Production of α-keto acids Part I. Immobilized cells ofTrigonopsis variabilis containing D-amino acid oxidase

Whole cells ofTrigonopsis variabilis were immobilized by entrapment in Ca²⁺-alginate and used for the production of α-keto acids from the corresponding D-amino acids. The D-amino acid oxidase within the immobilized cells has a broad substrate specificity. Hydrogen peroxide formed in the enzymatic reaction was efficiently hydrolyzed by manganese oxide co-immobilized with the cells. The amino acid oxidase activity was assayed with a new method based on reversed-phase HPLC. Oxygen requirements, bead size, concentration of cells in the beads, flow rate, and other factors were investigated in a “ trickle-bed ” reactor.     

Heat capacity, enthalpy and entropy of bismuth niobate and bismuth tantalate

The heat capacity and the heat content of bismuth niobate BiNbO₄ and bismuth tantalate BiTaO₄ were measured by the relaxation method and Calvet-type heat flux calorimetry. The temperature dependencies of the heat capacities in the form C_pm=128.628+0.03340 T−1991055/T²+136273131/T³ (J K^-1 mol^-1) and 133.594+0.02539 T−2734386/T²+235597393/T³ (J K^-1 mol^-1) were derived for BiNbO₄ and BiTaO₄, respectively, by the least-squares method from the experimental data. Furthermore, the standard molar entropies at 298.15 K S_m(BiNbO₄)=147.86 J K^-1 mol^-1 and S_m(BiTaO₄)=149.11 J K^-1 mol^-1 were assessed from the low temperature heat capacity measurements. To complete a set of thermodynamic data of these mixed oxides an attempt was made to estimate the values of the heat of formation from the constituent binary oxides.     

Activation entropy of electron transfer reactions

We report microscopic calculations of free energies and entropies for intramolecular electron transfer reactions. The calculation algorithm combines the atomistic geometry and charge distribution of a molecular solute obtained from quantum calculations with the microscopic polarization response of a polar solvent expressed in terms of its polarization structure factors. The procedure is tested on a donor–acceptor complex in which ruthenium donor and cobalt acceptor sites are linked by a four-proline polypeptide. The reorganization energies and reaction energy gaps are calculated as a function of temperature by using structure factors obtained from our analytical procedure and from computer simulations. Good agreement between two procedures and with direct computer simulations of the reorganization energy is achieved. The microscopic algorithm is compared to the dielectric continuum calculations. We found that the strong dependence of the reorganization energy on the solvent refractive index predicted by continuum models is not supported by the microscopic theory. Also, the reorganization and overall solvation entropies are substantially larger in the microscopic theory compared to continuum models.     

The thermal properties of poly(oxy-1,4-benzoyl), poly(oxy-2,6-naphthoyl), and its copolymers

The thermal properties, i.e., heat capacity, enthalpy, entropy, and Gibbs function, and the transition behavior of the copolymer system of 4-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid have been studied based on differential scanning calorimetry. The heat capacities of the glass, crystal, and anisotropic melt are shown to be largely additive on a molar basis. Additivity is lost in the two transition regions, glass transition and disordering transition. Isothermal crystallization experiments on the copolymers revealed the existence of two types of crystals which melt at high temperature (fast-grown crystals) and low temperature (slowly grown crystals). The ATHAS computation method is used to bring heat capacities of the solid state into agreement with approximate frequency spectra. The changes in heat capacity at the glass transitions occur at 434°K for the poly(oxy-1,4-benzoyl) [33.2 J/(K mol)] and at 420°K for poly(oxy-2,6-naphthoyl) [46.5 J/(K mol)]. The copolymers have a transition range of above 100°K. The anisotropic melt is linked to the well-known condis state of poly(oxy-1,4-benzoyl) by a continuous changes in disorder and mobility without an additional first-order transition.     

Glucose utilization by lysine-producing fluoroacetate-sensitive mutants ofCorynebacterium glutamicum

A fluoroacetate-sensitive mutant was isolated fromCorynebacterium glutamicum, ATCC 21513, following mutagenesis with NTG. Batch fermentations show that in terms of growth kinetics, glucose utilization, and lysine formation, there are significant differences between the mutant and the parent. The mutant’s specific growth rate (0.22/h) is lower than that for the parent (0.34/h). Also, the yield expressed as lysine/glucose consumed does not alter as a function of the glucose concentration for the mutant, and is about 0.22, whereas for the parent, this coefficient decreases with increasing glucose concentration. The maximum specific rate of lysine production for the mutant is 1.3 g/L/h that is about two-fold higher than that for the parent.     

A path following algorithm for a class of convex programming problems

We present a primal-dual path following interior algorithm for a class of linearly constrained convex programming problems with non-negative decision variables. We introduce the definition of a Scaled Lipschitz Condition and show that if the objective function satisfies the Scaled Lipschitz Condition then, at each iteration, our algorithm reduces the duality gap by at least a factor of (1–/n), where is positive and depends on the curvature of the objective function, by means of solving a system of linear equations which requires no more than O(n³) arithmetic operations. The class of functions having the Scaled Lipschitz Condition includes linear, convex quadratic and entropy functions.     

Continuous fermentation for the production of citric acid from glucose

Citric acid is finding new areas of use each year and the demand for the acid is constantly increasing. Being a bulk chemical, the continuous production of citric acid would be advantageous. The paper presents the results from ammonia limited batch and continuous fermentations using the yeast strainSaccharomycopsis (Candida) lipolytica (NRRL Y-7576). Mathematical models were developed for growth and glucose utilization in batch and continuous culture. Cell and acid yields appeared to be almost the same in batch and continuous culture. The specific production rates were found to be constant, equal to 0.053 g/g h, in the batch fermentations but varied in the continuous experiments from 0 to 0.11 g/g h depending on the fermentation conditions. Continuous production in a single stage CSTR was studied for over 1,000 hours without shutdown.     

Production and energetic use of biogas from energy crops and wastes in Germany

The production of biogas for reducing fossil CO₂ emissions is one of the key strategic issues of the German government and has resulted in the development of new process techniques and new technologies for the energetic use of biogas. Progress has been made in cultivating energy crops for biogas production, in using new reactor systems for anaerobic digestion, and in applying more efficient technologies for combined heat and power production. Recently, integration of fuel cells within the anaerobic digestion process was started, and new technologies for biogas upgrading and conversion to hydrogen were tested. This article describes the trends in Germany for achieving more efficient energy production.     

A nonequilibrium entropy for dynamical systems

It is proposed to define entropy for nonequilibrium ensembles using a method of coarse graining which partitions phase space into sets which typically have zero measure. These are chosen by considering the totality of future possibilities for observation on the system. It is shown that this entropy is necessarily a nondecreasing function of the timet. There is no contradiction with the reversibility of the laws of motion because this method of coarse graining is asymmetric under time reversal. Under suitable conditions (which are stated explicitly) this entropy approaches the equilibrium entropy ast+ and the fine-grained entropy ast–. In particular, the conditions can always be satisfied if the system is aK-system, as in the Sinai billiard models. Some theorems are given which give information about whether it is possible to generate the partition used here for coarse graining from time translates of a finite partition, and at the same time elucidate the connection between our concept of entropy and the entropy invariant of Kolmogorov and Sinai.Research supported in part by NSF grants PHY78-03816 and PHY78-15920.     

Heat-capacity measurements and thermodynamic functions of crystalline adenine; revised thermodynamic properties of aqueous adenine

The standard molar heat capacity C^°_p,m of adenine(cr) has been measured using adiabatic calorimetry over the range 6<(T/K)<310 and the results used to derive thermodynamic functions for adenine(cr) at smoothed temperatures. At T=298.15 K, C^°_p,m=(142.67±0.29) J · K⁻¹ · mol⁻¹ and the third law entropy S^°_m=(145.62±0.29) J · K⁻¹ · mol⁻¹. The standard molar Gibbs free energy of formation Δ_fG^°_m at T=298.15 K for crystalline adenine was calculated, using the standard molar enthalpy of formation for the compound and entropies of the elements from the literature, and found to be Δ_fG^°_m=(301.4±1.0) kJ · mol⁻¹. The results were combined with solution calorimetry and solubility measurements from the literature to yield revised values for the standard molar thermodynamic properties of aqueous adenine at T=298.15 K: Δ_fG^°_m=(313.4±1.0) kJ · mol⁻¹, Δ_fH^°_m=(129.5±1.4) kJ · mol⁻¹, and S_m^°=(217.68±0.44) J · K⁻¹ · mol⁻¹.