Cationic Graft Polymerization of 2-Oxazolines on Poly(vinyl alcohol) Derivatives

The graft polymerization of various monomers onto PVA has been studied by radical polymerization mechanism. Successful grafting of acrylonitrile (AN), acrylamide (AAm), acrylic acid, methyl methacrylate, and vinyl acetate was reported by using chemical (Minoet al., 1959; Ide, 1961; Maskimov et al., 1965) and radiation (Misra et al., 1987) methods. On the other hand, less attention has been paid to ionic graft polymerization. Sasson and Zilkha reported on grafting formaldehyde onto potassium-metallated PVA (Sasson and Zilkha, 1969). Galin studied grafting of AN and propane sulfone onto sodium-metallated PVA (Galin, 1971). We used the same anionic system for the polymerization of AAm (Ikeda and Suzuki, 1980).     

Sawtooth-shaped stringiness with front frame formation for polyacrylic pressure-sensitive adhesives with two different molecular structures

The formation of sawtooth-shaped stringiness during 90° peeling was investigated using crosslinked poly(n-butyl acrylate–acrylic acid) and poly(2-ethylhexyl acrylate–acrylic acid) random copolymers with an acrylic acid content of 5 wt.% and different crosslinking degrees as pressure-sensitive adhesives (PSAs). The gel fraction was measured by toluene extraction of PSA, and it increased with crosslinker content for both systems. The observed stringiness was sawtooth-shaped, but there were three different types; both the typical sawtooth shape and the frame formed at the front tip with interfacial failure, and the sawtooth shape formed with cohesive failure. The change in the stringiness shape was affected strongly by the gel fraction of PSA. The peel rate under constant peel load was measured and revealed that the peel rate was lowest upon formation of the front frame type. A good relation was found between peel rate and peel strength, with a greater peel strength upon formation of the front frame type. The concentrated stress at the peeling tip is released by progress of peeling and deformation of the adhesive layer (stringiness) for no frame type. On the other hand, the sufficient interfacial adhesion delays the progress of peeling, and the applied larger stress causes cavitation in the PSA layer for front frame type. The formed cavity grows and the front frame type formed as a result. That is, internal deformation occurred preferentially over peeling. In order to improve the peel strength, the front frame type is the most useful stringiness shape.     

Synthesis and Self-Organization of Fluorene-Conjugated Bisimidazolylporphyrin and Its Optical Properties

A conjugated-bisimidazolylporphyrin bridged by bis(ethynylfluorene) was synthesized and organized into linear polymer through self-coordination having mean molecular weights, M_w and M_n, of ~2.1 × 10⁵ Da and ~1.6 × 10⁵ Da, respectively. A large two-photon absorption cross section value of 3.4 × 10⁵ GM (per dimer unit) was observed. This value was comparable to that of the previously reported self-assembled linear polymer consisting of butadiyne-bridged imidazolylporphyrins. The two-photon absorption properties could be controlled by tuning the wavelength and absorption intensity of the one-photon absorption.     

Immunological Effects of Oenothein B,an Ellagitannin Dimer,on Dendritic Cells

Oenothein B is a unique macrocyclic ellagitannin dimer that has been found in various medicinal plants belonging to Onagraceae, Lythraceae, and Myrtaceae, with diverse biological activities. The immunological effects of tannins in terms of cytokine-release from macrophages and monocytes have been discussed, while the effects on other immunocompetent cells have been the subject of minimal investigation. We evaluated the immunomodulatory effects induced by tannin treatment in human dendritic cells (DCs), which play a critical role in the initial immune response, by measuring the changes in cytokine production, cell differentiation, and cell viability. Oenothein B showed significant down-regulation of the expression of cell surface molecules, CD1a and CD83, suggesting the inhibition of DC differentiation and/or maturation. The suppressive effect on DCs was associated with the induction of apoptosis without the activation of caspase-3/7, 8, and 9, and this was supported by the morphological features indicating significant nuclear condensation. Oenothein B also markedly suppressed the production of inflammatory cytokines, such as IL-1β and IL-6, in a dose-dependent manner. These data may, in part, be able to explain the traditional use of tannin-containing medicinal plants for the treatment of a variety of inflammatory diseases, including inflammatory bowel disease, celiac disease, and rheumatoid arthritis.     

Long Crack R-Curve of Aligned Porous Silicon Nitride

Long crack R -curve of a porous Si₃N₄ with aligned fibrous grains was investigated, using a chevron-notched beam technique. A crack was constrained to propagate normal to the grain alignment. The crack growth resistance of aligned porous Si₃N₄ was much larger compared with that of dense Si₃N₄ ceramics. Microstructure observations showed that pullouts of fibrous grains in aligned porous Si₃N₄ markedly increased during crack propagation relative to those of dense Si₃N₄, due to the existence of pores. The efficient grain pullouts in porous Si₃N₄ increased the bridging stress at the crack wake.     

Production of FAME from acid oil model using immobilized <Emphasis Type="Italic">Candida antarctica</Emphasis> lipase

Acid oil is a by-product in the neutralization step of vegetable oil refining and is an alternative source of biodiesel fuel. A model substrate of acid oil, which is composed of TAG and FFA, was used in experiments on the conversion to FAME by immobilized Candida antarctica lipase. FFA in the mixture of TAG/FFA were efficiently esterified with methanol (MeOH), but the water generated by the esterification significantly inhibited methanolysis of TAG. We thus attempted to convert a mixture of TAG/FFA to FAME by a two-step process comprising methyl esterification of FFA and methanolysis of TAG by immobilized C. antarctica lipase. The first reaction was conducted at 30°C in a mixture of TAG/FFA (1∶1, wt/wt) and 10 wt% MeOH using 0.5 wt% immobilized lipase, resulting in efficient esterification of FFA. The reaction mixture after 24 h was composed of 49.1 wt% TAG, 1.3 wt% FFA, 49.1 wt% FAME, and negligible amounts of DAG and MAG (<0.5 wt%). The reaction mixture was then dehydrated and used as a substrate for the second reaction, which was conducted at 30°C in a solution of the dehydrated mixture and 5.5 wt% MeOH using 6 wt% immobilized lipase. The activity of the lipase increased gradually when the reaction was repeated by transferring the enzyme to a fresh substrate mixture. The activity reached a maximum after 6 cycles, and the content of FAME achieved was >98.5 wt% after a 24-h reaction. The immobilized lipase was very stable in the first-and second-step reactions and could be used for >100 d without significant loss of activity.     

Synthesis of chemically modified chitosans with a higher fatty acid glycidyl and their adsorption abilities for anionic and cationic dyes

Novel chitosan‐based materials with a higher fatty acid glycidyl as the chemically modified agent were synthesized and the adsorption ability of the resulting polymers has been evaluated for typical anionic and cationic dyes. The successful modification was confirmed by the infrared spectroscopic measurements. As the degree of substitution was decreased, the adsorption ability of the chemically modified chitosans for anionic dyes at the higher dye concentration was increased, and the modified chitosans with a lower degree of substitution showed a higher adsorption ability than that of an activated carbon at the higher dye concentration. For cationic dyes, the chemically modified chitosan showed a good adsorption power, especially when the adsorption power was evaluated by the flow methods. The improved adsorption ability of a chemically modified chitosan material was also confirmed by comparing it with that of a crosslinked chitosan material. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2423–2428, 2005     

Uncertainty quantification via bayesian inference using sequential monte carlo methods for CO2 adsorption process

This work presents the uncertainty quantification, which includes parametric inference along with uncertainty propagation, for CO₂ adsorption in a hollow fiber sorbent, a complex dynamic chemical process. Parametric inference via Bayesian approach is performed using Sequential Monte Carlo, a completely parallel algorithm, and the predictions are obtained by propagating the posterior distribution through the model. The presence of residual variability in the observed data and model inadequacy often present a significant challenge in performing the parametric inference. In this work, residual variability in the observed data is handled by three different approaches: (a) by performing inference with isolated data sets, (b) by increasing the uncertainty in model parameters, and finally, (c) by using a model discrepancy term to account for the uncertainty. The pros and cons of each of the three approaches are illustrated along with the predicted distributions of CO₂ breakthrough capacity for a scaled‐up process. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3352–3368, 2016     

Identification and Characterization of D‐Succinylase,and a Proposed Enzymatic Method for D‐Amino Acid Synthesis

Chiral amino acids are important intermediates for the pharmaceutical industry. We have developed a novel one‐pot enzymatic method for D ‐amino acid synthesis by the dynamic kinetic resolution of N‐succinyl‐dl ‐amino acids using D ‐succinylase (DSA) and N‐succinylamino acid racemase (NSAR, EC 4.2.1.113). The DSA from Cupriavidus sp. P4‐10‐C, which hydrolyzes N‐succinyl‐D ‐amino acids enantioselectively to their corresponding D ‐amino acids, was identified for the first time by screening soil microorganisms. Subsequently, the DSA gene was cloned and overexpressed in Escherichia coli. DSA was shown to comprise two subunits with molecular masses of 26 kDa and 60 kDa. Additionally, the NSAR gene from Geobacillus stearothermphilus NCA1503, which racemizes N‐succinylamino acids, was also cloned and overexpressed in E. coli. The highly purified DSA and NSAR prepared from each recombinant E. coli were characterized and used for D ‐amino acid synthesis. A one‐pot enzymatic method converted 100 mM N‐succinyl‐dl ‐phenylalanine to D ‐phenylalanine in 91.1% conversion with 86.7% ee. This novel enzymatic method may be useful for the industrial production of many D ‐amino acids.

     

Freestanding HfO2 grating fabricated by fast atom beam etching

We report here the fabrication of freestanding HfO2 grating by combining fast atom beam etching (FAB) of HfO2 film with dry etching of silicon substrate. HfO2 film is deposited onto silicon substrate by electron beam evaporator. The grating patterns are then defined by electron beam lithography and transferred to HfO2 film by FAB etching. The silicon substrate beneath the HfO2 grating region is removed to make the HfO2 grating suspend in space. Period- and polarization-dependent optical responses of fabricated HfO2 gratings are experimentally characterized in the reflectance measurements. The simple process is feasible for fabricating freestanding HfO2 grating that is a potential candidate for single layer dielectric reflector.PACS: 73.40.Ty; 42.70.Qs; 81.65.Cf.