Effects of host-guest recognition on kinetics of Diels-alder reaction of quinocrown ethers with cyclopentadiene

Diels-Alder reactions of 15-21-membered quinocrown ethers 1a-c and 18-membered quinobenzocrown ether 1d with cyclopentadiene were catalyzed by the addition of alkali, alkaline earth metal and ammonium perchlorates, and scandium trifluoromethane-sulfonate. The alkali metal and ammonium ions brought about a fairly selective rate-acceleration for each crown ether due to the size-fitted ion-in-the-hole complexation. However, such a hole-size-selectivity was not observed for the reactions catalyzed by divalent alkaline-earth (Mg2+ to Ba2+) and trivalent Sc3+ ions. The wrapping complexation played a significant role in rate-acceleration in such a way that the smallest Mg2+ caused 160 times rate-enhancement for the most flexible 1c and the Sc3+ performed maximal 3700 times rate-increment for the 18-membered quinobenzocrown 1d. These effects of cation recognition were rationalized by the reduction of LUMO energy that is favored by the orbital interaction with the HOMO of cyclopentadiene. The magnitude of rate-enhancement was discussed in terms of the cation binding affinity and coordination geometry of quinocrown ethers as well as the valence of cations.     

Deoxygenation of dithiirane 1-oxides with Lawesson's reagent leading to the corresponding dithiiranes

3,3-Disubstituted dithiirane 1-oxides were efficiently reduced with Lawesson's reagent (LR) to give the corresponding dithiiranes. X-ray diffraction analysis of 3,3-di(1-adamantyl)dithiirane is reported. Reaction of (34)S-labeled 3,3-di(1-adamantyl)dithiirane 1-oxide with LR produced the corresponding dithiirane in which the (34)S atoms were retained quantitatively.     

Exact results for the thermal and magnetic properties of strong coupling ladder compounds

We investigate the thermal and magnetic properties of the integrable su(4) ladder model by means of the quantum transfer matrix method. The magnetic susceptibility, specific heat, magnetic entropy, and high field magnetization are evaluated from the free energy derived via the recently proposed method of high temperature expansion for exactly solved models. We show that the integrable model can be used to describe the physics of the strong coupling ladder compounds. Excellent agreement is seen between the theoretical results and the experimental data for the known ladder compounds (5IAP)2CuBr4.2H(2)O, Cu2(C5H12N2)2Cl4, etc.     

Complementary nucleobase interaction enhances peptide-peptide recognition and self-replicating catalysis

The availability of the complementary interaction of nucleobases for influencing the formation of peptide architectures was explored. Nucleobases were incorporated as additional recognition elements in coiled-coil peptides by employing nucleobase amino acids (NBAs), which are artificial L-alpha-amino gamma-nucleobase-butyric acids. The effect of the base-pair interaction on intermolecular recognition between peptides was evaluated through a self-replication reaction. The self-replication reactions of the peptides with complementary base pairs such as thymine-adenine or guanine-cytosine at the g-g' heptad positions were accelerated in comparison with those of the peptides with mismatched base pairs or without nucleobases. However, thymine-adenine pairs at the e-e' positions did not enhance the self-replication. In the presence of a denaturant, the enhancement effects of complementary base pairs on the reaction disappeared. Thermal denaturation studies showed that the thymine-adenine pairs contributed to stabilization of the coiled-coil structure and that the pairs at the g-g' positions were more effective than those at the e-e' positions. The peptide-peptide interaction was reinforced by complementary nucleobase interactions appropriately arranged in the peptide structure; these led to acceleration of the self-replication reactions.     

Chiral symmtry of Wilson fermions at finite temperature

Chiral properties of Wilson fermions at finite temperature are investigated by numerical methods. We show that when the quark mass is properly defined, for a given β and K (hopping parameter), its value is independent of whether the system is in the high-temperature phase or in the low-temperature phase. The temperature dependence of the pion screening mass at the chiral limit where the quark mass vanishes is consistent with the physical picture that the spontaneously broken chiral symmetry is recovered at T = T_c.     

The rate of increase in fluorescence intensity caused by deuteration of tryptophan

Tryptophan was rapidly transferred from ¹H₂O into a ²H₂O medium by a stopped-flow device, and a time-dependent fluorescence increase was traced. It has been shown that this fluorescence change is caused by the deuteration of the α-ammonium (—NH⁺₃) group.     

Nucleation-controlled growth in polyethylene single crystals: Growth and shape of {100} sectors

The nucleation rate and propagation rate of steps on the {100} faces of polyethylene crystals have been determined. For single crystals, under conditions where the width of the {100} sectors remains constant during growth, it is confirmed that the growth is in regime I or the crossover region between regime I and II. In {110} twinned crystals, the {100} sectors are well developed and the width increases linearly with time; therefore, the growth in the twins must be in regime II. It is shown that the differing growth regimes of {100} faces in single crystals and twins allow the independent determination of the nucleation rate and the propagation rate of steps. The nucleation rate and propagation rate of steps on the {100} faces were determined from measurements of the constant width of the {100} faces in single crystals and the growth rate of the {100} faces in single crystals and twins. The observed rates show abnormal dependence on supercooling and concentration. The results are attributed to a weaker dependence of the constant width of {100} sectors on supercooling and concentration than predicted.