Patents and literature

Protein engineering and site-directed mutagenesis is becoming immensely important in both fundamental studies and commercial applications involving proteins and enzymes in biocatalysis. Protein engineering has become a powerful tool to help biochemists and molecular enzymologists elucidate structure-function relationships in enzymic active sites, to understand the intricacies of protein folding and denaturation, and to alter the selectivity of enzymatic catalysis. Commercial applications of engineered enzymes are being developed to increase protein stability, widen or narrow substrate specificity, and to develop novel approaches for use of enzymes in organic synthesis, drug design, and clinical applications. In addition to protein engineering, novel expression systems have been designed to prepare large quantities of genetically engineered proteins. Recent US patents and scientific literature on protein engineering, site-directed mutagenesis, and protein expression systems related to protein engineering are surveyed. Patent abstracts are summarized individually and a list of literature references are given.     

Fundamentals of lead acid cells: Part IV. The reduction of porous PbO2 electrodes in sulphuric acid

The reduction behaviour of porous lead dioxide electrodes is shown to be independent of rotation speed in a large excess of 5 M H₂SO₄. The reduction peak is broadened by the porosity. This porosity broadening is interpreted in terms of the reaction being driven more deeply into the pore structure as the front of the electrode becomes progressively more ressstive. The effect of different potential sweep rates on the current response and the effects of progressive redox cycles can be fully explained on this model.     

Alysis of the volatile constituents of food by headspace GC-MS with reversal of the carrier gas flow during sampling

A technique has been developed for performing headspace GC-MS analysis of volatile components of food, in which the carrier gas flow is reversed during sampling in order to overcome problems caused by the diffusion of substances not retained by the cold trap. Chromatographic profiles of volatile compounds from cheeses, obtained at room temperature, provide confirmation of the validity of the reversed flow technique, and the versatility of the system is evidenced by its successful application to both solid and liquid matrixes: the absence of any discrimination against the various components reveals its efficacy for compounds with a wide range of volatility. Addition of internal standards to the sample enables the use of the technique for quantitative analysis.     

A new family of heavy transition metal coordination compounds and its application,I. Design,synthesis and characterization of volatile organohafnium precursors

The first three representatives of a new family of volatile organohafnium compounds suitable as metallo-organic chemical vapour deposition precursors were synthesized. A combination of cyclopentadienyl and alkoxo-ligands with a bicyclo[2.2.1]heptanc framework was used. Volatility at relatively low temperatures for hafnium compounds was found and the precursors were characterized by elemental analysis and spectroscopic methods (IR, ¹H and ¹³C NMR, mass spectrometry and mass-analysed ion kinetic energy spectroscopy). The outlook for use in hafnium functional materials synthesis was derived from the fragmentation data.     

Nucleation of bulk phases in the HCl/H2O system

We report experimental results on the low-temperature uptake of HCl on H(2)O ice (ice). HCl was deposited on the surface at greater than monolayer amounts at 85 K, and the ice substrate was heated. The temperature dependence of the HCl vapor pressure from this phase was measured from 110 to 150 K, with the nucleation of a bulk hydrate phase observed at 150 K. Measurements were conducted in a closed system by simultaneous application of gas phase mass spectrometry and surface spectroscopy to characterize vapor/solid equilibrium and the nucleation of bulk hydrate phases. Combining the nucleation data reported here with data we reported previously (180 to 200 K) and data from two other laboratories (165 and 170 K), the thermodynamic boundaries for the nucleation of both the metastable bulk solution and bulk hydrate phases subsequent to monolayer adsorption of HCl have been determined. The nucleation of the metastable bulk solution phase occurs promptly at monolayer coverage at the ice/liquid coexistence boundary on the binary bulk phase diagram. The nucleation of the bulk hexahydrate occurs from this metastable solution along a locus of points defining a state of constant solution free energy. This measured free energy is -51.2 +/- 0.9 kJ/mol. Finally, the temperature dependence of the HCl vapor pressure from the low-temperature phase is reported here for the first time and is consistent with that of the metastable solution predicted by this thermodynamic model of uptake, extending the range of validity of this model of adsorption followed by bulk solution and hydrate nucleation to a lower bound in temperature of 110 K.     

Facile high-yield synthesis of pure, crystalline Mg(BH4)2

Magnesium borohydride, Mg(BH4)2, a long-sought candidate for efficient hydrogen storage chemisorption technology, has been obtained in a pure and crystalline form by two new synthetic routes in a hydrocarbon solvent. A first synthetic approach involves a metathetical reaction between organometallic magnesium compounds; a second route consists of an insertion reaction of BH3 species, released from BH3.S(CH3)2, into the Mg-C bonds of MgR2, with complete replacement of R groups with BH4 groups. Both methods, based on commercially available reagents, afford identical, pure, polycrystalline materials, identified by X-ray diffraction as the so-called low-temperature hexagonal form of Mg(BH4)2, stable below 180 degrees C, recently shown to possess a complex, unpredictable, crystal structure.     

Risk Analysis in Transport and Storage of Monomers: An Accident Investigation

Summary: In this work the analysis of an accident in transport of dangerous goods is proposed. The objective of this study is to contribute to the determination of the causes that brought about the self-polymerization of commercial divinylbenzene (DVB 63%) contained in an iso-container, in order to prevent this accident to happen in the future. Time and conditions during transport and storage of monomers (in particular the storage temperature) are very important factors, that affect the self-polymerization aptitude of these substances. To stabilize this monomer, usually 4-tert-Butylcatechol (TBC) is added at a level of 900–1200 ppm by weight to act as an inhibitor to prevent the self-initiated autopolymerization of the material. In particular one hypothesis has been investigated: probably the quantity of oxygen in the tanker was insufficient to activate properly the inhibition mechanism of TBC. From this consideration the self-polymerization of DVB and the inhibition mechanism of TBC have been studied as a function of temperature and monomer exposure to air. Different calorimetric techniques have been applied, in particular Differential Scanning Calorimetry and Adiabatic Calorimetry, to investigate the causes of the accident.