Immobilization and Stabilization of Beta-Xylosidases from Penicillium janczewskii

β-Xylosidases are critical for complete degradation of xylan, the second main constituent of plant cell walls. A minor β-xylosidase (BXYL II) from Penicillium janczewskii was purified by ammonium sulfate precipitation (30% saturation) followed by DEAE-Sephadex chromatography in pH 6.5 and elution with KCl. The enzyme presented molecular weight (MW) of 301 kDa estimated by size exclusion chromatography. Optimal activity was observed in pH 3.0 and 70–75 °C, with higher stability in pH 3.0–4.5 and half-lives of 11, 5, and 2 min at 65, 70, and 75 °C, respectively. Inhibition was moderate with Pb⁺² and citrate and total with Cu⁺², Hg⁺², and Co⁺². Partially purified BXYL II and BXYL I (the main β-xylosidase from this fungus) were individually immobilized and stabilized in glyoxyl agarose gels. At 65 °C, immobilized BXYL I and BXYL II presented half-lives of 4.9 and 23.1 h, respectively, therefore being 12.3-fold and 33-fold more stable than their unipuntual CNBr derivatives (reference mimicking soluble enzyme behaviors). During long-term incubation in pH 5.0 at 50 °C, BXYL I and BXYL II glyoxyl derivatives preserved 85 and 35% activity after 25 and 7 days, respectively. Immobilized BXYL I retained 70% activity after 10 reuse cycles of p-nitrophenyl-β-D-xylopyranoside hydrolysis.

     

Behavior of disordered boron carbide under stress

Gibbs free-energy calculations based on density functional theory have been used to determine the possible source of failure of boron carbide just above the Hugoniot elastic limit (HEL). A range of B4C polytypes is found to be stable at room pressure. The energetic barrier for shock amorphization of boron carbide is by far the lowest for the B12(CCC) polytype, requiring only 6 GPa approximately = P(HEL) for collapse under hydrostatic conditions. The results clearly demonstrate that the collapse of the B12(CCC) phase leads to segregation of B12 and amorphous carbon in the form of 2-3 nm bands along the (113) lattice direction, in excellent agreement with recent transmission electron microscopy results.     

Synthesis,characterization, and thin‐film properties of 6‐oxoverdazyl polymers prepared by ring‐opening metathesis polymerization

Redox‐active 6‐oxoverdazyl polymers were synthesized via ring‐opening metathesis polymerization (ROMP) and their solution, bulk, and thin‐film properties investigated. Detailed studies of the ROMP method employed confirmed that stable radical polymers with controlled molecular weights and narrow molecular weight distributions (Ð < 1.2) were produced. Thermal gravimetric analysis of a representative example of the title polymers demonstrated stability up to 190 °C, while differential scanning calorimetry studies revealed a glass transition temperature of 152 °C. Comparison of the spectra of 6‐oxoverdazyl monomer 12 and polymer 13 , including FT‐IR, UV‐vis absorption, and electron paramagnetic resonance spectroscopy, was used to confirm the tolerance of the ROMP mechanism for the 6‐oxoverdazyl radical both qualitatively and quantitatively. Cyclic voltammetry studies demonstrated the ambipolar redox properties of polymer 13 (E_1/2,ox = 0.25 and E_1/2,red = ?1.35 V relative to ferrocene/ferrocenium), which were consistent with those of monomer 12 . The charge transport properties of thin films of polymer 13 were studied before and after a potential of 5 V was applied, revealing a drastic drop in the resistivity from 10⁶?10¹⁰ Ω m or more to 1.7 × 10⁴ Ω m and suggesting the potential usefulness of polymer 13 in bistable electronics. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1803–1813     

Redox polymers incorporating pendant 6-oxoverdazyl and nitronyl nitroxide radicals

Polymers comprised of redox-active organic radicals have emerged as promising materials for use in a variety of organic electronics, including fast-charging batteries. Despite these advances, relatively little attention has been focused on the diversification of the families of radicals that are commonly incorporated into polymer frameworks, with most radical polymers being comprised of nitroxide radicals. Here, we report two new examples prepared via ring-opening methathesis polymerization containing 6-oxoverdazyl and nitronyl nitroxide radicals appended to their backbones. The polymerization reaction and optoelectronic properties were explored in detail, revealing high radical content and redox activity that may be advantageous for their use as semiconducting thin films. Initial studies revealed that current–voltage curves obtained from thin films of the title polymers exhibited memory effects making them excellent candidates for use in resistive memory applications. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 309–319     

Entanglement irreversibility from quantum discord and quantum deficit

We relate the problem of irreversibility of entanglement with the recently defined measures of quantum correlation--quantum discord and one-way quantum deficit. We show that the entanglement of formation is always strictly larger than the coherent information and the entanglement cost is also larger in most cases. We prove irreversibility of entanglement under local operations and classical communication for a family of entangled states. This family is a generalization of the maximally correlated states for which we also give an analytic expression for the distillable entanglement, the relative entropy of entanglement, the distillable secret key, and the quantum discord.     

Modelling of particle layer detachment—Role of transient kinetic effects

Particle layers tend to build up on walls in many filtration and separation processes, calling for periodic removal in order to keep the apparatus running. Important factors are the adhesion of the layer on the substrate and the cohesion of the particles in the layer. Models describing such layer detachment generally assume constant and homogeneous conditions for the forces acting on the layer. But in reality detachment is extremely non-stationary concerning place and time, primarily due to changing conditi...