Radical Polymerizability of 6-Methyl-2-vinyl-3-pyridazinone in Protic Media

Abstract

Radical copolymerizability of 6-methyl-2-vinyl-3-pyridazinone (I) has been reinvestigated in acetic acid and also in the presence of polyacrylic acid (PAA). Copolymerization of styrene with I was carried out in a few solvents. A positive e₂ value was obtained in acetic acid while negative ez values were obtained in benzene and DMF. I was allowed to copolymerize with a few monomers such as styrene, methyl methacrylate, and acrolein in the presence of PAA to give block-type copolymers. All these observations indicate that polymerizability of I is controlled by the hydrogen bonding interaction between the carbonyl group of I and the hydroxyl group of the additive.     

Frustration-induced eta inversion in the S=1/2 bond-alternating spin chain

We study the frustration-induced enhancement of the incommensurate correlation for a bond-alternating quantum spin chain in a magnetic field, which is associated with a quasi-one-dimensional organic compound F5PNN. We investigate the temperature dependence of the staggered susceptibilities by using the density matrix renormalization group, and then find that the incommensurate correlation becomes dominant in a certain range of the magnetic field. We also discuss the mechanism of this enhancement on the basis of the mapping to the effective S=1/2 XXZ chain and a possibility of the field-induced incommensurate long-range order.     

Conformational and neighboring effects in graft polymerization of acrolein on 4(5)-vinylimidazole-acrylamide copolymer

The graft polymerization of acrolein (AL) on poly-4(5)-vinylimidazole or the copolymers of 4(5)-vinylimidazole(VIm) and acrylamide of varying composition were carried out kinetically in an ethanol–water mixture at 0°C. The graft polymerization rate R_p increased with an increasing concentration of water in the solvent. On the other hand, the R_p of the copolymer which incorporated 50 mol % VIm showed the highest value. These results were discussed by assuming interaction between amide and imidazole groups in copolymer.     

Effects of solvent on the free-radical copolymerizabilities of pyridazinones with styrene

Free-radical copolymerizations of N-methylpyridazinone (I) and N-phenylpyridazinone (II) with styrene (M₁) were carried out in various solvents. The copolymerization rates were found to increase linearly with increasing viscosities of the reaction mixtures. Monomer reactivity ratios were strongly affected by the reaction media. This might be due to solvation of the carbonyl group of the pyridazinone ring, because linear relationships between log 1/r1 and vc=o of the pyridazinones were obtained. It was also found that monomer concentration influences these copolymerizabilities.     

Tandem trimer pyrrole–imidazole polyamide probes targeting 18 base pairs in human telomere sequences

The binding of molecules to specific DNA sequences is important for imaging genome DNA and for studying gene expression. Increasing the number of base pairs targeted by these molecules would provide greater specificity. N-Methylpyrrole–N-methylimidazole (Py–Im) polyamides are one type of such molecules and can bind to the minor groove of DNA in a sequence-specific manner without causing denaturation of DNA. Our recent work has demonstrated that tandem hairpin Py–Im polyamides conjugated with a fluorescent dye can be synthesized easily and can serve as new probes for studying human telomeres under mild conditions. Herein, to improve their selectivities to telomeres by targeting longer sequences, we designed and synthesized a fluorescent tandem trimer Py–Im polyamide probe, comprising three hairpins and two connecting regions (hinges). The new motif bound to 18 bp dsDNA in human telomeric repeats (TTAGGG)_n, the longest sequence for specific binding reported for Py–Im polyamides. We compared the binding affinities and the abilities to discriminate mismatch, the UV-visible absorption and fluorescence spectra, and telomere staining in human cells between the tandem trimer and a previously developed tandem hairpin. We found that the tandem trimer Py–Im polyamide probe has higher ability to recognize telomeric repeats and stains telomeres in chemically fixed cells with lower background signal.