TG-DTA/FT-IR method for analyzing thermal decomposition mechanism of polyesters

An attempt to estimate the thermal decomposition mechanism of polymers using the simultaneous TG-DTA/FT-IR system was summarized. The library search of FT-IR spectra at various temperatures and of the subtraction spectrum obtained by subtracting the spectra at different temperatures were used to determine the types of evolved gases from poly(ethylene terephthalate) and poly(butylene terephthalate) at given stages of decomposition. The quantitative analysis of evolved gases was carried out using the specific gas profiles at the specific absorption band. The kinetic parameters were estimated from both TG and spectroscopic curves measured at various heating rates.     

Formation and Physicochemical Features of Hybrid Threadlike Micelles in Aqueous Solution

We investigate the construction of long, stable hybrid threadlike micelles consisting of polyelectrolytes and oppositely charged surfactants in aqueous solution and examine the physicochemical features such as their structure and viscoelastic behavior in aqueous solution. The most important point for their construction is the careful control of interactions, especially electrostatic interactions, caused between the surfactants and polyelectrolytes. Incorporated polyelectrolytes are fully extended in these hybrid threadlike micelles irrespective of the molecular weight of the polymer. The viscoelastic behavior of the hybrid threadlike micellar solution is similar to that of ordinary threadlike micellar systems consisting of low‐molecular‐weight substances. However, the inclusion of polymers in the micelles causes differences in their mechanical properties.     

X-ray crystal structure analyses and atomic charges of color former and developer. I. Color developers

The crystal and molecular structures of 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A, BPA) (1), benzyl 4-hydroxybenzoate (2), 1,7-bis(4-hydroxyphenylthio)-3,5-dioxaheptane (3) and 4-hydroxyphenyl 4-isopropoxyphenyl sulfone (4) have been determined by X-ray crystal structure analysis. Theoretical calculations of the steric hindrance and semiempirical quantum chemical calculations to determine the color characteristics have been carried out. It is clear that the energy barriers for the variation of the orientation of phenol group in 1 to 4 are due to steric hindrance caused by the other moiety and the peak profiles are due to repulsive interactions of the other moiety. Net atomic charges on the hydrogen of the OH group are larger than those on the other atoms in the molecules. This high electron charge of the para orientation will cause the different thermosensitivity and stabilization.     

Study of a high-dimensional chaotic attractor

The nature of a very high-dimensional chaotic attractor in an infinite-dimensional phase space is examined for the purpose of studying the relationships between the physical processes occurring in the real space and the characteristics of high-dimensional attractor in the phase space. We introduce two complementary bases from which the attractor is observed, one the Lyapunov basis composed of the Lyapunov vectors and the another the Fourier basis composed of the Fourier modes. We introduce the exterior subspaces on the basis of the Lyapunov vectors and observe the chaotic motion projected onto these exteriors. It is shown that a certain statistical property of the projected motion changes markedly as the exterior subspace goes out of the attractor. The origin of such a phenomenon is attributed to more fundamental features of our attractor, which become manifest when the attractor is observed from the Lyapunov basis. A counterpart of the phenomenon can be observed also on the Fourier basis because there is a statistical one-to-one correspondence between the Lyapunov vectors and the Fourier modes. In particular, a statistical property of the high-pass filtered time series reflects clearly the difference between the interior and the exterior of the attractor.     

On subharmonic functions dominated by certain functions

Given two kinds of functionsf(X) andh(y) defined on them-dimensional Euclidean spaceR ^m (m≧1) and the set of positive real numbers respectively, we give an estimation of growth of subharmonic functionsu(P) defined onR ^m+n (n≧1) such that $$u(P) \leqq f\left( X \right)h\left( {\left\| Y \right\|} \right)$$ for anyP=(X, Y),X ∈R ^m, Y ∈R ⁿ, where ‖Y ‖ denotes the usual norm ofY. Using an obtained result, we give a sharpened form of an ordinary Phragmén-Lindelöf theorem with respect to the generalized cylinderD ×R ⁿ, with a bounded domainD inR ^m.     

Syntheses of TiO2(B) nanowires and TiO2 anatase nanowires by hydrothermal and post-heat treatments

TiO₂(B) nanowires and TiO₂ anatase nanowires were synthesized by the hydrothermal processing in 10 M NaOH aq. at 150 °C followed by the post-heat treatment at 300-800 °C. As-synthesized Na-free titanate nanowires (prepared by the hydrothermal treatment and repeated ion exchanging by HCl (aq.) were transformed into TiO₂(B) structure with maintaining 1-D morphology at 300-500 °C, and further transformed into anatase structure at 600-800 °C with keeping 1-D shape. At 900 °C, they transformed into rod-shaped rutile grains. Microstructure of these 1-D TiO₂ nanomaterials is reported.     

New stage in living cationic polymerization: An array of effective Lewis acid catalysts and fast living polymerization in seconds

Our recent extensive research on Lewis acid catalysts with a weak base for the cationic polymerization of vinyl ethers led to unprecedented living reaction systems: fast living polymerization within 1–3 s; a wide choice of metal halides containing Al, Sn, Fe, Ti, Zr, Hf, Zn, Ga, In, Si, Ge, and Bi; and heterogeneously catalyzed living polymerization with Fe₂O₃. The use of added bases for the stabilization of the propagating carbocation and the appropriate selection of Lewis acid catalysts were crucial to the success of such new types of living polymerizations. In addition, the base‐stabilized living polymerization allowed the quantitative synthesis of star‐shaped polymers with a narrow molecular weight distribution via polymer‐linking reactions and the precision synthesis and self‐assembly of stimuli‐responsive block copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1801–1813, 2007.     

Host-guest interactions in the supramolecular incorporation of fullerenes into tailored holes on porphyrin-modified gold nanoparticles in molecular photovoltaics

Novel gold nanoparticles modified with a mixed self-assembled monolayer of porphyrin alkanethiol and short-chain alkanethiol were prepared (first step) to examine the size and shape effects of surface holes (host) on porphyrin-modified gold nanoparticles. The porphyrin-modified gold nanoparticles with a size of about 10 nm incorporated C60 molecules (guest) into the large, bucket-shaped holes, leading to the formation of a supramolecular complex of porphyrin-C60 composites (second step). Large composite clusters with a size of 200-400 nm were grown from the supramolecular complex of porphyrin-C60 composites in mixed solvents (third step) and deposited electrophoretically onto nanostructured SnO2 electrodes (fourth step). Differences in the porphyrin:C60 ratio were found to affect the structures and photoelectrochemical properties of the composite clusters in mixed solvents as well as on the SnO2 electrodes. The photoelectrochemical performance of a photoelectrochemical device consisting of SnO2 electrodes modified with the porphyrin-C60 composites was enhanced relative to a reference system with small, wedged-shaped surface holes on the gold nanoparticle. Time-resolved transient absorption spectroscopy with fluorescence lifetime measurements suggest the occurrence of ultrafast electron transfer from the porphyrin excited singlet states to C60 or the formation of a partial charge-transfer state in the composite clusters of supramolecular complexes formed between porphyrin and C60 leading to efficient photocurrent generation in the system. Elucidation of the relationship between host-guest interactions and photoelectrochemical function in the present system will provide valuable information on the design of molecular devices and machines including molecular photovoltaics.     

Photopolymerization of methyl methacrylate in the presence of tertiary amines

The sensitization effect of tertiary amines on the photopolymerization of methyl methacrylate was studied. N,N-Dimethylbenzylamine, triethylamine, and N,N-dimethylaniline increased the rate of polymerization in this order, but pyridine did not show any effect. A free-radical mechanism was confirmed by the tacticity of polymer, the retarding effect of hydroquinone, and the copolymer composition with styrene. On the basis of the detailed kinetics of the sensitized polymerization and the ultraviolet spectra of the reaction mixtures, a sensitization mechanism is proposed, in which the excited monomer and the amine form a complex and generate an initiating radical.