Theoretical Study of the Rate Coefficients for CH3NHNH2 + NO2 and Related Reactions

The kinetics and mechanisms of H atom abstraction reactions from CH₃NHNH₂ by NO₂ (R1) and related reactions have been investigated theoretically by using ωB97X‐D and CCSD(T)‐F12 quantum chemical calculations and the steady‐state unimolecular master equation analysis based on Rice–Ramsperger–Kassel–Marcus (RRKM) theory. For reaction (R1), both dissociation and isomerization steps between intermediate complexes were found to be important for the distribution of the dissociated bimolecular products. The dominant products of (R1) were found to be cis‐CH₃NHNH and HONO at lower temperature. The branching ratios for CH₃NNH₂ formation paths increased with increasing temperature. On the same reaction potential energy surface, six reactions including isomerization reactions between CH₃NNH₂ and cis‐/trans‐CH₃NHNH catalyzed by HONO were suggested to compete with the reverse reaction of (R1). The temperature‐ and pressure‐dependent rate expressions are proposed for kinetic modeling.     

A Note on a Practical Technique for Solving Elliptic Equations

In this paper, we propose a new method which is the SOR methodwithout the knowledge of the optimum accelerating factor, andthis method is compared with the optimum SOR method concernedwith the convergence rate.     

Convergence process with quasi-canonical localized orbital in all-electron SCF calculation on proteins

A convergence process with a new type of localized orbital (LO) is proposed for self-consistent field (SCF) molecular orbital (MO) calculations on proteins. Recently, an all-electron density functional (DF) calculation on cytochrome c was achieved by a convergence method in which the initial electron density of a peptide was constructed by linking the electron density of small peptides. However, its convergence was slow and insufficient in SCF calculations for long peptides. In this paper a new kind of LO called the ‘quasi-canonical localized orbital (QCLO)’ is formulated and a computational process with QCLOs is proposed to improve the SCF convergence. The QCLO is localized in a certain region of a molecule, but it is also the canonical MO of the region. In test calculations on a seven-residue peptide, the error in the initial total energy calculated with QCLOs was about one twentieth of that by cut and paste of the electron density, and the number of SCF iterations was reduced markedly. Future applications of QCLO to big and complex molecules are also discussed.     

LOW-TEMPERATURE HEAT CAPACITY AND THERMODYNAMIC FUNCTIONS OF 2-CHLORO-6-(TRICHLOROMETHYL)PYRIDINE

The heat capacity of 2- chloro- 6- (trichloromethyl)pyridine has heen measured with anadiabatic calorimeter in the range from 13 to 316K. There is no indication of any phasetransition or thermal anomaly in this temperature region for the present compound. Theresults have been compared with those reported in [1] in the overlapping temperaturerange. The experimental heat capacity data have been fitted to a smoothed curve by the aidof the effective frequency distribution method, and the heat capacities below 13K have beenobtained by extrapolating the fitting curve down to 0K. The standard molar thermodynamicfunctions between 0 and 400 K have been derived by combining the present heat capacitymeasurements with the previous ones. The values of C_p~o (T), S~o(T) - S~o(0), [H~o(T) -H~o(0)]/T, and - [G~o(T) - H~o(0)]/T at T = 298.15 K are 189.35, 244.60, 112 .45 and 132.15J·K~(-1)·mol~(-1), respectively.     

Numerical study of nanoscale lubrication and friction at solid interfaces

This study investigates lubrication and related frictional phenomena on the nanoscale using numerical simulations. Two models of lubrication, a two-layer and a three-layer, are considered, and for the three-layer model, a lubricant layer is introduced between the two solids. The kinetic frictional force shows resonance behaviour caused by multi-phonon excitations at the interface. It is found that these frictional effects cause a peculiar stick-slip motion of the driven plate and lubricants.     

MORE EFFICIENT EXCISION REPAIR OF PYRIMIDINE DIMERS IN THE SPECIFIC DNA SEQUENCE THAN IN THE GENOME OVERALL IN GOLDFISH CELLS

Excision repair of pyrimidine dimers induced by 254 nm UV was examined in the genome overall and in a specific sequence containing a transfected gene for hygromycin B resistance, in RBCF-1 cells derived from a goldfish, by the use of UV endonuclease of Micrococcus luteus and alkaline agarose gel electrophoresis. More than 40% of dimers were removed from the specific sequence, while about 20% were removed from the genome overall, within 24 h after exposure to UV (2.5-7.5 J/m2).     

ENHANCEMENT OF PHOTOREPAIR OF ULTRAVIOLET-DAMAGE BY PREILLUMINATION WITH FLUORESCENT LIGHT IN CULTURED FISH CELLS

Fluorescent light (FL) illumination of RBCF-1 cells, derived from a goldfish, prior to 254 nm UV-irradiation enhanced their ability to photorepair. The cells were illuminated with FL for 1 h (29 W/M2) and incubated for 8 h in the dark before being irradiated with 10 J/m2 UV. The surviving fraction of FL-treated cells after UV-irradiation rose about 7-fold (from 3 to 20%) by 20 min photorepair treatment with the same FL source, whereas 4-fold (from 1.6 to 6%) in the FL non-treated cells. Flow cytometric analysis showed that FL treatment did not affect the distribution of cell cycle phase at the time of UV-irradiation (8 h after FL treatment). Pyrimidine dimers induced by UV were measured by the use of UV endonuclease of Micrococcus luteus and alkaline agarose gel electrophoresis. Initial yields of dimers after exposure to 10 J/m2 UV were almost the same (about 0.11 dimer/kb) between FL treated and non-treated cells. But after 20 min photorepair treatment, about 70% of dimers were removed in the FL treated samples, while less than 20% were removed in the non FL-treated ones.     

A Paradox of Economic Growth and Relative Deprivation

Rapid economic growth sometimes intensifies people's frustration. In this article, we attempt to formulate this kind of paradox of economic growth, and to explain theoretically how economic growth increases people's dissatisfaction by way of the notion of relative deprivation by employing the theoretical framework of Yitzhaki's relative deprivation index. We introduce the problem of the China puzzle as the latest case of the paradox. Then, we introduce the definition of Yitzhaki's index of relative deprivation, and use this to explain the China puzzle. Besides, through a theoretical examination of Yitzhaki's index, we propose a proposition proving that an increase of relative deprivation in the society can occur even when the amount of wealth increases and the degree of inequality reduces.     

Decoupling by State Feedback in Infinite-Dimensional Systems

This paper studies the decoupling problem in infinite-dimensionalsystem using the so-called geometric approach of Wonham, andpresents necessary and/or sufficient conditions for the problemto be solvable for various cases, including (a) the case forwhich the input operator B satisfies dim (Im B) = k, where kis the number of output blocks, and (b) the case for which thepre-input operator G satisfies rank G = m, where m is the dimensionof the input space.     

Parameter-insensitive disturbance rejection for infinite-dimensional systems

In the framework of the so-called geometric approach, this paperstudies two parameter-insensitive disturbance-rejection problemswith state feedback and with incomplete state feedback for linearsystems defined in Hilbert spaces, and presents necessary and/orsufficient conditions for these problems to be solvable undercertain assumptions.