Alternative copolymerization of aziridines and carbon monoxide by γ-ray irradiation

The copolymerization of carbon monoxide and aziridines such as ethylenimine and propylenimine was carried out by γ-ray irradiation. Aziridines and carbon monoxide were allowed to copolymerize under γ-ray irradiation from a Co⁶⁰ source and gave a crystalline solid copolymer. The yield of the copolymer increased with reaction temperature. The composition of copolymers obtained did not depend on the feed ratio of monomers and was found to be almost equimolar. The copolymer of ethylenimine and carbon monoxide melted at about 322–335°C. with decomposition and has an infrared spectrum identical with that of poly-β-alanine obtained by the hydrogen-migration polymerization of acrylamide. The hydrolyzed product of the ethylenimine–carbon monoxide copolymer was confirmed to be β-alanine by paper chromatography. These results lead to the conclusion that the copolymerization of aziridines and carbon monoxide took place alternatively by γ-ray irradiation, and produced crystalline poly-β-alanines.     

Cationic polymerization of formaldehyde in liquid carbon dioxide. Part II: A kinetic study of the polymerization

The kinetic behavior on the polymerization of formaldehyde with and without acidic catalyst, in liquid carbon dioxide, in the temperature range of 30 to 50°C. was investigated. In the polymerization without catalyst both the polymer yield and the degree of polymerization increased with reaction time and also with rising temperature. With acidic catalyst, such as acetic acid and dichloroacetic acid, both the polymer yield and the degree of polymerization increased more than that in the polymerization without catalyst. The overall rate of polymerization with and without acidic catalyst was expressed by the first-order rate equation with respect to monomer concentration. From the results it was concluded that the polymerizations belonged to a type of successive polymerization with rapid initiation and no termination. The rate constant and the activation energy of each elementary process of polymerization were estimated on the basis of the results.     

NMR assignment methods for the aromatic ring resonances of phenylalanine and tyrosine residues in proteins

The unambiguous assignment of the aromatic ring resonances in proteins has been severely hampered by the inherently poor sensitivities of the currently available methodologies developed for uniformly 13C/15N-labeled proteins. Especially, the small chemical shift differences between aromatic ring carbons and protons for phenylalanine residues in proteins have prevented the selective observation and unambiguous assignment of each signal. We have solved all of the difficulties due to the tightly coupled spin systems by preparing regio-/stereoselectively 13C/2H/15N-labeled phenylalanine (Phe) and tyrosine (Tyr) to avoid the presence of directly connected 13C-1H pairs in the aromatic rings. The superiority of the new labeling schemes for the assignment of aromatic ring signals is clearly demonstrated for a 17 kDa calcium binding protein, calmodulin.     

Cationic polymerization of formaldehyde in liquid carbon dioxide. Part I

A cationic polymerization of formaldehyde which gave a high molecular weight polymer was studied in liquid carbon dioxide at 20–50°C. In the polymerization without any catalyst both the rate of polymerization and the molecular weight of the resulting polymer increased rapidly with a decrease in the loading density of the monomer solution to the reaction vessel, and also increased with an increase in the initial monomer concentration. From these results it was concluded that the initiating species could be ascribed to an impurity contained in the monomer solution. Both the rate of polymerization and the degree of polymerization of the polymer also increased with rising temperature. The carboxylic acid added acted as a catalyst in the polymerization because of increase in the polymer yield, the molecular weight of polymer formed, and the number of moles of polymer chain with increasing dissociation constant of acid used. It was concluded that the polymerization in liquid carbon dioxide proceeded by a cationic mechanism. Methyl formate had no influence on the polymerization, but methanol and water acted as a chain-transfer agent.     

Synthesis of stereoarray isotope labeled (SAIL) lysine via the "head-to-tail" conversion of SAIL glutamic acid

A stereoarray isotope labeled (SAIL) lysine, (2S,3R,4R,5S,6R)-[3,4,5,6-(2)H(4);1,2,3,4,5,6-(13)C(6);2,6-(15)N(2)]lysine, was synthesized by the "head-to-tail" conversion of SAIL-Glu, (2S,3S,4R)-[3,4-(2)H(2);1,2,3,4,5-(13)C(5);2-(15)N]glutamic acid, with high stereospecificities for all five chiral centers. With the SAIL-Lys in hand, the unambiguous simultaneous stereospecific assignments were able to be established for each of the prochiral protons within the four methylene groups of the Lys side chains in proteins.     

Determination of peptide φ angles in solids by relayed anisotropy correlation NMR

A solid state NMR method is presented for determination of a backbone dihedral angle φ in peptides, being based on the previously reported method, relayed anisotropy correlation (RACO) NMR [Y. Ishii et al., Chem. Phys. Lett. 256 (1996) 133]. In the present method, the and the dipolar tensors in the system are two-dimensionally (2D) correlated via polarization transfer from to under magic angle spinning (MAS). This method was applied to N-acetyl , -valine, and the H–C–N–H dihedral angle was determined to be 154.0±1.4° or 206.0±1.4°, the former agreeing with the X-ray value of 154±5°.