Mechanisms of orientational and photoelastic birefringence generation of methacrylates for the design of zero–zero‐birefringence polymers

The intrinsic birefringence Δn⁰ and photoelastic coefficient C of poly(methyl methacrylate), poly(2,2,2‐trifluroethyl methacrylate), poly(phenyl methacrylate), and poly(2,2,3,3,3‐pentafluorophenyl methacrylate) were determined. We categorized these methacrylate polymers into four birefringence‐types, even though their molecular structures differed only by the substituents on the side chains. Based on the results of Δn⁰ and C, novel polymers that exhibit neither orientational nor photoelastic birefringence, i.e., zero–zero‐birefringence polymers, were designed and synthesized by quaternary copolymerization system. Furthermore, we confirmed that the mechanisms of orientational birefringence and photoelastic birefringence generation were different in these methacrylate polymers. The conformation of the repeat unit of the polymers was nearly constant during the generation of orientational birefringence. In contrast, the conformation of the repeat unit of the polymers changed during the generation of photoelastic birefringence in the glassy state. These findings demonstrated the reasonability of evaluating orientational and photoelastic birefringence separately, as well as the adequacy of the classification of polymers into four birefringence‐types. Given these results and the fact that zero–zero‐birefringence polymers could be prepared successfully by four‐birefringence type monomers, we demonstrated the reasonability of the method for designing the zero–zero‐birefringence polymers. POLYM. ENG. SCI., 55:1330–1338, 2015. © 2015 Society of Plastics Engineers     

One-Step Generation of Multiple Gene-Edited Pigs by Electroporation of the CRISPR/Cas9 System into Zygotes to Reduce Xenoantigen Biosynthesis

Xenoantigens cause hyperacute rejection and limit the success of interspecific xenografts. Therefore, genes involved in xenoantigen biosynthesis, such as GGTA1, CMAH, and B4GALNT2, are key targets to improve the outcomes of xenotransplantation. In this study, we introduced a CRISPR/Cas9 system simultaneously targeting GGTA1, CMAH, and B4GALNT2 into in vitro-fertilized zygotes using electroporation for the one-step generation of multiple gene-edited pigs without xenoantigens. First, we optimized the combination of guide RNAs (gRNAs) targeting GGTA1 and CMAH with respect to gene editing efficiency in zygotes, and transferred electroporated embryos with the optimized gRNAs and Cas9 into recipient gilts. Next, we optimized the Cas9 protein concentration with respect to the gene editing efficiency when GGTA1, CMAH, and B4GALNT2 were targeted simultaneously, and generated gene-edited pigs using the optimized conditions. We achieved the one-step generation of GGTA1/CMAH double-edited pigs and GGTA1/CMAH/B4GALNT2 triple-edited pigs. Immunohistological analyses demonstrated the downregulation of xenoantigens; however, these multiple gene-edited pigs were genetic mosaics that failed to knock out some xenoantigens. Although mosaicism should be resolved, the electroporation technique could become a primary method for the one-step generation of multiple gene modifications in pigs aimed at improving pig-to-human xenotransplantation.     

Living cationic polymerization of p-methoxystyrene by hydrogen iodide/zinc iodide at room temperature

Summary Cationic polymerization of p-methoxystyrene initiated by HI/ZnI₂ in toluene afforded living polymers not only at low temperature (–15°C) but at room temperature (+25°C) as well. The number-average molecular weight of the polymers was directly proportional to monomer conversion and in excellent agreement with the calculated value assuming that one polymer chain forms per unit hydrogen iodide. On addition of a fresh feed of monomer at the end of the first-stage polymerization, the added feed was smoothly polymerized at nearly the same rate as in the first stage; the polymer molecular weight further increased in direct proportion to monomer conversion and was close to the calculated value for living polymer. Throughout these reactions, the molecular weight distribution of the polymers stayed very narrow (¯M_w/¯M_n<1.1). This is the first example of living cationic polymerizations of styrene derivatives that proceed even at room temperature.     

Living cationic polymerization of a vinyl ether with a triester pendant

Summary Cationic polymerization of CH₂=CH-O-CH₂CH₂C(COOC₂H₅)₃, a vinyl ether with three pendent esters, initiated by the HI/I₂ system in toluene at –40 °C afforded living polymers with a controlled molecular weight ( = 10³–10⁴) and a narrow molecular weight distribution ( = 1.1–1.2). The number-average molecular weight of the polymers was directly proportional to monomer conversion and the monomer-to-initiator (HI) feed ratio. The polymers obtained with BF₃O(C₂H₅)₂ had a fairly high molecular weight ( 10⁵, 5 × 10⁴) and a broad molecular weight distribution. The triester vinyl ether was similar in reactivity to alkyl counterparts and one order of magnitude more reactive than the corresponding mono- and diester vinyl ethers.     

Living cationic polymerization of isobutyl vinyl ether by the diphenyl phosphate/zinc iodide initiating system

Summary The first example of the living cationic polymerization of isobutyl vinyl ether via the phosphate counteranion has been achieved in toluene below 0°C with a new initiating system that consists of diphenyl phosphate and zinc iodide, (C₆H₅0)₂P(0)0H/ZnI₂. The number-average molecular weight of the polymers increased in direct proportion to monomer conversion, and was in excellent agreement with the calculated value assuming that one polymer chain forms per unit diphenyl phosphate. On addition of a fresh feed of monomer at the end of the polymerization, the added feed was smoothly polymerized at nearly the same rate as in the first stage, and the polymer molecular weight further increased in direct proportion to monomer conversion. Throughout the reaction, the molecular weight distribution of the polymers stayed very narrow (¯M/¯M_n 1.1). At room temperature (+25 °C), however, the molecular weight distribution of the polymers slightly broadened (¯M_w/¯M_n 1.2) at high conversions where the polymer molecular weight became smaller than the calculated value. Evidently, the (C₆H₅0)₂-P(0)0H/ZnI₂ system indeed generates a propagating species of a long life-time at room temperature, but the perfectly living polymerization by this system operates below 0°C.Living cationic polymerization of vinyl ethers by electrophile     

Constant-phase-mode operation of the light-addressable potentiometric sensor

The constant-phase-mode operation of the light-addressable potentiometric sensor (LAPS) is proposed and demonstrated. In this new operation mode, the temporal change and the spatial distribution of the analyte concentration are recorded in the form of the bias voltage applied to the LAPS sensor plate, which is servo-controlled to maintain the phase of the photocurrent at a constant value with respect to the light modulation. The constant-phase-mode LAPS is advantageous for its wider measurement range and reduction of artifacts.     

Damage to seagrass and seaweed beds in Matsushima Bay,Japan, caused by the huge tsunami of the Great East Japan Earthquake on 11 March 2011

Damage to seagrass and seaweed beds caused by the huge tsunami of the Great East Japan Earthquake on 11 March 2011 was investigated in Matsushima Bay, Miyagi Prefecture, Japan, by comparing satellite images taken before the tsunami in November 2009 and after the tsunami in May 2011. The results showed that the tsunami destroyed 220 ha of seagrass and seaweed beds, from 320 ha in 2009 to 100 ha just after the tsunami. Zostera marina beds on the sandy and muddy bottom were rather severely damaged compared with brown seaweed beds of Sargassum horneri on the rocky substrate. Substrates of the beds and directions of the tsunami seem to be responsible for the magnitude of the damage to the beds. Maps of the spatial distributions of the beds before and after the tsunami can provide information for the restoration of seagrass and seaweed beds as natural infrastructures of coastal fisheries resources.     

A novel bistable reflective display using quick‐response liquid powder

Abstract— We have developed new powder materials that exhibit liquid behavior, which can lead to the realization of novel bistable and reflective displays having paper‐white appearance, high contrast, and quick response. Two types of display were demonstrated, one had 160 × 160 array of pixels and the other had 320 × 320 in a 3.1‐in.‐diagonal viewable image size corresponding to 66 and 132 dpi, respectively. These displays were driven by passive‐matrix addressing. The displays showed a reflectivity of more than 41%, a contrast more than 1:10, and a pixel response time of less than 0.2 msec. The seven‐segment display for use in clocks was also demonstrated.     

Inhibition of char deposition using a particle bed in heating section of supercritical water gasification

Supercritical water gasification (SCWG) has attracted attention as a technology for utilizing wet biomass. We used a fluidized bed of alumina particles to prevent blockage of a SCWG reactor. A glucose solution was heated in the reactor with and without fluidized alumina particles. In the absence of alumina particles, char particles formed homogeneously in the reactor, but the use of a fluidized bed resulted in accumulation of char particles at the reactor’s exit rather than inside the reactor. Therefore, the fluidized bed was effective at preventing blockage of the reactor. However, the alumina particles did not remove deposits from the reactor’s walls. Instead, the fluidized bed caused larger char particles to form, preventing their adhesion to the reactor’s wall.