Study of molecular motion of block copolymers in solution by high-resolution proton magnetic resonance

Molecular motions of hydrophobic–hydrophilic water-soluble block copolymers in solution were investigated by high-resolution proton magnetic resonance (NMR). Samples studied include block copolymers of polystyrene–poly(ethylene oxide), polybutadiene–poly(ethylene oxide), and poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide). NMR measurements were carried out varying molecular weight, temperature, and solvent composition. For AB copolymers of polystyrene and poly(ethylene oxide), two peaks caused by the phenyl protons of low-molecular-weight (M?_n = 3,300) copolymer were clearly resolved in D₂O at 100°C, but the phenyl proton peaks of high-molecular-weight (M?_n = 13,500 and 36,000) copolymers were too broad to observe in the same solvent, even at 100°C. It is concluded that polystyrene blocks are more mobile in low-molecular-weight copolymer in water than in high-molecular-weight copolymer in the same solvent because the molecular weight of the polystyrene block of the low-molecular-weight copolymer is itself small. In the mixed solvent D₂O and deuterated tetrahydrofuran (THF-d₈), two peaks caused by the phenyl protons of the high-molecular-weight (M?_n = 36,000) copolymer were clearly resolved at 67°C. It is thought that the molecular motions of the polystyrene blocks are activated by the interaction between these blocks and THF in the mixed solvent.     

Mechanical relaxations in some ionene polymers. II. Influence of counterions and absorbed water

Six 6,10-ionenes with different counterions were prepared by ion exchange reactions in aqueous solutions. The counterions were Br, I, CIO₄, BF₄, SCN, and B(C₆H₅)₄. The dynamic mechanical properties of these polymers were investigated by use of a torsional braid analyser. Three relaxations α (25–140°C), β (?30–0°C), and γ (?140–120°C) were observed at the frequencies of 0.3–0.8 Hz. The temperature of the α and β relaxations were largely dependent on the size of counterions, but those of the γ relaxations had little variation. The effects of electrostatic forces in the polymers on each relaxation was discussed. The influence of absorbed water on the α, β, and γ relaxations was examined. The absorbed water in the polymers greatly depressed the temperature of the α relaxations and this phenomenon was interpreted to be the result of the specific hydration on ionic portions.     

Solvent-induced morphological change of microporous hollow fiber membranes

Microporous polyethylene hollow fiber membranes (EHF-1 and EHF-2) were subjected to solvent treatment, and the effects of this treatment on membrane morphology and permeating properties were studied. Membranes treated with various organic solvents exhibited enhanced permeability, enlarged pore size, and increased shrinkage in the longitudinal direction. These phenomena were found to depend on the surface tension of the solvent: the higher the surface tension of the solvent, the larger the change in morphology and permeation of the membrane. A mechanism to account for the effects of solvent treatment on the morphology of the membrane is proposed taking into consideration the influence of the type of solvent used for treatment. The enhanced morphological and permeation changes are ascribed to the formation of liquid bridges between two microfibrils of the membrane during drying followed by the deformation and adhesion of the adjacent microfibrils based on the surface tension of the solvent.     

Transformation of resonant Raman scattering into luminescence in CdxZn1−xTe mixed crystals: Time-resolved spectroscopy

We report an experimental study of time characteristics of secondary emission in Cd_xZn_1-xTe mixed crystals (x = 0.32) under resonant excitation with a picosecond dye laser. When the incident laser frequency is tuned on to the luminescence maximum of localized excitons, the decay curve of the intensity of “Raman-like” lines exhibits a single exponential decay. Off resonance, however, a short-lived component corresponding to Raman scattering appears in addition to the long-lived component. The intensity of the Raman component relative to that of the luminescence component increases with increase of the off-resonance frequency. From these temporal behaviors, we have found, for the first time, the transformation of resonant Raman scattering into luminescence in mixed crystals as a function of incident frequencies.     

Field Analysis of Pillbox Resonator with Radiation Loss Utilizing Finite-Element Beam Propagation Method Formulation

To deal with the radiation from an axially symmetric pillbox resonator embedded in LiNbO₃ substrate, an eigenvalue equation is derived from the expression of the finite-element beam propagation method in a cylindrical coordinate system. By solving the eigenvalue equation iteratively, the field distributions and the angular phase constants of the pillbox resonator are evaluated. The iterative scheme of solving the eigenvalue equation is an extension of our previous direct solution method which was described for a lossless case. The results obtained by this method are compared with those obtained analytically, and excellent agreement is found.     

An exact zooming method

This paper presents an efficient and exact formulation for finding stress concentration factors using a zooming analysis. A favorable characteristics of this method is its ability to perform a zooming analysis with computations taking place only in the zooming area under consideration with no need to treat the region outside the zooming area. At the final zooming step, the flexibility of a limited zooming area is determined for all nodes, including the new nodes created in the zooming processes as well as those of the original system before zooming.     

Synthetic studies on β-lactam antibiotics. VII. Mild removal of the benzyl ester protecting group with aluminum trichloride

The benzyl ester protecting group in β-lactam derivatives can be cleanly removed by treatment with aluminum trichloride under mild conditions, preferably in the presence of anisole, to give the corresponding free acids in high yields.     

Synthesis and dynamic mechanical properties of heterogeneous network polymers from poly(L-glutamic acid) and poly(oxyethylene glycol)

Heterogeneous network polymers composed of rigid polypeptide chains and flexible polyether chains were synthesized. That is, poly(L -glutamic acid) (PLGA) was crosslinked with poly(oxyethylene glycol) (PEG) at various carboxy/hydroxyl mole ratios K. The solubility tests and hydrolysis of heterogeneous network polymers suggest that the crosslinking reaction proceeds by esterification. The dynamic mechanical properties of these polymers(100 Hz, ?100–200°C) are greatly influenced by the presence of a trace of water and the weight per cent of PLGA. In addition, some of these polymers show only one maximum in the temperature dispersion of dynamic loss modulus E″ and tan δ, although their shape is rather broad. The x-ray photographs of these polymers show an amorphous halo or weak Debye-Sherrer rings. These findings suggest that these polymers are not simple adducts; neverthless PLGA and/or PEG domains exist.