Thermosensitive polyalcohols: Synthesis via living cationic polymerization of vinyl ethers with a silyloxy group

Thermosensitive homopolymers and copolymers with hydroxy groups were synthesized via the living cationic polymerization of Si‐containing vinyl ethers. The cationic homopolymerization and copolymerization of five vinyl ethers with silyloxy groups, each with a different spacer length, were examined with a cationogen/Et_1.5AlCl_1.5 initiating system in the presence of an added base. When an appropriate base was added, the living cationic polymerization of Si‐containing monomers became feasible, giving polymers with narrow molecular weight distributions and various block copolymers. Subsequent desilylation gave well‐defined polyalcohols, in both water‐soluble and water‐insoluble forms. One of these polyalcohols, poly(4‐hydroxybutyl vinyl ether), underwent lower‐critical‐solution‐temperature‐type thermally induced phase separation in water at a critical temperature (T_PS) of 42 °C. This phase separation was quite sensitive and reversible on heating and cooling. The phase separation also occurred sensitively with random copolymers of thermosensitive and hydrophilic or hydrophobic units, the T_PS values of which in water could be controlled by the monomer feed ratio. The thermal responsiveness of this polyalcohol unit made it possible to prepare novel thermosensitive block and random copolymers consisting solely of alcohol units. One example prepared in this study was a 20 wt % aqueous solution of a diblock copolymer consisting of thermosensitive poly(4‐hydroxybutyl vinyl ether) and water‐soluble poly(2‐hydroxyethyl vinyl ether) segments, which transformed into a physical gel above 42 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3300–3312, 2003     

Nanoparticles in Emissions and Atmospheric Environment: Now and Future

Journal of Nanoparticle Research -     

A generating function of higher-dimensional Apostol-Zagier sums and its reciprocity law

We introduce higher-dimensional Dedekind sums with a complex parameter z, generalizing Zagier's higher-dimensional Dedekind sums. The sums tend to Zagier's higher-dimensional Dedekind sums as z→∞. We show that the sums turn out to be generating functions of higher-dimensional Apostol-Zagier sums which are defined to be hybrids of Apostol's sums and Zagier's sums. We prove reciprocity law for the sums. The new reciprocity law includes reciprocity formulas for both Apostol and Zagier's sums as its special case. Furthermore, as its application we obtain relations between special values of Hurwitz zeta function and Bernoulli numbers, as well as new trigonometric identities.     

Photoelectron spectroscopic study of simple hydrogen-bonded dimers. I. Supersonic nozzle beam photoelectron spectrometer and the formic-acid dimer

In this paper we describe several characteristics of our supersonic nozzle beam photoelectron spectrometer recently constructed for studying hydrogen-bonded dimers in the gas phase by HeI (58.4 nm) radiation. Using this photoelectron apparatus, we have reinvestigated the HeI photoelectron spectrum of the formic-acid dimer (HCOOH)₂ which is well known as a fairly strong doubly hydrogen-bonded dimer. It was found that the (HCOOH)₂ spectrum deduced here from the spectrum of the monomer—dimer mixture considerably differs from that reported by Carnovale et al. in the region beyond 16.5 eV. New spectral assignments are given for four ionization bands beyond 16.5 eV. It is also indicated that the lower bound of the dissociation energy of (HCOOH)₂⁺ is estimated to be 1.0 ± 0.1 eV from the threshold of the dimer band (11.0 eV) obtained in this experiment. This value is considerably smaller than the value of 1.7 ± 0.2 eV recently reported for the water dimer cation (H₂O)₂⁺.     

Aerosol Generation Method for Measuring Particles Suspended in Water – Detection of Particulate Impurities in Ultrapure Water and Sizing of Fine Powders –

The method described is based on the fact that the measurement of particles in the gaseous phase is generally easier than that in the liquid phase for fine particles smaller than 1 μm in diameter. The system consists of a liquid nebulizing unit, evaporator, condenser, mixing diluter and two different aerosol sizing instruments. It has been found that this method can continuously detect particulate impurities in ultrapure water in situ and can measure the size distribution of fine powders in the submicron particle size range down to about 0.05 μm.     

A trifluoromethanesulfonic acid-catalyzed reaction of arylhydrazines with benzene

Arylhydrazines reacted with benzene in the presence of trifluoromethanesulfonic acid (TFSA) to give aminobiphenyls. This is a general method for the synthesis of aminobiphenyls.