pH,Definition and measurement at high temperatures

In this review paper, the NBS scale and its limitations are briefly discussed. The magnitude of liquid junction potentials and some calculated values are presented. The use of a molality scale for hydrogen electrode concentration cells at high temperatures is described, and results from measurements on ionization equilibria are summarized. Use of this scale is also recommended for certain circumstances with cells without liquid junction. As an alternative activity scale, use of the Pitzer ion-interaction treatment for ions is recommended for special cases. Finally, reference data are presented for _±HCl in HCl(aq) to 350°C and (HCl+NaCl)(aq) to 200°C that were derived by use of the Pitzer ion-interaction treatment.Presented at the Second International Symposium on Chemistry in High Temperature Water, Provo, UT, August 1991.     

Reaction Engineering Aspects of α-l,4-D-Glucan Phosphorylase Catalysis

Some important process properties of α-l,4-D-ghican phosphorylases isolated from the bacteriumCorynebacterium callunae and potato tubers (Solatium tuberosum) were compared. Apart from minor differences in their stability and specificity (represented by the maximum degree of maltodextrin conversion) and a 10-fold higher affinity of the plant phosphorylase for maltodextrin (K _M of 1.3 g/L at 300 mM of orthophosphate), the performances of both enzymes in a continuous ultrafiltration membrane reactor were almost identical. Product synthesis was carried out over a time course of 300–400 h in the presence or absence of auxiliary pullulanase (increasing the accessibility of the glucan substrate for phosphorolytic attack up to 15–20%). The effect of varied dilution rate and reaction temperature on the resulting productivities was quantitated, and a maximum operational temperature of 40°C was identified.     

A comparative quantum-chemical analysis of electronic structures and spectroscopic parameters of cycloalkanes and cyclopolysilanes

A comparative quantum-chemical analysis of the electronic structures and spectroscopic parameters of the cycloalkanes C₃H₆, C₄H₈, C₅H₁₀, and C₆H₁₂ and their silicon analogs Si₃H₆, Si₄H₈, Si₅H₁₀ and Si₆H₁₂ was performed in the framework of the SCF MO LCAO method in the INDO approximation. Qualitative interpretation of “abnormal” ionization potentials and energies of electronic absorption spectra of cyclopolysilanes has been given. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1105–1108, June, 1997.     

Cellulose production based on hemicellulose hydrolysate from steam-pretreated willow

The production cost of cellulolytic enzymes is a major contributor to the high cost of ethanol production from lignocellulosics using enzymatic hydrolysis. The aim of the present study was to investigate the cellulolytic enzyme production ofTrichoderma reesei Rut C 30, which is known as a good cellulase secreting micro-organism, using willow as the carbon source. The willow, which is a fast-growing energy crop in Sweden, was impregnated with 1–4% SO₂ and steam-pretreated for 5 min at 206°C. The pretreated willow was washed and the wash water, which contains several soluble sugars from the hemicellulose, was supplemented with fibrous pretreated willow and used for enzyme production. In addition to sugars, the liquid contains degradation products such as acetic acid, furfural, and 5-hydroxy-methylfurfural, which are inhibitory for microorganisms. The results showed that 50% of the cellulose can be replaced with sugars from the wash water. The highest enzyme activity, 1.79 FPU/mL and yield, 133 FPU/g carbohydrate, was obtained at pH 6.0 using 20 g/L carbon source concentration. At lower pHs, a total lack of growth and enzyme production was observed, which probably could be explained by furfural inhibition.     

Tailoring approach for exploring electron densities and electrostatic potentials of molecular crystals

Experimental and theoretical studies of electron densities and the corresponding derived entities such as electrostatic potentials have been the primary means of understanding the chemical nature and electronic properties of crystalline substances. Conventional crystal calculation methods such as the embedded cluster models are capable of performing calculations on small and medium-sized molecules, while periodic ab initio methods can treat crystals with up to 200 atoms per unit cell. A linear scaling method, viz. the molecular tailoring approach, has recently been developed for obtaining ab initio quality one-electron properties. In the present study, the molecular tailoring approach is employed to generate electron density, electrostatic potential and interaction density maps with the ibuprofen crystal as a test case. The interaction density and electrostatic potential maps produced in the present work succinctly bring out the actual crystalline environment around a given reference molecule by including the interactions with atoms in its neighborhood. The results obtained from the molecular tailoring approach may thus be expected to enhance our understanding of the environment in the crystalline material with reasonably small computational effort.Contribution to the Jacopo Tomasi Honorary Issue     

Parametric study of catalytic reforming process?

Summary A parametric study of catalytic reforming process in a pilot plant was carried out by varying the pressure, H₂/HC ratio, and space velocity. The results show that lower aromatics and higher hydrogen yields can be accomplished by increasing the space velocity in existing reformers, which will also result in better C₅⁺yield.     

甲烷氧化细菌催化二氧化碳生物合成甲醇的研究

甲烷氧化细菌中包含的甲烷单加氧酶(MMO)、甲醇脱氢酶(ADH)、甲醛脱氢酶(FaldDH)、甲酸脱氢酶(FateDH)经过一系列反应能够把甲烷深度氧化生成二氧化碳，并生成一定的能量物质．把二氧化碳还原为甲醇是一个需要能量的过程，目前还没有已知的有机体在温和条件下完成这一反应．研究发现，甲基弯菌Methylosi-nus trichosporium IMV 3011可以催化二氧化碳生物转化生成甲醇．在休眠的悬浮细胞中充人二氧化碳后，反应一段时间在反应液中检测到了甲醇．二氧化碳转化成甲醇是一个需要能量推动的反应，为了补充反应所消耗的能量．反应一段时间后需要用甲烷进行再生，以恢复细胞中的还原当量NADH．我们进行了反应再生的交替连续批式反应，甲醇积累量能够维持在一个比较稳定的水平．理论上，反应不会增加温室效应，这是一个有效的、环境友好的、可恢复的反应过程．     

Absolute rate calculations: atom and proton transfers in hydrogen-bonded systems.

We calculate energy barriers of atom- and proton-transfer reactions in hydrogen-bonded complexes in the gas phase. Our calculations do not involve adjustable parameters and are based on bond-dissociation energies, ionization potentials, electron affinities, bond lengths, and vibration frequencies of the reactive bonds. The calculated barriers are in agreement with experimental data and high-level ab initio calculations. We relate the height of the barrier with the molecular properties of the reactants and complexes. The structure of complexes with strong hydrogen bonds approaches that of the transition state, and substantially reduces the barrier height. We calculate the hydrogen-abstraction rates in H-bonded systems using the transition-state theory with the semiclassical correction for tunneling, and show that they are in excellent agreement with the experimental data. H-bonding leads to an increase in tunneling corrections at room temperature.     

Fitting complex potential energy surfaces to simple model potentials: application of the simplex-annealing method

A stochastic method of optimization, which combines simulated annealing with simplex, is implemented to fit the parameters of a simple model potential. The main characteristic of the method is that it explores the whole space of the parameters of the model potential, and therefore it is very efficient in locating the global minimum of the cost function, in addition to being independent of the initial guess of the parameters. The method is employed to fit the complex intermolecular potential energy surface of the dimer of water, using as a reference the spectroscopic quality anisotropic site-site potential of Feller et al. The simple model potential chosen for its reparameterization is the MCY model potential of Clementi et al. The quality of the fit is assessed by comparing the geometry of the minimum, the harmonic frequencies, and the second virial coefficients of the parameterized potential with the reference one. Finally, to prove more rigorously the robustness of this method, it is compared with standard nonstochastic methods of optimization.