Mechanistic study on radiation-induced grafting into fluorinated polymer solid films using a swelling-induced detachment of grafted polymers

The radiation-induced graft polymerization (RGP) of styrene into poly(ethylene-co-tetrafluoroethylene) films was performed at various monomer concentrations and solvents at 60 °C. The grafted polystyrene (g-PS) was isolated using the swelling-induced detachment phenomenon, and the number-averaged molecular weight (Mn) and the number of g-PS (Np) were determined using gel permeation chromatography. The Mn increased consistently with an increase in the grafting time up to 2–3 hours, indicating very low termination rates, which was a result of the “gel effect”. This is the first direct evidence of the gradual Mn increase over time using RGP in thermally and chemically stable polymer films such as fluorinated polymers. When the Mn and Np were plotted as a function of the degree of grafting (DOG), sudden Np drops along with rapid Mn increases were observed in the DOG region of 80–90%, indicating negligible initiation and propagation; however, a recombination termination between two propagating g-PS radicals dominated the later part of the grafting process. Further increases in both Mn and Np were observed subsequently, implying that reinitiation and propagation events were triggered by morphological changes, as observed by small- and ultrasmall-angle X-ray scattering experiments, which liberated the dormant radicals from the lamellar crystals.     

Two-loop double-pole counter lagrangian

On the basis of the background field method, extended one-loop counterterm formulae are derived, and a method to get the two-loop double-pole counter lagrangian is given. As an example, the double-pole divergences of ξ²X³ counterterms are obtained.     

Chromatic-distortion compensation in splitting and focusing of femtosecond pulses by use of a pair of diffractive optical elements

We propose a simple optical system to compensate for chromatic distortion that occurs during fan-out of femtosecond pulses by diffractive optics. The proposed system comprises a pair of diffractive elements, one for splitting an incoming pulse and the other for focusing the split pulses. With an appropriate separation between the elements, chromatic distortion resulting from the spectral bandwidth of a femtosecond pulse is removed, and an array of focused pulses with the same dimensions can be obtained. The theory has been verified through optical and processing experiments with 100-fs, 800-nm pulses.     

TETRAMETHOPRIM and PENTAMETHOPRIM: Synthesis,Antibacterial Properties and X-Ray Structures

TETRAMETHOPRIM ( 9 ) and PENTAMETHOPRIM ( 10 ), both prepared from the corresponding benzaldehydes 3 and 6 by conventional procedures, did not exhibit noteworthy antibacterial activity in vitro. A single crystal X-ray analysis of 9 and 10 provided evidence that the out-of-plane methoxy groups in the two compounds created a completely different topographical situation to that present in TRIMETHOPRIM , and less ideal for the binding to bacterial dihydrofolate reductase.     

Widely useful DMAP-catalyzed esterification under auxiliary base- and solvent-free conditions

With regard to atom economy and E-factor, catalytic condensation of carboxylic acids with equimolar amounts of alcohols is the most desirable. Although several highly active dehydration catalysts have been reported, more efficient alternatives are still strongly needed because the dehydrative esterification of tertiary alcohols, phenols, acid-sensitive alcohols, amino acids, and hardly soluble alcohols has never proceeded satisfactorily. Here we report new insights into the classical DMAP-catalyzed acylation of alcohols: surprisingly, only a 0.05-2 mol % of DMAP can efficiently promote acylation of alcohols with acid anhydrides under auxiliary base- and solvent-free conditions to give the corresponding esters in high yields. Furthermore, we achieved the recovery and reuse of commercially available polystyrene-supported DMAP without using any solvents. These serendipitous findings provide widely useful and environmentally benign esterification methods, which might be more practical and reliable than catalytic dehydrative condensation methods, in particular, for the less reactive alcohols which hardly condense with carboxylic acid directly.