Classical trajectory calculations of intramolecular vibrational energy redistribution. I. Methanol-water complex

Intramolecular vibrational energy redistributions of the O-H stretching (nuOH) vibration for the methanol monomer and its water complex, the methanol-water dimer, are investigated by using ab initio full-dimensional classical trajectory calculations. For the methanol monomer, in the high-energy regime of the 5nuOH overtone, the time dependence of the normal-mode energies indicates that energy flowed from the initial excited O-H stretching mode to the C-H stretching mode. This result confirms the experimental observation of energy redistribution between the O-H and C-H stretching vibrations [L. Lubich et al., Faraday Discuss. 102, 167 (1995)]. Furthermore, a lot of dynamical information in the time domain is contained in the power spectra, whose density is given by the Fourier transformation of the total momentum obtained from trajectory calculations. For the methanol-water hydrogen-bonded complex, at the high-energy level of the 5nuOH overtone, the calculated power spectrum shows considerable splitting and broadening, indicating significant energy redistribution through strong coupling between the O-H stretching vibration and other vibrations. It is thus clear that the A-H...B hydrogen-bond formation facilitates energy redistribution subsequent to the vibrational excitation of the hydrogen-bonded A-H stretching mode.     

A new method for the synthesis of some 9-β-D-arabinofuranosylpurines by a combination of chemical and enzymatic reactions

An enzymatic transarabinosylation between 2-chlorohypoxanthine and 1-β-$\text{D}$-arabinofuranosyluracil gave 9-β-$\text{D}$-arabinofuranosyl-2-chlorohypoxanthine which was chemically converted to 9-β-$\text{D}$-arabinofuranosylguanine and its derivatives.     

FLUORESCENCE LIFETIME OF ACRIDINE ORANGE IN SODIUM DODECYL SULFATE PREMICELLAR SOLUTIONS

Abstract— The absorption and fluorescence spectra, and the fluorescence lifetime of acridine orange (AO) were measured in a wide range of the sodium dodecyl sulfate (SDS) concentration below and above the critical micelle concentration (cmc). The fluorescence consisted of two components with different lifetimes; short (<3 ns) and long (>3 ns). The short and long lifetime components are attributed to the AO monomer and dimer associated with detergent, respectively. The lifetime of the dimer increased with increasing the SDS concentration just below the cmc. It decreased suddenly to a constant value just above the cmc. The lifetime of the monomer showed only a slight increase in the concentration range of SDS employed.     

Molecular orbital study for Na, Mg, and Al adsorption on the Si (111) surface

We investigated the interactions between the Si(111) surface and the Na, Mg, and Al atoms using cluster model calculations. Calculations were performed at levels of complete-active-space self-consistent-field (CASSCF) and multi-reference singly and doubly excited configuration interaction (MRSDCI) calculations using the model core potential method. Our calculations revealed that the most favorable sites of Na, Mg, and Al adsorption on Si(111) are on top (T₁), bridge (B₂), and 3-fold filled (T₄) sites, respectively. The nature of chemical bonds between these metal atoms and the dangling bonds of the surface Si atoms are found to be essentially covalent.     

Oxythallation of norbornene derivatives with thallium(III) acetate in methanol

Treatment of norbornene, norbornadiene, benzonorbornadiene, and chloro- and methoxy-benzonorbornadiene with thallium(III) acetate in methanol affords only the corresponding cis-exo-acetoxythallation adducts in a sharp contrast to oxymercuration of such strained olefins where methoxymercuration prevails. In the cases of substituted benzonorbornadienes the products are obtained as the regioisomeric mixtures, the isomer ratio being determined by ¹³C NMR. In the cases of 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2-methyl-2,3-dicarboxylic anhydride, and 5-norbornen-2-endo-carboxylic acid, lactonization occurs to give a trans-oxythallation adduct having a lactone ring, no introduction of either methoxy or acetoxy groups being observed. ¹H and/or ¹³C NMR data for several new oxythallation adducts are provided. The alkaline sodium borohydride reduction of adducts in methanol affords mainly the parent olefin together with 10–16% yields of the corresponding exo-alcohol.     

Duplex dissociation of telomere DNAs induced by molecular crowding

Because of the importance of telomere DNAs, the structures of these DNAs in vivo are currently of great research interest in the medical, pharmaceutical, chemical, and industrial fields. To understand the structure of biomolecules in vivo, their properties studied in vitro are extrapolated to the in vivo condition, while the condition in a living cell is inherently molecularly crowded and a nonideal solution contains various biomolecules. We investigated the effect of molecular crowding, which is one of the most important cellular environmental conditions, on the structure and stability of the telomere and G-rich and C-rich DNAs using circular dichroism (CD) spectra, CD melting curves, and isothermal titration calorimetry (ITC). The CD spectra and CD melting curves of G-rich DNA, C-rich DNA, and the 1:1 mixture of G-rich and C-rich DNAs showed that each G-rich DNA, C-rich DNA, and the 1:1 mixture form the antiparallel G-quadruplex, I-motif, and duplex, respectively, in the noncrowding condition as previously considered. On the contrary, the G-rich and C-rich DNAs individually form the parallel G-quadruplex and I-motif, respectively, in the molecular crowding condition, and the 1:1 mixture folds into the parallel G-quadruplex and I-motif but does not form a duplex. The ITC measurements indicated that the thermodynamic stability (DeltaG degrees (20)) of the duplex formation between the G-rich and C-rich DNAs in the noncrowding condition was -10.2 kcal mol(-)(1), while only a small heat change was observed in the ITC measurements in the molecular crowding condition. These ITC results also demonstrated that the molecular crowding condition prevents any duplex formation between G-rich and C-rich DNAs. These results indicate that a structural polymorphism of the telomere DNAs is induced by molecular crowding in vivo.     

Peroxotungstate immobilized on ionic liquid-modified silica as a heterogeneous epoxidation catalyst with hydrogen peroxide

Peroxotungstate immobilized on ionic liquid-modified SiO2 is capable of heterogeneously epoxidizing a wide range of olefins with the maintenance of the catalytic activity of homogeneous analogue. The epoxidation was immediately stopped by the removal of the catalyst, and no tungsten species could be found in the filtrate after the removal of the catalyst. These results can rule out any contribution to the observed catalysis from the tungsten species that leached into the reaction solution, and the observed catalysis is truly heterogeneous in nature. Furthermore, the catalyst was reusable without the loss of the catalytic performance.     

Reactivity and catalytic activity of cationic lonomers for the nucleophilic substitution reactions

Polystyrene-based crosslinked cationic ionomers containing ammonium or phosphonium chlorides (AxRCI and PxBuCI) were reacted with decyl methanesulfonate. The kinetic data were correlated with the swelling behavior of the ionomers and the solution viscosity of the corresponding linear ionomers. The reactivity of the ionomers was independent of the particle size of the ionomer beads, indicating no diffusion control of the reaction. The solvent and the ion content of the ionomers greatly affect the reactivity. In nonpolar solvents with a low acceptor number, A_N, such as toluene, the aggregation of ionic groups with an increasing ion content reduces the reactivity. A solvent with a high value of A_N, such as chloroform, led a very low reactivity independent of the ion content. Aprotic polar solvent, such as acetonitrila, promoted the dissociation of the ionic groups and furnished a relatively high reactivity independent of the ion content. Several catalytic substitution reactions were carried out under liquid-solid-solid triphase conditions. The kinetic results were accounted for in terms of slow nucleophile transport and fast chemical reaction within the ionomer particles. © 1994 John Wiley & Sons, Inc.     

Rate constants for the reactions of a series of alkylperoxy radicals with NO

The rate constants for the gas-phase reactions of isopropyl- and tert-butylperoxy radicals with nitric oxide (NO) have been studied at 298 +/- 2 K and a total pressure of 3-4 Torr (He buffer) using a laser flash photolysis technique coupled with a time-resolved negative-ionization mass spectrometry. The alkyl peroxy radicals were generated by the reaction of alkyl radicals with excess O(2), where alkyl radicals were prepared by laser photolysis of several precursor molecules. The rate constants were determined to be k(i-C(3)H(7)O(2) + NO) = (8.0 +/- 1.5) x 10(-12) and k(t-C(4)H(9)O(2) + NO) = (8.6 +/- 1.4) x 10(-12) cm(3) molecule(-1) s(-1). The results in combination with our previous studies are discussed in terms of the systematic reactivity of alkyl peroxy radicals toward NO.