Sequential co-immobilization of <Emphasis Type="Italic">β</Emphasis>-glucosidase and yeast cells on single polymer support for bioethanol production

Co-immobilization of enzymes and microorganism is an effective way to enable cells to use nonmetabolizable substrates and accelerate reaction rate of overall process. Herein, a facile strategy to separately co-immobilize β-glucosidase (BG) and yeast cells on non-woven fabrics was developed. The BG was firstly in situ entrapped into poly(ethylene glycol) (PEG) network grafted on non-woven fabrics by visible light induced living/controlled graft polymerization. Then re-graft polymerization was performed on the as-formed BG loaded layer by taking advantage of living-grafting polymerization on its surface to in situ encapsulate yeast cells into the second PEG network layer. This layered structure of co-immobilization avoided possible interference between enzyme and cells. Viability assay of yeast cells demonstrated that most of cells were viable after immobilization. While immobilized BG showed decreased V_max compared to free BG, indicating that entrapping BG into inner PEG network layer restricted its accessibility with substrates. This co-immobilization sheet could successfully convert cellobiose to ethanol and a maximum of 98.6% bioethanol yield can be obtained after 48 h of simultaneous saccharification and fermentation (SSF). The co-immobilization sheet showed excellent reusability and could still reach more than 60% of original ethanol yield after reusing for 7 batches. Compared with the mixed co-immobilization, the sequential layered immobilization in this system showed better stability and higher ethanol yield.     

氧化镁表面辐射接枝聚合反应机理研究

氧化镁表面辐射接枝聚合反应机理研究蒋波＊黄光琳（四川联合大学原子核科学技术研究所成都６１００６４）（四川联合大学化学系成都）关键词氧化镁，反应机理，辐射接枝，甲基丙烯酸甲酯１９９６－０５－２１收稿，１９９６－０８－２６修回辐射诱发有机单体在固体表面聚...     

Selective functionalization of 3-D polymer microstructures

We demonstrate the selective functionalization of 3-D polymer microstructures that were created using multiphoton absorption polymerization. By fabricating different portions of the structures with acrylic and methacrylic polymers, we are able to take advantage of the differential reactivities of these materials to perform functionalization chemistry on a single polymeric component. We demonstrate the selective deposition of metal to create structures, such as a functional microinductor. Our strategy is quite general and can be extended readily to the deposition of materials, such as metal oxides and biomolecules.     

Simultaneous Grafting Polymerization of Acrylic Acid and Silver Aggregates Formation by Direct Reduction Using γ Radiation onto Silicone Surface and Their Antimicrobial Activity and Biocompatibility

The modification of medical devices is an area that has attracted a lot of attention in recent years; particularly, those developments which search to modify existing devices to render them antimicrobial. Most of these modifications involve at least two stages (modification of the base material with a polymer graft and immobilization of an antimicrobial agent) which are both time-consuming and complicate synthetic procedures; therefore, as an improvement, this project sought to produce antimicrobial silicone (PDMS) in a single step. Using gamma radiation as both an energy source for polymerization initiation and as a source of reducing agents in solution, PDMS was simultaneously grafted with acrylic acid and ethylene glycol dimethacrylate (AAc:EGDMA) while producing antimicrobial silver nanoparticles (AgNPs) onto the surface of the material. To obtain reproducible materials, experimental variables such as the effect of the dose, the intensity of radiation, and the concentration of the silver salt were evaluated, finding the optimal reaction conditions to obtain materials with valuable properties. The characterization of the material was performed using electronic microscopy and spectroscopic techniques such as ¹³C-CPMAS-SS-NMR and FTIR. Finally, these materials demonstrated good antimicrobial activity against S. aureus while retaining good cell viabilities (above 90%) for fibroblasts BALB/3T3.     

Ozone-induced graft polymerization onto polymer surface

Ozone-induced graft polymerization was carried out to improve polymer surfaces. The polymers were exposed to ozone and the surface density of peroxides formed was determined by three methods; iodide, DPPH, and peroxidase method. The peroxide production could be readily controlled by the ozone concentration and the ozone exposure time. In addition, it was dependent on the kind of polymer. Further, it seemed probable that the ozone oxidation introduced peroxides not only on the outermost surface but also into a layer deeper from the outermost surface. Such polymeric peroxides were capable of initiating graft polymerization onto PU. All the physical and biological measurements on the grafted surface indicated that ozone-induced graft polymerization has effectively made the PU surface covered with the grafted water-soluble chains, their location being restricted to the film surface region. The interaction of the PU surface with blood components could be greatly reduced by the surface graft polymerization. © 1993 John Wiley & Sons, Inc.     

Synthesis and characterization of 4‐vinyl pyridine‐grafted Teflon‐PFA film for water technologies

To get highly reactive polymeric materials for selective studies of enzyme immobilization, water purification, separation, and enrichment technologies, we attempted to graft 4‐vinyl pyridine (4‐VP) onto Teflon‐PFA by simultaneous γ‐ray initiation. The resulting graft copolymers were quaternized by treatment with some alkylating agents. Optimum conditions for grafting were evaluated through the variation of the total dose of radiation, the amount of water, and the monomer concentration. The effect of the solvent composition (H₂O/MeOH) was also studied. In the presence of MeOH, grafting occurred less often and was nonselective as 4‐VP was incorporated on both sides in comparison with highly selective grafting in an aqueous medium. The percentages of the grafting, total conversion, and grafting efficiency and the rates of the polymerization, grafting, and homopolymerization were also evaluated. Some other monomers such as methacrylic acid, methyl methacrylate, maleic acid, acrylonitrile, and vinyl imidazole were not incorporated onto the backbone film under the optimum grafting reaction conditions evaluated for the grafting of 4‐VP. Although some grafting occurred, the graft yield was too low to be considered of any significance. The grafted films were quaternized with benzyl chloride, and quaternized and unquaternized films were used for the immobilization of lipase. The former showed high activity with lipase and has potential for development as a bioreactor. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4506–4518, 2000     

Organometallics meet colloid chemistry: a case study in three phases based on molecular carbonyl precursors containing zinc and manganese

Two organometallic compounds containing zinc and manganese in different ratios are used as single-source precursors for the preparation of various new, bimetallic oxide materials with nanoscaled dimensions. It is shown that the materials synthesis can be performed in the solid-state, the liquid-phase, and even in the gas-phase. The molecular composition of the precursors determines the composition of the resulting materials. In addition, two novel methods for the preparation of highly crystalline metal oxide colloids are presented: The coupling between a gas-phase process and a colloidal approach, and the application of ozone as an oxidant for the transformation of metal carbonyls into oxides in the liquid phase.     

Development of methods for synthesis of surface-modified fluoropolymer-containing composite materials

The results of studies into development of methods for synthesizing new modified fluoropolymer-containing composite materials were summarized. The issues covered include: new modes and initiation methods of graft polymerization of fluoromonomers onto the surface of items of various nature and dispersity without homopolymer formation; nature of the surface active centers of the modified material and how it affects the kinetics and mechanism of both postradiation graft polymerization of tetrafluoroethylene and the subsequent chemical modification of the graft-polymer; major mechanisms and methods of blocking the terminal radicals of the grafted fluoropolymer layer, including those based on reaction with some perfluoroolefins at their double bond, yielding stable long-lived radicals, which allows controlling the physicochemical properties of composite materials; and new methods of synthesis of selective biocompatible sorbents with specific adsorption properties. Accelerating effect of oxygen on polymerization was analyzed, and the phenomenon of ozone initiation of low-temperature polymerization of tetrafluoroethylene was revealed and examined; a new class of high-performance polymerization initiators, namely, perflouroolefin ozonides, was synthesized; and new methods of initiation of polymerization and copolymerization of fluoromonomers, as well as of some other monomers with their use were developed.     

Ozone‐Induced Band Bending on Metal‐Oxide Surfaces Studied under Environmental Conditions

Ozone adsorption and decomposition on metal oxides is of wide interest in technology and in atmospheric chemistry. Here, ozone‐adsorption‐induced band bending is observed on Ti‐ and Fe‐oxide model surfaces under dry and humid conditions. Photoelectron spectroscopic studies indicate the effect of charge transfer to O₃, which limits the surface coverage of the precursor to decomposition reactions. This is also consistent with the negative pressure dependence observed in previous studies. These results contribute to our fundamental understanding of ozone adsorption and decomposition mechanisms on metal oxides of environmental and technological relevance.     

Luminescent Graphene-Based Materials via Europium Complexation on Dipyridylpyridazine-Functionalized Graphene Sheets

Graphene-based materials exhibit outstanding physical properties and so are potentially applicable in a great variety of fields. Unlike their corresponding oxides, graphite and graphene are not prone to functionalization. Diels–Alder reactions are among the scarce reactions that they can occur without disrupting their conjugated sp² systems. Herein, the reaction between graphite and 3,6-di(2-pyridyl)-1,2,4,5-tetrazine under different conditions affords several graphene-based materials consisting of dipyridylpyridazine-functionalized few-layer graphene, multilayer graphene and graphite, the sheets of which act as ligands for the grafting of a europium complex. These three materials show strong red emission under 365 nm UV radiation. Their emitting particles can be visualized by confocal microscopy. The rich coordination chemistry of dipyridylpyridazine ligands has potential novel properties for similarly functionalized graphene-based materials grafted with other metal complexes.     

Metal-plated carbon and basalt fabrics for shielding of electromagnetic radiation

The possibility of using metal-plated carbon and basalt fabrics for shielding electromagnetic radiation in a wide frequency range was demonstrated. The electrophysical characteristics of carbon, metal-plated carbon, and metal-plated basalt fabrics were compared. The optimum conditions of metal plating of complex textile structures, ensuring high electrophysical properties of the resulting combined materials, were determined, including the optimum conditions for pretreatment of nonconducting fibers and fabrics prior to metal plating and compositions of low-temperature electrolytes for electroless copper and nickel plating, with which uniform distribution of the metals can be obtained on each element of the textile structure.     

Vapor phase polymerization of 3,4‐ethylenedioxythiophene on flexible substrate and its application on heat generation

An oxidative chemical vapor phase polymerization process is applied to coat flexible polyethylene terephthalate (PET) fabrics with a uniform poly(3,4‐ethylenedioxythiophene) (PEDOT) film. This vapor phase polymerization method is a solventfree technique, which could yield a low resistance in the PEDOT‐coated PET fabric. The resistance as low as 52 Ω square^?1 is achieved. The polymerization conditions, such as the concentration of oxidant, reaction time, and temperature, have been systematically investigated. The coated fabric samples exhibit an increase in temperature when subjected to a fixed DC voltage. This result indicates a potential application of these PEDOT‐coated fabrics as electric heating materials. Copyright © 2009 John Wiley & Sons, Ltd.     

Polyaniline‐Intercalated Molybdenum Oxide Nanocomposites: Simultaneous Synthesis and their Enhanced Application for Supercapacitor

A new and universal synthetic strategy to hybridize metal oxides and conduct polymer nanocomposites has been proposed in this work. The simultaneous reaction process, which includes the generation of metal oxide layers, the oxidation polymerization of monomers, and the in situ formation of polymer–metal oxides sandwich structure is successfully realized and results in the unique hybrid polyaniline (PANI)‐intercalated molybdenum oxide nanocomposites. The peroxomolybdate proved to play a dual role as the precursor of the inorganic hosts and the oxidizing agent for polymerization. The as‐obtained hybrid nanocomposites present a flexible lamellar structure by oriented assembly of conductive PANI chains in the MoO₃ interlayer, and thus inherit excellent electrical performance and possess the potential of active electrode materials for electrochemical energy storage. Such uniform lamellar structure together with the anticipated high conductivity of the hybrid PANI/MoO₃ nanocomposites afford high specific capacitance and good stability during the charge–discharge cycling for supercapacitor application.     

Preparation of Metal Oxide Nanotubes Using Gelators as Structure-Directing Agents

Summary: Cationic gelators, capable of gelling alcohols, were developed as structure-directing agents for preparing metal oxides. The sol-gel polymerization of metal alkoxides using the gelators as templates afforded metal oxide nanotubes. The unique structure of metal oxides was created by transferring the shape of fibrous aggregates of gelator. The electrostatic interaction between cationic gelator and anionic metal oxide precursor plays an important role for acting as templates.     

Synthesis of morphology-controllable mesoporous Co3O4 and CeO2

Recently, extensive works have been devoted to the morphology control of mesoporous materials with respect to their use in various applications. In this paper, we used two kinds of mesoporous silica, SBA-15 rods and spheres as hard templates to synthesize morphology-controllable mesoporous metal oxides. By carefully controlling the loading of metal precursors in the mesopores of the hard template, mesoporous Co₃O₄ and CeO₂ with different morphologies, such as micrometer-sized rod, hollow sphere, saucer-like sphere, and solid sphere were conveniently obtained. The structural properties of these materials were characterized by XRD, BET, SEM and TEM. In addition, it is found that the differences observed in the textural properties of the two mesoporous metal oxides nanocasted from the same template can be attributed to the properties of metal precursors and the interaction between metal oxide and SiO₂. Thus-obtained mesoporous metal oxides with such special morphologies may have a potential application in the field of environmental catalytic oxidation.     

Heavy metal immobilization in aqueous solution using calcium phosphate and calcium hydrogen phosphates

This study examines the possibilities for removing heavy metal cations from water with calcium phosphate, calcium hydrogen phosphate, and calcium dihydrogen phosphate at 293 K. It was reported that immobilization of aqueous heavy metal cations, which is known to be one of the characteristic properties of calcium hydroxyapatite, proceeded favorably with these phosphates. Calcium phosphate, calcium hydrogen phosphate, and calcium dihydrogen phosphate could favorably remove Pb2+ from aqueous solution. Calcium hydrogen phosphate also removed aqueous Cu2+, Co2+, and Cd2+, whereas these cations were not immobilized by calcium phosphate and calcium dihydrogen phosphate. A contribution of the dissolution-precipitation mechanism to immobilization with these phosphates is suggested.     

In Situ Immobilization of Palladium Nanodots in C−C Bonded 2D Conjugated Polymers through Suzuki Polymerization at the Liquid–Liquid Interface

Traditional methods for immobilization of noble metal nanodots in 2D materials (2DMs) need multiple steps and unfriendly reaction conditions. Herein, a one-step method was developed by immobilizing in situ palladium nanodots during the preparation of the 2D conjugated polymer (2DCP) through Suzuki polymerization on interface under mild conditions. Through this method, three 2D conjugated nanosheets carrying palladium nanodots were synthesized.     

Ordered Mesoporous Silica as Supports in the Heterogeneous Asymmetric Catalysis

Enantioselective synthesis of organic compounds has been studied by homogeneous catalysts for several years. However, these catalysts have yet to make a significant impact on industrial scales for fine chemical synthesis. A primary reason is the designing of a homogeneous asymmetric catalyst, which requires relatively bulky ligands and catalyst recovery and recycling often causes problems. One of the convincing ways to overcome this problem is to immobilise the asymmetric catalyst onto a solid support and the resulting heterogeneous asymmetric catalyst system can, in principle, be readily re-used. A large number of supports such as inorganic oxides including zeolites, alumina, zirconia, silica and organic polymers have been employed as supports in heterogeneous asymmetric catalysis. Therefore, in this review article we have summarized the work done by us in our laboratory on the immobilization of chiral transition metal complexes such as Ru, Ir, Mn and Ti onto ordered mesoporous silica and its asymmetric catalysis. All these immobilized catalysts were well characterized by different physicochemical techniques to confirm the structural retention of the support as well as the active metal complex after immobilization. This report includes our asymmetric catalytic investigations in enantioselective reactions such as hydrogenation of ketones, olefins, oxidation of sulfides and oxidative kinetic resolution of alcohols and sulfoxides through immobilized heterogeneous catalyst systems.     

A short review of radiation-induced raft-mediated graft copolymerization: A powerful combination for modifying the surface properties of polymers in a controlled manner

Surface grafting of polymeric materials is attracting increasing attention as it enables the preparation of new materials from known and commercially available polymers having desirable bulk properties such as thermal stability, elasticity, permeability, etc., in conjunction with advantageous newly tailored surface properties such as biocompatibility, biomimicry, adhesion, etc. Ionizing radiation, particularly γ radiation is one of the most powerful tools for preparing graft copolymers as it generates radicals on most substrates. With the advent of living free-radical polymerization techniques, application of γ radiation has been extended to a new era of grafting; grafting in a controlled manner to achieve surfaces with tailored and well-defined properties. This report presents the current use of γ radiation in living free-radical polymerization and highlights the use of both techniques together as a combination to present an advance in the ability to prepare surfaces with desired, tunable and well-defined properties.