D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity

The one‐step synthesis of D_3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η³‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η³‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.     

A -series identity and the arithmetic of Hurwitz zeta functions

Using a single variable theta identity, which is similar to the Jacobi Triple Product identity, we produce the generating functions for values of certain expressions of Hurwitz zeta functions at non-positive integers.     

Re-entrant phase transitions of the Blume-Emery-Griffiths model

We have investigated the spin-1 Ising model on the simple cubic lattice with bilinear, biquadratic interaction and anisotropic energy (BEG model). We have been specially interested in the case of antiferro biquadratic interaction, because the interaction will cause the competition with bilinear interaction and anisotropy. A two-sublattice ordering, so called the staggered quadrupole (SQ) phase, occurs as long as biquadratic interaction is negative large enough. We have obtained a full phase diagram in the whole interaction parameter space (for the positive bilinear interaction) by the Bethe approximation, and found several kinds of phase transitions, such as successive, re-entrant and double re-entrant transitions. These transitions are also confirmed by Monte Carlo simulations on simple cubic lattices.     

Synthesis and biological activities of analogs of a lipid A biosynthetic precursor: 1-O-phosphonooxyethyl-4'-O-phosphono-disaccharides with (R)-3-hydroxytetradecanoyl or tetradecanoyl groups at positions 2, 3, 2' and 3'.

Two novel analogs of a biosynthetic precursor of lipid A (2) were synthesized. The one analog (3) has acyl groups identical to those of 2, and the other (4) has tetradecanoyl groups in place of the (R)-3-hydroxytetradecanoyl groups of 2. Both 3 and 4 possess an alpha-glycosidically-bound phosphonooxyethyl group in place of the alpha-glycosyl phosphate group of 2. Compounds 3 and 4 exhibited definite antitumor activity against Meth A fibrosarcoma and low toxicity in rabbits, as the original compound 2 does. The replacement of the hydroxytetradecanoyl groups with tetradecanoyl groups barely affected the antitumor activity, but slightly enhanced the toxicity in rabbits.     

Calculation of heat transfer and uniformity of chemical amplification during post-exposure bake

Heat transfer in a resist-coated silicon wafer using a bake process is theoretically evaluated by modeling the three-dimensional diffusion process, focusing on the controllability of the lithographic performance of chemically amplified resists. Six models of various ambient conditions are used. The proximity gap between the hotplate and the wafer is found to have a dominant influence on the heat transfer process for the whole system. Because the atmosphere near the wafer acts as a thermal diffusion buffer layer, no temperature gradient occurs in the resist, even when it is subjected to convective heat transfer from the resist surface. Experimental results obtained by X-ray lithography confirm the calculation results.     

A SAXS study of the nanometer scale hybrid structure of Si---Ti---C---O amorphous fibers

A small-angle X-ray scattering (SAXS) study was performed to reveal the nanometer scale hybrid structure of Si---Ti---C---O fibers prepared by the pyrolysis of polytitanocarbosilane. The SAXS profile for Si---Ti---C---O fibers is attributed to two different types of scattering entities: an anisotropic contribution from long filaments with diameters hundreds to thousands of Ångströms and an isotropic contribution from β-SiC fine clusters of about a nanometer in diameter. A drastic degradation in the tensile strength of the fibers is correlated to the characteristic variations in their long-and medium-range structure.     

Synthesis of self‐photosensitizing polyesters containing donor–acceptor norbornadiene moieties and benzophenone groups and their photochemical reactions

The ring‐opening copolymerization of a glycidyl ester derivative having a benzophenone group and the donor–acceptor norbornadiene (D‐A NBD) dicarboxylic acid, 5‐(4‐methoxyphenyl)‐1,4,6,7,7‐pentamethyl‐2,5‐norbornadiene‐2,3‐dicarboxylic acid, monoglycidyl ester derivatives with D‐A NBD dicarboxylic anhydride using tetraphenylphosphonium bromide as a catalyst proceeded smoothly to give novel self‐photosensitizing NBD polymers in good yields. The molecular weight of these polyesters was about 4,000, and lower than that of analogous NBD polymers having no benzophenone group. All the synthesized NBD polymers isomerized smoothly to the corresponding quadricyclane (QC) polymers upon UV irradiation in tetrahydrofuran (THF) solution and in the film state. The rate of the photoisomerization of the D‐A NBD moieties in these polymers was higher than that of the D‐A NBD moieties in the polymer having no photosensitizing group. Furthermore, the rate of the photoisomerization of the D‐A NBD moieties in these polymers was also higher than that of the NBD polymer with low molecular weight photosensitizer in dilute solution. The photo‐irradiated polymers having QC moieties released thermal energies of 146–180 J/g. The D‐A NBD moieties contained in these NBD polymers possessed fair to good fatigue resistance. The degradation of the NBD moieties in these polymers was 15–30% after 50 repeated cycles of interconversion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2978–2988, 2007