Variation of free volume parameters of polyalkylmethacrylate derivatives in the range from 15 to 300 K probed by positron annihilation lifetime measurement

Positron annihilation lifetime measurements of PMMA, PEMA, PiPMA, PnPMA and PnBMA were performed in the temperature range between 15 and 300 K, where , and relaxational transitions occur for these polyalkylmethacrylates. The variations of free volume size and content calculated from the longest lifetime component against temperature are correlated to the results obtained by dielectric, viscoelastic and dynamic mechanical relaxation data of the polymers. The variations of free volume sizes and contents, apparent free volume fraction and size distribution of the polyalkylmethacrylates are well correlated with the rotational transitions of side chains. The location of free volumes, in which positronium annihilates can be estimated near the vicinity of alkyl groups bound to oxygen atom of side ester chains.     

Mössbauer and ESR study of the formation of phthalocyanineiron(II) pyridine adduct in the supercage of NaY,KY, and RbY zeolite

Phthalocyanineiron(II) (FePc) and phthalocyaninato[(2-)bispyridine]iron(II) (FePc(py)₂) synthesized in supercage of NaY, KY and RbY zeolite have been characterized by Mössbauer and ESR spectroscopy. The yield of formation of the pyridine adduct depends on the ionic radius of the alkali ions introduced into the supercage, but not on the number of iron ions trapped in the cages, suggesting that free space in the supercage was the most important factor for the formation of the FePc-py-adducts.     

A conducting crystal based on a single-component paramagnetic molecule, [Cu(dmdt)(2)] (dmdt = dimethyltetrathiafulvalenedithiolate)

A single-component conducting molecular crystal composed of paramagnetic copper complexes, [Cu(dmdt)2]0+, was prepared. The crystal has an unprecedented three-dimensionally packed molecular arrangement and exhibits a fairly high conductivity (1 S cm-1 at room temperature). The magnetic susceptibility measurements revealed that [Cu(dmdt)2]0+ molecule keeps most of S = 1/2 spin moments. The difference of the bond lengths between [Cu(dmdt)2]0+ and [Cu(dmdt)2]2- is consistent with the result of the molecular orbital calculation.     

Polyaddition reaction of biscarbodiimides. II. Synthesis of polyguanidines by polyaddition reaction of biscarbodiimides with diamines

A series of polyguanidines was prepared by the polyaddition reaction of biscarbodiimides with diamines. The polyaddition reaction was carried out in solution. The polymers thus obtained had intrinsic viscosities up to 0.84 and molecular weights up to 15000. The structure of the polymers was identified by comparison of their infrared spectra with those of model compounds, elementary analysis, and a study of the reaction conditions. Thermogravimetric study indicated that the polyguanidines decomposed over 170°C under nitrogen. The polyguanidines were highly resistant to hydrolytic degradation by strong acid or alkali. The polyguanidines had basic groups and formed stable hydrochloric salts when they were treated with hydrochloric acid.     

Synthesis and metal-ion binding properties of monoazathiacrown ethers

Synthetic procedures for monoazathiacrown ethers were explored, and monoazatrithia-12-crown-4, monoazatetrathia-15-crown-5, and monoazapentathia-18-crown-6 were obtained in moderate yields by the reaction of bis(2-chloroethyl)amine with the appropriate dithiols in the presence of lithium hydroxide in THF. To evaluate metal-ion binding properties of the monoazathiacrown ethers by solvent extraction, lipophilic dodecyl and dodecanoyl groups were incorporated onto the monoazathiacrown ethers. The solvent extraction experiments suggested that monoazathiacrown ethers have Ag(+) and Hg(2+) selectivities and that the relative selectivity between Ag(+) and Hg(2+) depends on their nitrogen atom properties and numbers of sulfur atoms reflecting the respective affinities of nitrogen and sulfur atoms to Hg(2+) and Ag(+). An interesting ability to bind Mg(2+) was observed in the case of N-dodecyl monoazatrithia-12-crown-4.     

Structural features of aliphatic N-nitrosamines of 7-azabicyclo[2.2.1]heptanes that facilitate N-NO bond cleavage

N-Nitrosamines can be considered as potential nitric oxide (NO)/nitrosonium ion (NO(+)) donors. However, the relation of the structures of N-nitrosamines, in particular of aliphatic N-nitrosamines, to the characteristics of release of NO or NO(+) remains unclear. Here we show that aliphatic N-nitrosoamines of 7-azabicyclo[2.2.1]heptanes can undergo heterolytic N-NO bond cleavage. On the basis of the observation of reduced rotational barriers of the N-NO bonds in solution and nitrogen-pyramidal structures of the N-nitroso group in the solid state, we postulate that N-NO bond cleavage of N-nitrosamines is enhanced by a reduction of the resonance in the N-NO group. Computational studies suggest that these structural features of the N-nitrosamines of 7-azabicyclo[2.2.1]heptane are derived from angle strain imposed on the CNC angles.     

Enantioselective crystallization of D,L-amino acids induced by spontaneous asymmetric resolution of D,L-asparagine

Racemic D,L-asparagine induced spontaneous asymmetric resolution of co-existing D,L-phenylalanine or D,L-tryptophan by recrystallization from a homogeneous aqueous solution, and the enantiomeric excess of phenylalanine or tryptophan in the resulting crystals correlated linearly with that of asparagine crystallized with phenylalanine or tryptophan.