Functional monomers and polymers. CVIII. Photodimerization of pendant thymine bases in thymine containing poly-lysine derivatives

The photodimerization reaction of pendant thymine bases in thymine-containing poly-lysine derivatives was studied over a wide range in aqueous solution. It was found that the quantum yield of the photodimerization of pendant thymine bases is affected mainly by the conformation of the polymers in solution. The differences in photoreaction behavior were discussed for poly-D -, poly-L -, and poly-DL -lysine derivatives.     

Diastereoselective construction of small building blocksvia [2+2] cycloadditions involving ketenes: A direct incorporation of α-, β-, and γ-amino acids into peptides

Data concerning diastereoselective construction of peptidesvia β-lactams obtained from [2+2] cycloaddition reactions with participation of ketenes are summarized.     

Functional monomers and polymers. CXVII. Photochemical reactions on oligo- and polyethyleneimines containing pendant thymine bases: Effect of the spacer

The photodimerization reaction of thymine bases incorporated in the modified oligo- and polyethyleneimines, in which α-alanine or ß-alanine unit was inserted between the main chain and the pendant thymine bases, was studied both in aqueous and in dimethyl sulfoxide solutions. It was found that the quantum yields for the photodimerization for the oligomers were closely related to the intramolecular interaction in the ground state, while those of the copolymers were not related to the ground state interaction. It was suggested that the singlet energy migration was present in the case of the polyethyleneimine derivatives. This result is discussed in terms of the effects of the nearest-neighboring thymine units, the structure of the side chain, and the singlet energy migration, particularly for the copolymers.     

Functional monomers and polymers. XCIV. Photochemical reactions on the synthetic polymers containing thymine bases in the presence of adenine derivatives

Photodimerization reactions of polyacrylate and polymethacrylate derivatives and the dimer model compound containing thymine bases were studied in the presence of adenine derivatives in dimethyl sulfoxide; N,N-dimethylformamide; and dimethyl sulfoxide–ethylene glycol solutions. The photodimerization of thymine bases both in the polymers and in the dimer model compound was found to be quenched by the addition of adenine derivatives. Base-base interaction in the ground state was also studied by ultraviolet (UV) spectroscopy in the three solvents. The quenching of the photodimerizationof thymine bases in the presence of adenine derivatives was discussed in terms of the specific interaction between adenine and thymine bases both in ground and excited states.     

Functional monomers and polymers. CIV. Synthesis and properties of oligomer models of polyethyleneimine derivatives with spacer-separated nucleic acid bases

A series of polyethyleneimine derivatives and their oligomer models with pendant thymine or adenine bases separated by β-alanyl groups as spacers were prepared by an activated ester method. To elucidate the nature of intramolecular interaction of thymine and adenine bases ultraviolet (UV) spectrophotometric studies were undertaken for the series of compounds and the results were compared with those obtained for the corresponding oligomers without spacers. In the thymine derivatives, the nature of the intramolecular interaction resembled that of the corresponding compounds without β-alanyl units, although larger hypochromicities were found in the series with β-alanyl units. In the adenine derivatives, contrary to the corresponding thymine systems, UV hypochromicities of the compounds decreased by incorporation of the spacer group into side chains. It became evident that the intramolecular interaction of adenine bases was due to stacking neutral species, hydrogen bonding, and residual hypochromicity for the protonated species.     

Mass flows and angular momentum density for px + ipy paired fermions in a harmonic trap

We present a simple two-dimensional model of a p_x + ip_y superfluid in which the mass flow that gives rise to the intrinsic angular momentum is easily calculated by numerical diagonalization of the Bogoliubov-de Gennes operator. We find that, at zero temperature and for constant director l, the mass flow closely follows the Ishikawa-Mermin-Muzikar formula .     

Functional Monomers and Polymers. XLV. Activation Parameters for Polymerization of N-[btilde]-Methacryloyloxyethyl Type Monomers Containing Nucleic Acid Bases

In order to determine the effect of functional structure of ester groups on the stereoregularity of polymers, polymerization of N-[btilde]-methacryloyloxyethyl type monomers containing nucleic acid bases was made by using a free-radical initiator. From the NMR spectrometric determination of the stereoregularity of the polymers obtained, it was found that for polymerization of the monomer with adenine as the side group in dimethyl sulfoxide solution, syndiotactic placement appears to be favored by the additional enthalpy of activation required for isotactic placement.     

Vinyl Polymerization by Metal Complexes. XXXI. Initiation by Chitosan-Copper(II) Complex

The polymerization of methyl methacrylate and acrylonitrile can be initiated by the chitosan-copper(II) complex and its monomeric form, glucosamine-copper(II) complex, in the presence of carbon tetrachloride. The chitosan complex system was found to be more active for initiating the polymerization of methyl methacrylate than acrylonitrile at neutral pH. On the other hand, the glucosamine complex system showed no activity at neutral pH region, but had high activity at higher pH, because of the reducing endgroup of the glucosamine. Formation of the copper(II) complexes was studied by pH titration and visible spectroscopy. The relationship between complex formation and the activity for initiating the polymerization is discussed.     

Photodimerization of Thymine-Containing Polymers: Applicability to Reversible Photoresists

The intramolecular photodimerization of thymine bases present on the side chain of a variety of synthetic oligomers and polymers was studied in detail in various organic solvents, and particularly in the case of thymine-containing polylysines, over a wide range of pH. Effects of solvents, presence of the complementary base, and spacers on the photoreaction were examined, and the conformational changes of the polymers were discussed in relation to their functionalities. Intermolecular photodimerization was further studied, and its applicability to photoresists was shown.     

Deposition of Ethylene-Hexafluoropropene Gradient Plasma-Copolymer Using Dielectric Barrier Discharge Reactor at Atmospheric Pressure: Application to Release Coatings on Pressure-Sensitive Tape

Plasma-polymerized hexafluoropropene (PPHFP) film deposited using a dielectric barrier discharge reactor at atmospheric pressure had low enough adhesive strength, 22.2 Nm^–1, for use as a release coating of pressure-sensitive adhesive tapes, but the bond strength between PPHFP film and a poly (ethylene terephthalate) (PET) substrate film was slightly weak: some part of the PPHFP deposits could be peeled from the PET substrate. Since the XPS results indicated that the bond strength between plasma-polymerized ethylene (PPE) film and PET substrate was strong enough, we tried to deposit PPE and plasma-polymerized ethylene - hexafluoropropene gradient plasma-copolymer between the PET substrate and the PPHFP film. This multi-layer film (MLF) had low enough adhesive strength, 36.6 Nm^–1, for use as the release coating; this value was near that of a control sample, Teflon sheet, 21.6 Nm^–1. Moreover, the bond strength between MLF and PET substrate became stronger than that between PPHFP and PET films.