Photoiniferter-based thermoresponsive graft architecture with albumin covalently fixed at growing graft chain end

The aim of this study was to develop a novel surface graft architecture in which albumin is covalently fixed at the growing chain end of the hydrophilic polymers: poly(N, N-dimethylacylamide), PDMAM, and poly(N-isopropylacrylamide), PNIPAM. Photoiniferter-based surface-grafted polymers were prepared using either an albuminated iniferter or a nonalbuminated iniferter, both of which were derivatized on glass surfaces, and ultraviolet (UV)-light-irradiated in the presence of a DMAM or NIPAM monomer. Surface chemical composition analysis by X-ray photoelectron spectroscopy, contact angle measurement, immunostaining using fluorescence labeled antibody and the measurement of graft thickness, as determined from force-distance curves obtained in water at 25 degrees C and 37 degrees C by atomic force microscopy, evidenced that the thickness of graft layer increased with photoirradiation time and albumin molecules exist at growing chain ends. For PNIPAM-grafted surfaces, the interconversion between swollen and collapsed graft chains was observed below and above the lower critical solution temperature of PNIPAM. The potential application of a thermoresponsive graft with albumin covalently fixed at its growing chain end was discussed in terms of "active" nonfouling surface design based on the temperature-dependent switching of phase transition.     

Radiation-induced emulsion polymerization of ethylene. IV. Effect of pressure,temperature, and additives on rate in connection with number of polymer particles

The effects of pressure, temperature, and additives on the rate of radiation-induced emulsion polymerization of ethylene with FC-143 as emulsifier were studied kinetically. The rate of polymerization was proportional to the 2.5 power of ethylene fugacity, and the apparent rate constant (rate of polymerization/2.5 power of ethylene fugacity) was constant below 78°C. Above this temperature, the rate constant decreased with an apparent activation energy of ?8.2 kcal/mole. These facts can be interpreted in connection with the polymer structure and the change of rate of escape of radicals from the polymer structure and the change of rate of escape of radicals from the polymer particle into the aqueous phase. The rate of polymerization decreased on addition of a series of n-aliphatic alcohols due to the chain-transfer reaction and consequent escape of radicals to the aqueous phase. On the other hand, the addition of tert-butyl alcohol increased the rate of polymerization, probably because of its effect in increasing swelling of the polymer particles. Addition of electrolytes increased the rate of polymeriaztion as a result of the increase of the number of polymer particles.     

Effect of temperature on the radiation-induced polymerization of ethylene in various media

The effects of temperature on the radiation-induced polymerization of ethylene in bulk and in the presence of ethyl alcohol, n-butyl alcohol, tert-butyl alcohol, cyclohexane, 2,2,4-trimethylpentane, and 2,2,5-trimethylhexane were studied. The changes of the amounts of polymerized monomer with the reaction temperature were different from each other in these reaction systems, especially in the range lower than 60–80°C. At temperatures lower than 60–80°C, as the reaction temperature increases, the amount of polymerized monomer decreased in bulk and in the presence of tert-butyl alcohol. The amount was almost constant in the presence of ethyl alcohol and 2,2,4-trimethylpentane, and it increased in the presence of n-butyl alcohol, cyclohexane, and 2,2,5-trimethylhexane. However, in the temperature range higher than 60–80°C, the amount of polymerized monomer increased with increasing temperature in every reaction system except for bulk polymerization. The molecular weight of polymer decreased with increasing temperature in every reaction system except at temperatures lower than 25°C. The molecular weight of polymer formed in bulk, in tert-butyl alcohol, and also in 2,2,4-trimethylpentane were relatively higher than that in other reaction systems. A bimodal molecular weight distribution was observed for the polymer formed in bulk and in tert-butyl alcohol at 40–60°C. These results are discussed in connection with the heterogeneity of the reaction system. The differences due to temperature in each reaction system are explained as due to the difference in affinity of the reaction system for the propagating chain and in the facility of chain transfer to the medium.     

Synthesis and photochemical surface fixation of hydroxylated cascade molecules

A novel supramolecularly assembled surface architectural method was developed, which involved a self-assembling process of amphiphilic molecules and a subsequent photochemical process. The specially designed molecules were cascade “tree” molecules composed of a phenylazido group as root, an aliphatic hydrocarbon chain as stem, and two or three tris(hydroxymethyl)aminomethane groups as leaves. Using a horizontal lifting method, unimolecular assemblies which formed at an air/water interface were transferred to polyethylene (PE) surfaces. Upon ultraviolet irradiation, these molecules were covalently fixed on the surfaces due to the photochemical reactivity of the phenylazido group. Treated surfaces became wettable with water, indicating that hydrophilic hemispheres were located at the outer surface region of the PE surfaces. Bimolecular assemblies composed of cascade molecules and noncascade molecules with a hydroxyl group at a terminus exhibited lower advancing and receding contact angles and reduced hysteresis than those of unimolecular ones, indicating that these bimolecular assemblies have a well-structured molecular organization with a high degree of packing. © 1997 John Wiley & Sons, Inc.     

Laser-irradiation-induced surface graft polymerization method

A laser-induced surface graft polymerization method is reported in which surface radicals generated upon laser irradiation initiated radical polymerization. The radical concentrations generated upon excimer laser irradiation under vacuum on poly-(ethylene terephthalate) film surfaces were measured using a radical scavenger, 1,1-diphenyl-2-picrylhydrazyl. The density of surface radicals increased with laser fluence at low fluences but decreased at high fluences. Upon laser irradiation and subsequent treatment with gaseous N,N-dimethylacrylamide, surface graft polymerization occurred. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 747–750, 1997     

A new reagent for activating carboxyl groups: diphenyl 2-oxo-3-oxazolinylphosphonate

Diphenyl 2-oxo-3-oxazolinylphosphonate serves as a carboxyl-activating reagent to permit a direct preparation of versatile intermediate, 3-acyl-2-oxazolones or a one-step formation of amides from carboxylic acids.     

Effect of molecular weight on the crystalline structure of polytetrafluoroethylene as-polymerized

Melting and crystallization behavior of polytetrafluoroethylene as polymerized in emulsion and suspension is shown to depend on molecular weight. DSC heating curves for virgin PTFE with low molecular weight below 3 × 10⁵ have a single peak, whereas curves for higher molecular weight samples have double peaks. With increasing heating rate the areas of higher melting peaks become larger than the lower melting peaks. The morphology of polymer exhibiting double melting peaks is mainly folded ribbons or granular particles. The phenomenon of double melting is explained on the basis of two different crystalline states which correspond to the “fold regions” and the “linear segments” in a folded ribbon. The melting temperature of virgin PTFE is almost constant at ca. 330°C for molecular weights below 1 × 10⁶, and rises as the molecular weight increases above 1 × 10⁶. The heat of melting of virgin PTFE is nearly independent of molecular weight. On the basis of these results, we propose a model for melting and crystallization of low and high molecular weight PTFE and for the crystal structure.     

Molecular weight distribution and molecular structure of polyethylene produced by radiation-induced polymerization

The molecular weight distribution of polyethylene produced by radiation was calculated according to a kinetic scheme. The calculated molecular weight distribution was compared with the results deduced from gel-permeation chromatography. The observed distribution curve from GPC was broader and showed a lower degree of polymerization than the calculated one. Discrepancies between observed and calculated curves can be explained if the polymer contains nonsteady-state products and if the reaction mechanism includes chain transfer to dead polymer. By this reaction long-chain branching would occur. Several long-chain branches per polymer molecule were indeed found, as inferred from solution properties.     

Magnetic hyperfine structure of muonic and electronic atoms

The magnetic hyperfine structure of atoms is studied. A new compact expression is introduced for the magnetic hyperfine anomaly. A theoretical foundation is given for an empirical formula discovered by Moskowitz and Lombardi. The effects of core polarization and mesonic exchange currents are discussed. There are two kinds of core polarization, Δl = 0 and Δl = 2. The latter is shown to be important to explain certain isotope shifts, though it is smaller than the former Δl = 0 effect.