Theoretical Study of the Reaction Mechanism of Phenol-Epoxy Ring-Opening Reaction Using a Latent Hardening Accelerator and a Reactivity Evaluation by Substituents.

The mechanism of the phenol-epoxide ring-opening reaction using tetraphenylphosphonium-tetraphenylborate (TPP-K) was investigated using the density functional theory (DFT) method. The reaction was initiated by breaking the P-B bond of TPP-K. The generated tetraphenylborate (TetraPB-) reacted with phenol to form a phenoxide ion, which combined with tetraphenylphosphonium (TPP+) to produce the active species, i.e., tetraphenylphosphonium phenolate (TPP-OPh). The phenoxide ion in TPP-OPh nucleophilically attacked the epoxide. Simultaneously, the H atom in the phenolic OH group moved to the O atom of the ring-opened epoxide. The formed phenoxide ion bound to TPP+ again, and TPP-OPh was regenerated. The rate-determining steps in the reaction were the cleavage of the P-B bond and the triphenylborane-forming reaction. The free energies of activation were calculated to be 36.3 and 36.1 kcal/mol, respectively. It is also suggested that these values in the rate-determining steps could be manipulated by substituents introduced on the Ph group of TetraPB-. Based on these results, it is possible to construct new design guidelines for latent hardening accelerators such as TPP-K.

Theoretical investigation of the molecular structures and excitation spectra of triphenylamine and its derivatives.

The molecular geometries, electronic structures, and excitation energies of NPh(3), NPh(2)Me, NPhMe(2), and NMe(3), were investigated using DFT and post-Hartree Fock methods. When the structural stabilities of these compounds were compared to results obtained by using MP4(SDQ) method, it was confirmed that the optimized geometries by using MP2 method were sufficiently reliable. The excited states with large oscillator strengths consisted of transition components from the HOMO. It should be noted that the orbitals of the nitrogen atom mix with the π-orbital of the phenyl group in an anti-bonding way in the HOMO, and the orbital energy increases with this mixing. The unoccupied orbitals are generated from bonding and anti-bonding type interactions between the π-orbitals of the phenyl groups; therefore, the number of phenyl groups strongly affects the energy diagram of the compounds studied. The differences in the energy diagram cause a spectral change in these compounds in the ultraviolet region.

Towards the development of synthetic routes using theoretical calculations: an application of in silico screening to 2,6-dimethylchroman-4-one.

This study describes an attempt to develop a synthetic route using theoretical calculations, i.e., in silico synthesis route development. The KOSP program created four potential synthetic routes for generating 2,6-dimethylchroman-4-one. In silico screening of these four synthetic routes was then performed. In silico screening involves theoretical analysis of synthetic routes prior to actual experimental work. A synthetic route using the Mitsunobu reaction had already been reported by Hoddgets et al. Theoretical investigations were also conducted on two S(N)Ar reactions as well as a Michael reaction before they were examined experimentally. In silico screening using DFT calculations indicated that only the Michael reaction was likely to produce the target. Experimental work confirmed that the target was obtained in a yield of 76.4% using the Michael reaction. The other two routes, except for the Mitsunobu reaction, failed to generate the target. Our results demonstrate that theoretical calculations can be used to narrow down the number of experiments that need to be conducted when developing novel synthetic routes.

Hydrophobically modified biodegradable poly(ethylene glycol) copolymers that form temperature-responsive Nanogels.

Biodegradable copolymers consisting of a hydrophilic poly[l-aspartic acid-alt-poly(ethylene glycol)] (poly(l-Asp-alt-PEG)) backbone and hydrophobic capryl units as side chains were synthesized. The amphiphilic copolymer was found to form nanosized hydrogel particles (nanogels) of approximately 15 nm in size by self-assembly at 20 degrees C in aqueous media, and the nanogel solutions displayed phase-transition in response to temperature. The transition of the nanogel solution was reversible and tunable in the range from 19 to 55 degrees C by variation of the amounts of capryl units introduced and the solution concentration. The nanogels were gradually degraded within days in a phosphate buffer solution (PBS) at 37 degrees C. Temperature-responsive biodegradable nanogel systems consisting of biocompatible PEG may have potential utility for high biocompatibility temperature-responsive nanodevices such as microreactor systems, molecular-chaperones, and drug delivery vehicles.

Isolation and characterization of microsatellite markers from the hosta species Hosta albomarginata (Liliaceae).

Hostas are very popular ornamental plants in gardens in the United States, Europe, and East Asia. We have developed nine microsatellite loci from an enrichment library of genomic DNA in Hosta albomarginata. We characterized these nine microsatellite loci for 20 individuals from a population of H. albomarginata. The primers developed in this study yielded an average of 12.4 alleles per locus (range five to 20) and an average expected heterozygosity of 0.86 (range 0.65 to 0.95). These markers will be powerful tools for breeding programmes of hosta cultivars, studies of population genetics, and the conservation of wild hosta species.