Effect of diffusion on rates and molecular weights in graft polymerization

A theoretical analysis has been made of the graft polymerization process in terms of the quantitative interrelationship between the initiation rate R_i, the k_p/k_t^1/ ratio of the monomer, the equilibrium solubility M of the monomer in the polymer, the polymer film thickness L, and the diffusivity D of the monomer in the polymer. It is shown how the values of these parameters in any grafting system interact to lead to diffusion-controlled graft polymerization. Whether graft polymerization is diffusion-free or diffusion-controlled depends on the values of K_p, d, k_p/k_p^1/2, and L as gathered in the parameter A = [(K_p/k_t^1/2)R_i, D,/^1/2] L/2. When the values of the various terms are such that A is less than 0.1 (i.e., D is large while R_i, k_p, and L are small), the reaction is diffusion-free. When A is greater than 3 (i.e., D is small while R_i, k_p, and L are large), the reaction is diffusion-controlled. The derived equations showing the relationship between kinetic and diffusional parameters are theoretically applicable to all grafting systems, i.e., for all monomer-polymer combinations under all conditions of reaction temperature, radiation intensity and polymer film thickness. The theoretical analysis has been verified for the rate and degree of polymerization for the radiation-induced graft polymerization of styrene to polyethylene.     

Spectral Analysis for HSS Preconditioners

In this paper,we are interested in HSS preconditioners for saddle point lin- ear systems with a nonzero(2,2)-th block.We study an approximation of the spectra of HSS preconditioned matrices and use these results to illustrate and explain the spectra obtained from numerical examples,where the previous spectral analysis of HSS precon- ditioned matrices does not cover.     

Structural and Functional Analysis of the Pyridoxal Phosphate Homeostasis Protein YggS from Fusobacterium nucleatum

Pyridoxal 5′-phosphate (PLP) is the active form of vitamin B6, but it is highly reactive and poisonous in its free form. YggS is a PLP-binding protein found in bacteria and humans that mediates PLP homeostasis by delivering PLP to target enzymes or by performing a protective function. Several biochemical and structural studies of YggS have been reported, but the mechanism by which YggS recognizes PLP has not been fully elucidated. Here, we report a functional and structural analysis of YggS from Fusobacterium nucleatum (FnYggS). The PLP molecule could bind to native FnYggS, but no PLP binding was observed for selenomethionine (SeMet)-derivatized FnYggS. The crystal structure of FnYggS showed a type III TIM barrel fold, exhibiting structural homology with several other PLP-dependent enzymes. Although FnYggS exhibited low (<35%) amino acid sequence similarity with previously studied YggS proteins, its overall structure and PLP-binding site were highly conserved. In the PLP-binding site of FnYggS, the sulfate ion was coordinated by the conserved residues Ser201, Gly218, and Thr219, which were positioned to provide the binding moiety for the phosphate group of PLP. The mutagenesis study showed that the conserved Ser201 residue in FnYggS was the key residue for PLP binding. These results will expand the knowledge of the molecular properties and function of the YggS family.     

Synthesis and characterization of thermally crosslinkable hole‐transporting polymers for PLEDs

Two new thermally crosslinkable hole‐transporting polymers, X‐PTPA and X‐PCz, were synthesized via Yamamoto coupling reactions. The number‐averaged molecular weights (M_n) of X‐PTPA and X‐PCz were found to be 45,000 and 48,000, respectively, and therewith, polydispersity indices were of 1.8 and 1.7, respectively. Thermally crosslinked X‐PTPA and X‐PCz exhibit excellent solvent resistance and stable optoelectronic properties. The UV–visible maximum absorption peaks of X‐PTPA and X‐PCz in the thin film state are at 389 and 322 nm, respectively. The HOMO levels of X‐PTPA and X‐PCz are estimated to be ?5.27 and ?5.39 eV, respectively. Multilayered devices (ITO/crosslinked X‐PTPA or X‐PCz/SY‐PPV/LiF/Al) were fabricated with SY (SuperYellow) as the emitting layer. The maximum efficiency of the multilayered device with a crosslinked X‐PTPA layer is approximately three times higher than that of the device without a crosslinked X‐PTPA layer and much higher than that of the crosslinked X‐PCz device. This result can be explained by the observations that crosslinked X‐PTPA produces increased electron accumulation within the emitter, SY, and also efficient exciton formation due to improved charge balance. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5111–5117     

Magnetic properties of neutron irradiated RPV steel

The neutron irradiated reactor pressure vessel (RPV) steels at various dose of 0–10¹⁸ n/cm² have been studied with Mössbauer, x-ray diffraction, and VSM. The Mössbauer data shows that the value of magnetic hyperfine field of Fe atom that exist at martensite is 330 kOe at site 1 and 305 kOe at site 2. At room temperature, the total absorption area of Mössbauer spectra with respect to irradiation of neutron is constant for the dose of 0–10¹⁶ n/cm², while over the dose of 0–10¹⁷ n/cm² the absorption area decreases rapidly. But the doublet area for the dose of 0–10¹⁶ n/cm² is constant, while over the dose of 10¹⁷ n/cm² it increases with increasing the fluence level of neutron. The coercivity and remanence of the neutron irradiated samples do not change significantly. But the maximum induction decreases by 5% at 10¹⁸ n/cm², compared with that of the as-received sample.     

Subcentimeter depth resolution using a single-photon counting time-of-flight laser ranging system at 1550 nm wavelength

We demonstrate subcentimeter depth profiling at a stand off distance of 330 m using a time-of-flight approach based on time-correlated single-photon counting. For the first time to our knowledge, the photon-counting time-of-flight technique was demonstrated at a wavelength of 1550 nm using a superconducting nanowire single-photon detector. The performance achieved suggests that a system using superconducting detectors has the potential for low-light-level and eye-safe operation. The system's instrumental response was 70 ps full width at half-maximum, which meant that 1 cm surface-to-surface resolution could be achieved by locating the centroids of each return signal. A depth resolution of 4 mm was achieved by employing an optimized signal-processing algorithm based on a reversible jump Markov chain Monte Carlo method.     

Comment on "direct observation of laser filamentation in high-order harmonic generation"

We argue for a different physical interpretation of the results given in the recent Letter by Painter et al. [Opt. Lett.31, 3471 (2006)] in which an elongated Ti:saphire beam with two distinct waists is considered as direct evidence of laser filamentation. As the pulse power is well below the critical power for self-focusing, the authors pleaded for new examination of the n(2) value for He. A three-dimensional numerical modeling, using the published n(2) value for He, reproduces very well the measured data and invalidates the filamentation hypothesis.     

Local Thermodynamic Description of Isothermal Single-Phase Flow in Simple Porous Media

Transport in Porous Media - Darcy’s law for porous media transport is given a new local thermodynamic basis in terms of the grand potential of confined fluids. The local effective pressure...     

Associated Primes of the Example of Brenner and Monsky

Recently, Brenner and Monsky found an example of an ideal in a hypersurface ring whose tight closure does not commute with localization, thus answered the localization problem in tight closure theory in the negative. In this article, we use Monsky's calculations to analyze the set of associated primes of the Frobenius powers of this ideal and show that this set is infinite.