Relation between location of elements in periodic table and affinity for the malignant tumor (author's transl)

Affinity of many inorganic compounds for the malignant tumor was examined, using the rats which were subcutaneously transplanted with Yoshida sarcoma. And the relations between the uptake rate into the malignant tumor and in vitro binding power to the protein were investigated in these compounds. In these experiments, the bipositive ions and anions had not affinity for the tumor tissue with a few exceptions. On the other hand, Hg, Au and Bi, which have strong binding power to the protein, showed high uptake rate into the malignant tumor. As Hg++, Au+ and Bi+++ are soft acids according to classification of Lewis acids, it was thought that these elements would bind strongly to soft base (R-SH, R-S-) present in the tumor tissue. In many hard acids (according to classification of Lewis acids), the uptake rate into the tumor was shown as a function of ionic potentials (valency/ionic radii) of the metal ions. It is presumed that the chemical bond of these hard acids in the tumor tissue is ionic bond to hard base (R-COO-, R-PO3(2-), R-SO3-, R-NH2).     

A theoretical study of the dielectric solvent effect on vicinal spin coupling constants

The dielectric solvent effect on HCCH, HCNH and HCNC spin coupling constants in ethane, tetrachloroethane and trans N-methylformamide has been calculated by finite perturbation theory based on the INDO and CNDO/2 approximations incorporating solvaton theory. The available experimental data are interpreted using the calculated variations of spin coupling constants. The effect of dielectric constant on the general form of the Karplus relation is included in the finite perturbation calculations.     

In Situ Processing of Nano Crystalline Oxide Particles/Polymer Hybrid

Nano sized crystalline particles/polymer hybrids were synthesized form designed metal-organic precursors. The newly developed method is composed of the synthesis of organic matrix by polymerization and the in situ nucleation and growth of crystalline oxide particles in the organic matrix below 100°C. The design of metal-organic precursor modified with polymerizable ligand and the selection of reaction conditions does influence the size and crystallinity of ceramic particles in organic matrix. The nano-sized magnetic particle/polymer hybrid exhibits the interesting feature of superparamagnetism and quantum size effect. The crystalline particles of BaTiO₃/, PbTiO₃/, and KNbO₃/polymer hybrids behave to be dielectric and show the typical electro-rheological behavior.     

Electron spin resonance of hydrogen-absorbed graphite-potassium intercalation compounds

The conduction electron spin resonance (CESR) of the graphite—potassium intercalation compounds, C₈ K and C₂₄ K, was studied in hydrogen gas. An enhancement of CESR absorption and a decrease in asymmetry parameter were observed for C₈K in the initial stage of hydrogen absorption, attributed to paramagnetic hydrogen atoms stabilized in the matrix of the compound.     

Absolute stereochemistries and total synthesis of (+)-arisugacins A and B, potent, orally bioactive and selective inhibitors of acetylcholinesterase

In the current studies, we used the Kakisawa-Kashman modification of the Mosher NMR method to determine the complete absolute stereochemistry of arisugacins. We also report the convergent total synthesis of (+)-arisugacins A and B by a sequence including (i) ruthenium complex-catalyzed asymmetric reduction of the cyclohexenone derivative; (ii) stereoselective construction of the arisugacin skeleton by a Knoevenagel-type reaction of an α,β-unsaturated aldehyde derivative with production of a 4-hydroxy-2-pyrone derivative as a key reaction; and (iii) stereoselective dihydroxylation to give the diol derivative, followed by deoxygenation. Accordingly, we defined the absolute structures of arisugacins A and B as 4a-(R),6a-(R),12a-(R), and 12b-(S). Finally, we characterized the bioactivities of the synthetic intermediates to understand the structure-activity relationships of the arisugacins.     

Perturbation analysis for the rotational spectrum of the NiBr radical in the X2Pi3/2 and A2Delta5/2 states

The millimeter- and submillimeter-wave spectra of the NiBr radical in the X (2)Pi(3/2) and A (2)Delta(5/2) states were observed by a source-modulated microwave spectrometer. The NiBr radical was generated in a dc glow discharge through the mixture of Br(2) vapor and Ar gas by the sputtering reaction with a Ni cathode. Observed transition frequencies were independently analyzed for both electronic states using a standard polynomial expression of a Hund's case (c) approximation. Anomalous behavior of the effective molecular constants in the X (2)Pi(3/2) state was interpreted as the result of the perturbation between the X (2)Pi(3/2) and A (2)Delta(5/2) states. The deperturbed molecular constants were derived using a simplified supermultiplet Hamiltonian including the interaction terms between the two electronic states.     

Chiral self-dimerization of vanadium complexes on a SiO2 surface: the first heterogeneous catalyst for asymmetric 2-naphthol coupling

The self-dimerized chiral assembly of vanadium-Schiff-base complexes was found to occur on a SiO2 surface and to be the first heterogeneous catalyst for the asymmetric oxidative coupling of 2-naphthol with 100% selectivity and 90% enantioselectivity.     

An approach to analysis of pigment release from microcapsules with size distribution

We have studied the release curve for microcapsules with size distribution. On the basis of an analogy to the relaxation phenomena with multiple characteristic times, we propose a stretched exponential release curve for the system with size distribution and relate the release curve to the size distribution function of the microcapsule. This method was successfully applied to the transfer of azo-pigments from inner medium of dioctyl phthalate to dispersing medium of methanol through poly(ureaurethane) microcapsule membrane.     

Deuterium substitution effect on proton relaxation times as a direct means for elucidating molecular interaction in solution. An application to 2′,3′-isopropylideneadenosine

Proton T₁ measurement with the Fourier transform method combined with quenching of dipolar coupling through selective deuterium substitution is shown to be a useful method for elucidating intra- and intermolecular interactions in solution, with 2′,3′-isopropylideneadenosine as an example. Average distances between H-8 and ribose protons are determine in combination with carbon-13 T₁ measurement. The method is compared with the nuclear Overhauser effect.