DIBAL-mediated reductive transformation of trans-dimethyl tartrate acetonide into ε-hydroxy α,β-unsaturated ester and its derivatives

Stepwise, selective DIBAL reduction of the acetonide diester derived from tartaric acid followed by the Horner-Emmons reaction effectively provided desymmetrized hydroxy mono-olefination products in a one-pot operation.     

Quantum proton transfer in hydrated sulfuric acid clusters: a perspective from semiempirical path integral simulations

We have carried out path-integral molecular dynamics simulations for hydrated sulfuric acid clusters to understand acid-dissociation and hydrogen-bonded structural rearrangement processes in these clusters from a quantum mechanical viewpoint. The simulations were performed using the PM6 semiempirical electronic structure level whose parameters were modified on the basis of the specific reaction parameters strategy so that relative energies of optimized structures, as well as water binding energies reproduce ab initio and density-functional theory calculations. We have found that the acid dissociation processes, first and second deprotonation, effectively occur in a hydrated cluster with a specific cluster size. The mechanisms of the proton-transfer processes were analyzed in detail and it was found that the distance between O in sulfuric acid and O in the proton-accepting water is playing an important role. We also found that the water coordination number of the poton-accepting water is important in the proton-transfer processes.     

Nuclear quantum effect on the hydrogen-bonded structure of guanine�Ccytosine pair

The structure of Watson?CCrick type guanine?Ccytosine (G?CC) base pair has been studied by classical hybrid Monte Carlo (HMC) and quantum path integral hybrid Monte Carlo (PIHMC) simulations on the semiempirical PM6 potential energy surface. For the three NH?X hydrogen-bonded moieties, the intramolecular NH bonds are found systematically longer while the H?X distance shorter in the PIHMC simulation than in the HMC simulation. We found that the hydrogen bonded length N?X correlates with the H?X distance, but not with the NH distance. A correlation is also between the neighboring hydrogen bonds in the G?CC base pair.     

Spin fluctuations of Y(Mn1−xAlx)2 and Y1−xScxMn2

The thermal expansion and low temperature and low temperature specific heat were measured for Y_1−xScxMn2. The results are discussed in terms of spin fluctuations and compared with those of Y(Mn_1−xAl_x)₂, which show al local moment character. It is revealed that Y_1−xSc_xMn₂ is a typical nearly antiferromagnet in which giant spin fluctuations are thermally excited.     

Capillary electrophoretic discrimination of single nucleotide polymorphisms using an oligodeoxyribonucleotidepolyacrylamide conjugate as a pseudo-immobilized affinity ligand: optimum ligand length predicted by the melting temperature values.

We developed a weak-affinity separation system for single-nucleotide polymorphisms (SNPs) based on capillary electrophoresis. In this approach, single-stranded DNA (ssDNA)-polyacrylamide (polyAAm) conjugate was used as a pseudo-immobilized affinity ligand to separate the target DNA, cytochrome P450 2C9 (CYP2C9), and its point mutant. The ligand DNA was designed to be complementary to the normal DNA, and the target DNA was electrophoretically separated by the difference in the affinity with the pseudo-immobilized ligand in the capillary. We showed that the separation efficiency was closely associated with the Tm value of double-stranded DNA (dsDNA) consisting of the target and ligand DNA, which depends on the measurement conditions, such as the base number of the ligand DNA and the concentration of Mg2+ in the buffer solution.     

Prediction of carcinogenicity of polynuclear aromatic hydrocarbons on the basis of their chemical structures

The carcinogenicities of polynuclear aromatic hydrocarbons in particulates extracted from diesel engine exhaust are predicted on the basis of the combined bay-L region theory proposed earlier, in conjunction with pattern recognition techniques. The predicted carcinogenicities agree well with experimental data, thus showing the validity of the proposed model equations.     

Spectral Gap and Exponential Decay of Correlations

We study the relation between the spectral gap above the ground state and the decay of the correlations in the ground state in quantum spin and fermion systems with short-range interactions on a wide class of lattices. We prove that, if two observables anticommute with each other at large distance, then the nonvanishing spectral gap implies exponential decay of the corresponding correlation. When two observables commute with each other at large distance, the connected correlation function decays exponentially under the gap assumption. If the observables behave as a vector under the U(1) rotation of a global symmetry of the system, we use previous results on the large distance decay of the correlation function to show the stronger statement that the correlation function itself, rather than just the connected correlation function, decays exponentially under the gap assumption on a lattice with a certain self-similarity in (fractal) dimensions D < 2. In particular, if the system is translationally invariant in one of the spatial directions, then this self-similarity condition is automatically satisfied. We also treat systems with long-range, power-law decaying interactions.