The Biocatalytic Potential of Aromatic Ammonia-Lyase from Loktanella atrilutea.

Characterization of the aromatic ammonia-lyase from Loktanella atrilutea (LaAAL) revealed reduced activity towards canonical AAL substrates: l-Phe, l-Tyr, and l-His, contrasted by its pronounced efficiency towards 3,4-dimethoxy-l-phenylalanine. Assessing the optimal conditions, LaAAL exhibited maximal activity at pH 9.5 in the ammonia elimination reaction route, distinct from the typical pH ranges of most PALs and TALs. Within the exploration of the ammonia source for the opposite, synthetically valuable ammonia addition reaction, the stability of LaAAL exhibited a positive correlation with the ammonia concentration, with the highest stability in 4 M ammonium carbamate of unadjusted pH of ~9.5. While the enzyme activity increased with rising temperatures yet, the highest operational stability and highest stationary conversions of LaAAL were observed at 30 °C. The substrate scope analysis highlighted the catalytic adaptability of LaAAL in the hydroamination of diverse cinnamic acids, especially of meta-substituted and di-/multi-substituted analogues, with structural modelling exposing steric clashes between the substrates' ortho-substituents and catalytic site residues. LaAAL showed a predilection for ammonia elimination, while classifying as a tyrosine ammonia-lyase (TAL) among the natural AAL classes. However, its distinctive attributes, such as genomic context, unique substrate specificity and catalytic fingerprint, suggest a potential natural role beyond those of known AAL classes.

Carbohydrate-derived alkylcobalt carbonyl:([(1,2:5,6-di-O,O-isopropylidene-alpha-D-glucofuranos-3-yl)oxycarbonyl]methyl)cobalt tricarbonyl triphenylphosphene.

A carbohydrate-derivative alkylcobalt carbonyl,([(1,2:5,6-di-O,O-isopropylidene-alpha-D-glucofuranos-3-yl)oxycarbonyl]methyl)cobalt tricarbonyl triphenylphosphene(3) was prepared and characterized by IR, NMR, and CD spectra, as well as by X-ray diffraction. The supramolecular chemistry in the crystalline P2(1)2(1)2(1) (chiral) phase and in solution was analyzed and compared. The bulky carbohydrate-based ligand stabilized one chiral conformation, which, however, is less ordered than for analogous compounds with more flexible and less bulky chiral groups. Intermolecular, H-bond interactions are more important in the P2(1)2(1)2(1) phase of complex 3 than at other analogous compounds.

Sublimation properties of CoF(3): mass spectrometric and quantum chemical studies.

The sublimation of cobalt trifluoride was studied using the Knudsen effusion method combined with mass spectrometry. The pressure of F was directly measured for decomposition of CoF(3)(s) into CoF(2)(s). The average kinetic energy of CoF(2)(+), CoF(+) and Co(+) fragment ions was determined and the relative ionisation cross section curves measured from 6 eV to 100 eV. Thermodynamic functions of gaseous CoF(3) and Co(2)F(6), were evaluated from geometrical and vibrational parameters provided from theoretical calculations. Heats of formation of CoF(3)(s), CoF(3)(g), Co(2)F(6)(g) were established as (-784 +/- 6) kJ/mol, (-565 +/- 11) kJ/mol and (-1289 +/- 22) kJ/mol, respectively.

Mass spectrometric determination of appearance energies for ions formed from CoF(4) and CoF(3) molecules.

Knudsen cell mass spectrometry was applied to the evaluation of the ionization efficiency curves for the ions originating from CoF(4) molecules. Cobalt tetrafluoride was obtained in the gas phase over the CoF(3)(s)-TbF(4)(s) system in the temperature range from 640 to 690 K. From the ionization efficiency curves the appearance energies of the ions formed from the CoF(4) molecules were determined by means of Vogt's deconvolution method. Clausius-Clapeyron plots for the ions from CoF(4) molecules were measured. Evaporation of pure CoF(3)(s) was carried out, and the appearance energies of the ions formed from CoF(3) molecules were determined. The ionization energies for CoF(4) and CoF(3) molecules were found to be (14.3 +/- 0.2) and (13.3 +/- 0.1) eV, respectively.

Diastereoselection through chiral conformations.

Chiral conformations of flexible molecules may develop in a concerted manner if the molecule is crowded enough to assure sufficient level of through-the-space contacts. Higher number (> 4) of groups connected to the same atom, as in many coordination compounds, can be advantageous in this respect. The case study of R,S-[(sec-butoxycarbonyl)methyl]cobalt tricarbonyl triphenylphosphine is presented here. X-ray diffraction shows that the possible number of enantiomeric and diastereomeric conformations is reduced by 75% (from 8 to 2) by concerted development of the molecular conformations in crystalline phase.

Knudsen cell mass spectrometric investigation of the PbO-ZrO(2)-TiO(2) system.

Knudsen effusion mass spectrometry (KEMS) was used for direct determination of lead oxide activity as a function of temperature in various regions of the PbO-ZrO(2)-TiO(2) system. From the results, the enthalpy, Gibbs free energy and entropy of formation of PbTiO(3) (PT), PbZrO(3) (PZ) and Pb(Zr,Ti)O(3) (PZT) were evaluated. In addition, the single phase widths of Pb(Zr(0.5)Ti(0.5))O(3) and PbTiO(3) perovskite structures were determined at 1100 K. The reaction rate of PZT synthesis in vacuo was followed by direct measurement of the change of PbO activity with time. Lead oxide activity in stoichiometric Pb(Zr(0.5)Ti(0.5))O(3), PbTiO(3) and Pb(0.968)(Zr(0.5)Ti(0.5))O(2.968) (3% lead deficient) at 850 degrees C was found to be 0.40, 0.45 and 0.1, respectively. PZT, PT and PZ powder samples prepared by a solid state procedure were also measured, all revealing lead deficiency. Copyright 1999 John Wiley & Sons, Ltd.