Anionic grafting polymerization of propylene sulfide onto human hair in water

Natural human hair was modified by the graft polymerization of propylene sulfide in an aqueous medium. The amount of the polymer grafted onto the reduced hair was 0.15–0.19 g on 1.0 g of hair. The grafted polymer was isolated by the hydrolysis of the hair in the polymer‐grafted hair under basic conditions and was confirmed to be poly(propylene sulfide) by ¹H NMR, ¹³C NMR, and Fourier transform infrared spectra. The number‐average molecular weights of the isolated polymers from the grafted products were 10,000–12,000. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3778–3786, 2006     

Synthesis of copolymers containing a spiro orthocarbonate moiety and evaluation of the volume change during their cationic crosslinking

Spiro orthocarbonate (SOC) monomers having either an exomethylene group {3,3‐dimethyl‐9‐methylene‐1,5,7,11‐tetraoxaspiro[5.5]undecane (ExoSOC)} or an allyl group {9‐allyl‐3,3‐dimethyl‐1,5,7,11‐tetraoxaspiro[5.5]undecane (AllylSOC)} were radically copolymerized with vinyl monomers at several feed ratios to obtain the corresponding copolymers having SOC moieties in the side chain. The obtained copolymers were crosslinked via the double ring‐opening polymerization of the SOC moieties by a treatment with boron trifluoride etherate. The volume changes during the crosslinking of the copolymers were evaluated by density measurements with a gas pycnometer. As the SOC moiety composition increased, the volume shrinkage during the crosslinking was suppressed, and that finally changed into volume expansion. The volume changes during the crosslinking of the copolymers from AllylSOC were slightly larger than those of the copolymers from ExoSOC. The higher volume expansions in the crosslinking of AllylSOC‐based copolymers were ascribable to the lower steric hindrance around the SOC moieties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 7040–7053, 2006     

New Chiral Kemp's Acid Diamides for Chiral Amine Recognition by 1 H NMR

Two Kemp's acid diamides were synthesized and applied to chiral amine recognition using ¹H NMR analysis. One derivative based on 1-(1-naphthyl)ethylamine had good chiral recognition of six amines and was useful to determine the optical purity for three amines, i.e., methylbenzylamine, 1-(1-naphthyl)ethylamine and 1- henylpropylamine,however, the cyclohexylethylamine derivative showed little discrimination for the amines studied. Together with the results for alkylamines, it was shown that aromatic structure was important for aromatic shielding anisotropy and –– interactions between host and guest. The structure of the 1-(1-naphthyl)ethylamine derivative in solution was also considered based on ¹H NMR data and computer simulation.     

Tetrakis-acridinyl peptide: a novel fluorometric reagent for nucleic acid analysis based on the fluorescence dequenching upon DNA binding

Tetrakis-acridinyl peptide 1 assuming a right-handed helical stacked conformation of the acridinyl units can bind to DNA duplex with a very high affinity of 10(8) (M-bp)(-1) even at a high salt concentration of 0.2 M NaCl, irrespective of the base composition. Peptide 1 gave rise to 1600-times enhancement of its fluorescence upon binding to an AT polymer due to the collapse of this stacked structure, but the fluorescence is not enhanced with a GC polymer, though the binding constants of 1 for both polymers were the same.     

Pressure response of Raman spectra of water and its implication to the change in hydrogen bond interaction

In situ Raman spectroscopic measurements of water in the region of OH vibration were conducted up to 0.4 GPa at 23 and 52 degrees C. The frequencies of the decomposed OH stretching bands initially decreased with increasing pressure, reached a minimum at 0.15 GPa and increased up to 0.3 GPa and then decreased, which corresponds to the variations of the strength of hydrogen bonding. This variation was observed at 23 degrees C, but not at 52 degrees C, which suggests a change in pressure dependence on the hydrogen bond interaction between these two temperatures. Based on the equilibration model between hydrogen-bonded and nonhydrogen-bonded molecules, the present experimental results indicate that the pressure variation of the viscosity depends on the ratio of hydrogen-bonded molecules, rather than the strength of hydrogen bonding between molecules.     

Photodimerization of benzene -photochromism of layered dithiacyclophane-

A novel cage compound was obtained by irradiation of a quadruple-layered dithiacyclophane and showed thermally reverse reaction.     

Thermolysis of reactive oligo(p-phenylene sulfide) containing disulfide bond

Oligo(phenylene sulfide) (OPS) containing one disulfide bond at the end of the chain, which was obtained by the oxidative polymerization of diphenyl disulfide, had a relatively low Td_10%(temperature for 10% weight loss) of 412 °C because of degradation of the disulfide bond. But this thermal cleavage of the disulfide bond promoted the curing reaction through thiophenoxy radical formation. OPS was allowed to react with diiodobenzene at 220 °C. The thermal stability of OPS was improved through the consumption of the disulfide bond and the coupling of the chain.     

Borderline of hydrogen bonding of silanols

Two new silanols bearing very bulky silyl groups, (i-Pr₃ Si)₃SiOH and (t − BuMe₂Si)₃SiOH were prepared by peracidoxidation of their respective silanes. The X − ray crystallographic analysis revealed that (t − BuMe₂Si)₃ SiOH forms a dimeric structure with hydrogen bonding, while (i − Pr₃ Si)₃ SiOH exists as a monomer in the crystal. The effects of the size of the substituents as well as the reactivity of these silanols are discussed.