Direct polyesterification with thionyl chloride in pyridine improved by a modification of monomer sequences in copolymers

The direct polyesterification with thionyl chloride (SOCl₂) in pyridine was further investigated. Copolycondensations of dicarboxylic acids, bisphenols, and hydroxybenzoic acids were significantly affected by the reaction temperatures and combinations of monomers which could change relative rates of alcoholyses of the activated dicarboxylic acids and the hydroxyacids consequently to vary monomer sequences in the copolymers resulted. The sequences were tried to be varied more directly by stepwise reactions of monomers in copolycondensations of dicarboxylic acids, bisphenols, and p-hydroxybenzoic acid (PHB), as well as PHB and m-hydroxybenzoic acid (MHB). The reactions proceeded smoothly and satisfactorily when carried out by initial reaction of dicarboxylic acids and PHB followed by bisphenols likely to favor sequential to random distributions of monomers. Reverse addition of PHB and bisphenols, and then dicarboxylic acids resulted in rapid precipitation due to some oligomerization of PHB at an earlier stage of reaction, and largely retarded the reaction. This was also the case for the copolycondensation of PHB and MHB. Copolymers of high inherent viscosities with up to 65 mol% PHB could be obtained by initial reaction of MHB followed by PHB.     

Induction of a remarkable conformational change in a human telomeric sequence by the binding of naphthyridine dimer: inhibition of the elongation of a telomeric repeat by telomerase

The binding of a dimeric form of the 2-amino-1,8-naphthyridine derivative (naphthyridine dimer) to a human telomeric sequence, TTAGGG, was investigated by UV melting, CD spectra, and CSI-MS measurements. Both the 9-mer d(TTAGGGTTA) and the 15-mer d(TTAGGGTTAGGGTTA) showed apparent melting temperatures (T(m)) of 45.6 and 63.6 degrees C, respectively, in the presence of naphthyridine dimer (30 microM) in sodium cacodylate buffer (50 mM, pH 7.0) containing 100 mM NaCl. The CD spectra at 235 and 255 nm of the 9-mer increased in intensity accompanied with strong induced CDs at 285 and 340 nm upon complex formation with naphthyridine dimer. UV titration of the binding of naphthyridine dimer to the 9-mer at 320 nm showed a hypochromism of the spectra. A Scatchard plot of the data showed the presence of multiple binding sites with different association constants. Cold spray ionization mass spectrometry of the complex between naphthyridine dimer and the 9-mer clearly showed that one to three molecules of the ligand bound to the dimer duplex of the 9-mer. Telomeric repeat elongation assay showed that the binding of naphthyridine dimer to the telomeric sequence inhibits the elongation of the sequence by telomerase.     

Regioselective Borylation of Porphyrins by C?H Bond Activation under Iridium Catalysis to Afford Useful Building Blocks for Porphyrin Assemblies

Highly regioselective and efficient borylation of a variety of porphyrins has been achieved by reaction with bis(pinacolato)diboron through C? H bond activation under iridium catalysis on the basis of the synthetic protocol developed by Miyaura, Hartwig, and Smith. A boryl group can be selectively introduced at sterically uncongested positions in the peripheral aryl groups of porphyrin substrates whose peripheral β‐positions are sterically hindered. Curiously, β substituents adjacent to the aryl group to be borylated have unexpectedly large effects on the regioselectivity, because the iridium catalyst can discriminate between subtle steric differences. Chemoselective borylation was also achieved for several functionalized porphyrins. This borylation protocol can be applied to various monomeric and oligomeric functional porphyrins, hence offering an efficient route to elaborate multiporphyrin‐based molecular constructs.     

Hydrogen bonding in macrocyclic receptor systems

Abstract

The interactions of macrocyclic polyethers with alkali and alkaline earth cations have been well studied and much about their chemistry is now well understood. Less well examined or comprehended are hydrogen bond interactions. A combination of ion selective electrode binding constant determination techniques and fast atom bombardment mass spectrometry are brought to bear on this problem. It is found that all-oxygen crown ethers and their derivatives exhibit quite different complexation behaviour with ammonium salts than do their various azacrown counterparts.     

Synthesis of ZrO<Subscript>2</Subscript> nanoparticles for liquid scintillators used in the detection of neutrinoless double beta decay

We synthesized liquid scintillators incorporating ZrO₂ nanoparticles for application in neutrinoless double beta decay experiments. ZrO₂ nanoparticles of less than 10 nm in size were synthesized with sub- and supercritical hydrothermal methods. The Zr concentrations in the liquid scintillators were determined to be up to 1.4 wt% with inductively coupled plasma analysis, and the liquid scintillators were transparent to scintillation. These results indicate that these methods are applicable for the preparation of liquid scintillators for neutrinoless double beta decay experiments.     

Convenient Synthesis of Cerpegin

A convenient procedure for the preparation of cerpegin is described.