the catalytic hydrocracking of vegetable oils to hydrocarbons. The special role of the catalyst as a key to efficient technology is outlined, together with the other important factors that affect the yield and quality of the product, including feedstock-related properties and various system conditions.

Next-Generation Biofuels: Survey of Emerging Technologies and Sustainability Issues

Next-generation biofuels, such as cellulosic bioethanol, biomethane from waste, synthetic biofuels obtained via gasification of biomass, biohydrogen, and others, are currently at the center of the attention of technologists and policy makers in search of the more sustainable biofuel of tomorrow. To set realistic targets for future biofuel options, it is important to assess their sustainability according to technical, economical, and environmental measures. With this aim, the review presents a comprehensive overview of the chemistry basis and of the technology related aspects of next generation biofuel production, as well as it addresses related economic issues and environmental implications. Opportunities and limits are discussed in terms of technical applicability of existing and emerging technology options to bio-waste feedstock, and further development forecasts are made based on the existing social-economic and market situation, feedstock potentials, and other global aspects. As the latter ones are concerned, the emphasis is placed on the opportunities and challenges of developing countries in adoption of this new industry.

A glucose/hydrogen peroxide biofuel cell that uses oxidase and peroxidase as catalysts by composite bulk-modified bioelectrodes based on a solid binding matrix.

An improved composite bulk-modified bioelectrode setup based on a solid binding matrix (SBM) has been used to develop a glucose/hydrogen peroxide biofuel cell. Fuel is combined through a catalytically promoted reaction with oxygen into and oxidized species and electricity. The present work explores the feasibility of a sugar-feed biofuel cell based on SBM technology. The biofuel cell that utilizes mediators as electron transporters from the glucose oxidation pathway of the enzyme directly to electrodes is considered in this work. The anode was a glucose oxidase (GOx, EC 1.1.3.4)/ferrocene-modified SBM/graphite composite electrode. The cathode was a horseradish peroxidase (HRP, EC 1.11.1.7)/ferrocene-modified SBM/graphite composite electrode. The composite transducer material was layered on a wide polymeric surface to obtain the biomodified electrodic elements, anodes and cathodes and were assembled into a biofuel cell using glucose and H(2)O(2) as the fuel substrate and the oxidizer. The electrochemical properties and the characteristics of single composite bioelectrodes are described. The open-circuit voltage of the cell was 0.22 V, and the power output of the cell was 0.15 microW/cm(2) at 0.021 V. The biofuel cell proved to be stable for an extended period of continuous work (30 days). The reproducibility of the biotransducers fabrication was also investigated. In addition, an application of presented biofuel cell, e.g. the use of hydrolyzed corn syrup as renewable biofuels, was discussed.

Amperometric biosensors based on solid binding matrices applied in food quality monitoring

Solid binding matrix (SBM) based composite transducers have been used for development of series of multibiosensor systems applicable in various fields. Here we present two hybrid three-channel multibiosensors for simultaneous amperometric operation in food quality control, i.e. glucose/fructose/ethanol multibiosensor, based on glucose oxidase/fructose dehydrogenase/alcohol dehydrogenase surface-modified enzyme electrodes and L-lactate/L-malate/sulfite multibiosensor, based on L-lactate dehydrogenase/L-malate dehydrogenase/sulfite oxidase surface-modified enzyme electrodes. Different parameters have been studied in order to optimize the response of the multibiosensor systems. The multibiosensor showed a good sensitivity, linear range and storage stability. The multibiosensors were used for the determination of glucose, fructose, ethanol, L-lactate, L-malate and sulfite in samples of wine, resulting in a good agreement with data certified by the supplier. Comparison of various designs, surface-modified, bulk-modified and thick-cover, of SBM based biosensors is studied on the example of fructose biosensor.

Composite Transducers for Amperometric Biosensors. The Glucose Sensor

A new concept of a composite transducer for amperometric biosensors based on the use of a solid substance with amphiphilic character (called a solid binding matrix, SBM) is presented. The electrochemical properties of the transducers prepared with five different SBMs and the characteristics and performance of SBM-based glucose sensors prepared by three different methods are described. Biosensor stability is evaluated and discussed. The biosensor was used for the determination of glucose in wine, yielding results which were consistent with those obtained with the commercially available Glucose Enzyme Photometric Kit. The average accuracy was 6% for the whole range of analyzed concentrations (0.2-47 g/L) using the same sample dilution in a buffer.

Structure-based design of inhibitors of NS3 serine protease of hepatitis C virus

We have designed small focused combinatorial library of hexapeptide inhibitors of NS3 serine protease of the hepatitis C virus (HCV) by structure-based molecular design complemented by combinatorial optimisation of the individual residues. Rational residue substitutions were guided by the structure and properties of the binding pockets of the enzymes active site. The inhibitors were derived from peptides known to inhibit the NS3 serine protease by using unusual amino acids and alpha-ketocysteine or difluoroaminobutyric acid, which are known to bind to the S1 pocket of the catalytic site. Inhibition constants (Ki) of the designed library of inhibitors were predicted from a QSAR model that correlated experimental Ki of known peptidic inhibitors of NS3 with the enthalpies of enzyme-inhibitor interaction computed via molecular mechanics and the solvent effect contribution to the binding affinity derived from the continuum model of solvation. The library of the optimised inhibitors contains promising drug candidates-water-soluble anionic hexapeptides with predicted Ki* in the picomolar range.

Renewable H2 from Glycerol Steam Reforming: Effect of La2O3 and CeO2 Addition to Pt/Al2O3 catalysts.

Glycerol is the main byproduct of biodiesel production and its increased production volume derives from the increasing demand for biofuels. The conversion of glycerol to hydrogen-rich mixtures presents an attractive route towards sustainable biodiesel production. Here we explored the use of Pt/Al(2)O(3)-based catalysts for the catalytic steam reforming of glycerol, evidencing the influence of La(2)O(3) and CeO(2) doping on the catalyst activity and selectivity. The addition of the latter metal oxides to a Pt/Al(2)O(3) catalyst is found to significantly improve the glycerol steam reforming, with high H(2) and CO(2) selectivities. A good catalytic stability is achieved for the Pt/La(2)O(3)/Al(2)O(3) system working at 350 degrees C, while the Pt/CeO(2)/Al(2)O(3) catalyst sharply deactivates after 20 h under similar conditions. Studies carried out on fresh and exhausted catalysts reveal that both systems maintain high surface areas and high Pt dispersions. Therefore, the observed catalyst deactivation can be attributed to coke deposition on the active sites throughout the catalytic process and only marginally to Pt nanoparticle sintering. This work suggests that an appropriate support composition is mandatory for preparing high-performance Pt-based catalysts for the sustainable conversion of glycerol into syngas.

HYBRID BIOSENSOR FOR THE DETERMINATION OF SUCROSE

Abstract Yeast cell walls of Saccharomyces cerevisiae as a source of invertase together with glucose oxidase were used for the construction of a hybrid sucrose sensor. The biocatalytic layer was prepared by co-immobilizing yeast cell walls and glucose oxidase on a nylon network via glutardialdehyde and was fixed to the Clark oxygen electrode. The mutarotation of α- to β-glucose was accelerated by phosphate ions instead of mutarotase. The influence of pH, temperature and optimum composition of the biocatalytic layer was tested. Test samples and real samples were examined and the results were compared with those obtained by means of a glucose electrode. The sensor is stable for more than 2 months and the linear range extends to 1.3 × 10 −3 mol l −1 .

Composite alcohol biosensors based on solid binding matrix

Abstract A group of solid compounds with amphiphilic character called solid binding matrices (SBMs), which present a new concept of solid composite transducer for amperometric biosensors, were used for construction of robust solid alcohol biosensors. The enzymes, alcohol dehydrogenase (ADH) and diaphorase (DP) were either placed on the surface of the SBM-based transducer containing NAD + or they were incorporated together with NAD + directly into the transducer. The use of various mediators (organic dyes, vitamin K 3 , hexacyanoferrate(III), ferrocene) and methods of biosensor construction were studied. The electrochemical properties and the characteristics of the composite ethanol biosensors are described. The electrode response was fast and reproductible. As the response to ethanol in the range 0·2–4·0 mM was not linear, the calibration curves were transformed (1/ Δi = f (1/ c )) to obtain the linear dependencies. The biosensors were used for the determination of ethanol in samples of wine, resulting in a good agreement with data determined by photometric measurements after distillation of the sample (average percentage accuracy was 2% for surface layer-modified and 2·5% for bulk-modified bioelectrodes). The surface-modified sensors remained stable for at least 3 months. The sensitivity of bulk-modified sensors decreased to 60–85% of the initial value after 1 month, but after electrode surface renewal about 90% of initial sensitivity was found.

Design of oseltamivir analogs inhibiting neuraminidase of avian influenza virus H5N1

Neuraminidase is an important target for design of antiviral agents in the prophylaxis and treatment of avian influenza virus infections. We have shown the applicability of computer-assisted combinatorial techniques in the design, focusing and in silico screening of a virtual library of analogs of oseltamivir (Tamiflu) with the goal to find potent inhibitors of influenza A neuraminidase N1 that fill the cavity found adjacent to the active site. Crystal structure of oseltamivir-N1 complex was used in the structure-based focusing and virtual screening of the designed library. A target-specific Piecewise Linear Potential type 1 scoring function fitted for a training set of 14 carbocyclic inhibitors and validated for three other inhibitors was used to select virtual hits with predicted inhibitory activities in the subnanomolar range. The results of this computational study are useful as a rational guide for synthetic and medicinal chemists who are developing new drugs against the avian influenza virus H5N1.