Methanol synthesis from CO2-H2 and from CO-H2 under atmospheric pressure over Pd and Cu catalysts

Under atmospheric pressure, methanol was produced from CO₂–H₂ over Pd/ZnO and from CO–H₂ over Pd/MgO catalyst. Similar support effects were observed over Cu catalysts.     

Automatic semi-microcolumn liquid chromatographic determination of catecholamines in rat plasma utilizing peroxyoxalate chemiluminescence reaction

A fully automated and highly sensitive method with a semi-microcolumn liquid chromatography system for the determination of rat plasma catecholamines (CAs) was developed. Automated on-line extraction of CAs in diluted plasma using a precolumn packed with strong acidic cation exchange resin was coupled with separation of CAs on a semi-microcolumn (250 x 1.5 mm id). fluorogenic derivatization with ethylenediamine and finally postcolumn peroxyoxalate chemiluminescence detection utilizing bis[2-(3,6,9-trioxadecanyloxycarbonyl)-4-nitrophenyl]oxalate (TDPO) and hydrogen peroxide. The detection limits were 0.91, 0.36 and 1.1 fmol for norepinephrine (noradrenaline), epinephrine (adrenaline) and dopamine, respectively, at a signal-to-noise ratio of 3. A good linearity of the calibration curve for each CA was observed in the range of 5.0 to 500 fmol for each CA using N-methyldopamine (N-MeDA) as an internal standard. The RSD for the proposed method (n = 5) were 3.7-9.5% for the intra-day assay and 6.6-10.0% for the inter-day assay. The volume of rat plasma required for the determination of CAs was 10 microliters.     

Catalytic reduction of nitrogen dioxide with propene in the presence and absence of oxygen over various metal oxides

Over metal oxides (SiO₂, ZrO₂, Al₂O₃, MgO, La₂O₃, and CaO) with-H values of metal oxide formation higher than 700 kJ/mol, C₃H₆ reacts with NO₂ in preference to O₂.     

How effective for fold recognition is a potential of mean force that includes relative orientations between contacting residues in proteins?

We estimate the statistical distribution of relative orientations between contacting residues from a database of protein structures and evaluate the potential of mean force for relative orientations between contacting residues. Polar angles and Euler angles are used to specify two degrees of directional freedom and three degrees of rotational freedom for the orientation of one residue relative to another in contacting residues, respectively. A local coordinate system affixed to each residue based only on main chain atoms is defined for fold recognition. The number of contacting residue pairs in the database will severely limit the resolution of the statistical distribution of relative orientations, if it is estimated by dividing space into cells and counting samples observed in each cell. To overcome such problems and to evaluate the fully anisotropic distributions of relative orientations as a function of polar and Euler angles, we choose a method in which the observed distribution is represented as a sum of delta functions each of which represents the observed orientation of a contacting residue, and is evaluated as a series expansion of spherical harmonics functions. The sample size limits the frequencies of modes whose expansion coefficients can be reliably estimated. High frequency modes are statistically less reliable than low frequency modes. Each expansion coefficient is separately corrected for the sample size according to suggestions from a Bayesian statistical analysis. As a result, many expansion terms can be utilized to evaluate orientational distributions. Also, unlike other orientational potentials, the uniform distribution is used for a reference distribution in evaluating a potential of mean force for each type of contacting residue pair from its orientational distribution, so that residue-residue orientations can be fully evaluated. It is shown by using decoy sets that the discrimination power of the orientational potential in fold recognition increases by taking account of the Euler angle dependencies and becomes comparable to that of a simple contact potential, and that the total energy potential taken as a simple sum of contact, orientation, and (phi,psi) potentials performs well to identify the native folds.     

Determination of the sulfur components of gasoline streams by capillary column gas chromatography with sulfur chemiluminescence detection

A method using a sulfur chemiluminescence detector (SCD) has been developed for the qualitative and quantitative determination of sulfur components in stabilized gasoline-range process streams, including blended gasolines containing between 1 and > 4000 ppm total sulfur. The detection limit per sulfur component was approximately 50 ppb. On-column injection was employed for optimum precision and accuracy. A new probe material was found which did not soften under FID operating conditions. A new method, using a hydrogen sulfide permeation tube, was developed for rapid alignment of the probe in the FID.     

Speciation of sulfur-containing compounds in diesel by comprehensive two-dimensional gas chromatography

Sulfur-containing compounds in diesel have been speciated by comprehensive two-dimensional gas chromatography (GCxGC) with a sulfur chemiluminescence detector (SCD). The advantages of GCxGC technique are higher resolution and greater sensitivity. GCxGC-SCD can achieve the class separation of sulfur-containing compounds with an appropriate separation column combination. The major classes of sulfur-containing compounds in diesel are benzothiophenes and dibenzothiophenes. Relative concentration of each class as well as each carbon number family can be quantitated by the summation of the integrated areas corresponding to the individual group(s) in the GCxGC space. In practical applications, GCxGC-SCD can be used to characterize different diesels and to reflect desulfurization process efficiency. In this study, GCxGC-SCD has demonstrated its value in speciation of sulfur-containing compounds classes, which is difficult to accomplish by any other single technique.     

The reaction between nitrous oxide and carbon monoxide over magnesium oxide

The title reaction was carried out with the help of the transient response method over MgO. It was concluded that no catalyst reduction occurred over this catalyst and the reaction proceeded through the reaction between adsorbed nitrous oxide and adsorbed carbon monoxide without participation of MgO oxygen.

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A method for the measurement of catechol-O-methyltransferase activity using norepinephrine, an endogenous substrate

We propose a highly sensitive method for the measurement of catechol-O-methyltransferase (COMT) activity with norepinephrine (NE), an endogenous native substrate. The product, normetanephrine, was determined by high-performance liquid chromatography (HPLC)-peroxyoxalate chemiluminescence reaction detection or, if required, less sensitive fluorescence detection. For the measurement of membrane-bound (MB)-COMT activity in the rat erythrocyte, the HPLC-peroxyoxalate chemiluminescence reaction detection was employed. Soluble (S)- and MB-COMT activities in the rat erythrocyte were 22.9 +/- 2.5 and 4.62 +/- 1.23 pmol min-1 (mg protein)-1, respectively (n = 5). The Km values obtained for S- and MB-COMT were 366 +/- 31 mumol l-1 and 12.0 +/- 1.1 mumol l-1, respectively (n = 5), suggesting that the use of NE as a substrate would give more precise information on the role of both isoenzymes. However, with dihydroxybenzoic acid as an artificial substrate, the Km values for S- and MB-COMT were similar, with values of 69.2 +/- 11.4 mumol l-1 and 72.2 +/- 9.2 mumol l-1, respectively. The proposed method is thought to be useful for the measurement of both S-COMT and MB-COMT activities, and would give us critical information on the role of metabolism of catecholamines in rat tissues.     

Effects of the Calcination and Reduction Conditions on a Cu/ZnO Methanol Synthesis Catalyst

The CuO crystallite size of the catalysts obtained from aurichalcite greatly depends on the heating rate of calcination for highly active and selective Cu/ZnO catalyst was prepared by reduction with methanol at 443 K for 17 h.