The Probiotic Lactobacillus johnsonii NCC 533 produces high-molecular-mass inulin from sucrose by using an inulosucrase enzyme

NARCIS (Netherlands)

Anwar, Munir A.; Kralj, Slavko; van der Maarel, Marc J. E. C.; Dijkhuizen, Lubbert

Fructansucrase enzymes polymerize the fructose moiety of sucrose into levan or inulin fructans, with beta(2-6) and beta(2-1) linkages, respectively. The probiotic bacterium Lactobacillus johnsonii strain NCC 533 possesses a single fructansucrase gene (open reading frame AAS08734) annotated as a

Stillage as a Source of Growth Promoting Biofactors and a Stimulator of Levan and Extracellular Levansucrase Synthesis for Zymomonas mobilis

Directory of Open Access Journals (Sweden)

Mara Grube

2002-01-01

Full Text Available In the present work, the fermentation of simultaneous production of ethanol and levan by Zymomonas mobilis grown on different growth media has been studied. Yeast extract, rye stillage or sugar beet molasses stillage were used as additives to the basic sucrose media and the chemical composition, including vitamins, of the cultivation liquids have been determined. It has been shown that 0.5 % of yeast extract dry weight additive could be substituted by 10.0 % of native stillage additive. It was established that molasses stillage stimulates the ethanol synthesis, but rye stillage additive is more preferable for levan production. The extracellular levansucrase obtained from the culture liquid resulted in similar fructooligosaccharide-producing activities using all the above-mentioned media additives.

High Vacuum Techniques for Anionic Polymerization

KAUST Repository

Ratkanthwar, Kedar; Hadjichristidis, Nikolaos; Mays, Jimmy

2015-01-01

Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization

High Vacuum Techniques for Anionic Polymerization

KAUST Repository

Ratkanthwar, Kedar

2015-09-01

Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization reactor, it is the best way to avoid any termination of living polymers during the number of steps for the synthesis of polymers with complex structure. In this chapter, we describe the different polymerization reactors and HVTs for the purification of monomers, solvents, and other reagents for anionic polymerization as well as few model reactions for the synthesis of polymers with simple to complex structure.

Bacillus amyloliquefaciens levansucrase-catalyzed the synthesis of fructooligosaccharides, oligolevan and levan in maple syrup-based reaction systems.

Science.gov (United States)

Li, Mengxi; Seo, Sooyoun; Karboune, Salwa

2015-11-20

Maple syrups with selected degree Brix (°Bx) (15, 30, 60) were investigated as reaction systems for levansucrase from Bacillus amyloliquefaciens. The enzymatic conversion of sucrose present in the maple syrup and the production of the transfructosylation products were assessed over a time course of 48h. At 30°C, the use of maple syrup 30°Bx led to the highest levansucrase activity (427.53μmol/mg protein/min), while maple syrup 66°Bx led to the highest converted sucrose concentration (1.53M). In maple syrup 30°Bx, oligolevans (1080%). In maple syrup 66°Bx, the most abundant products were oligolevans at 30°C and levans (DP≥30) at 8°C. The acceptor specificity study revealed the ability of B. amyloliquefaciens levansucrase to synthesize a variety of hetero-fructooligosaccharides (FOSs) in maple syrups 15°Bx and 30°Bx enriched with various disaccharides, with lactose being the preferred fructosyl acceptor. The current study is the first to investigate maple-syrup-based reaction systems for the synthesis of FOSs/oligolevans/levans. Copyright © 2015 Elsevier Ltd. All rights reserved.

Application of fractional factorial design to levan production by Zymomonas mobilis Aplicação do planejamento fatorial fracionário para a produção de levana por Zymomonas mobilis

Directory of Open Access Journals (Sweden)

I.R. Melo

2007-03-01

Full Text Available Levan is a non-toxic, biologically active, extra cellular polysaccharide composed solely by fructose units. Optimization of levan production by Zymomonas mobilis strain ZAG-12 employing a 2(4-1 fractional factorial design was performed to analyze the influence of the temperature (20, 25 e 30ºC agitation (50, 75 e 100 rpm, and the initial concentrations of both sucrose (150, 200 e 250 g.L-1 and yeast extract (2.0, 3.5 e 5.0g.L-1 on final levan concentration. Aerobic fermentation was performed batchwise in 500mL Pyrex flasks for 72 hours. Biomass, ethanol, levan and sucrose were determined at beginning and also at end of the fermentations. The experiments showed that the final levan concentration depended on initial sucrose concentration, temperature and agitation velocity and that the initial concentration of yeast extract did not influence levan production. However, when the production of ethanol and biomass were considered, it became evident that yeast extract was a significant variable. The best conditions for levan production occurred at 100 rpm agitation, 20ºC and 250g.L-1 of initial sucrose resulting in 14.67g.L-1 of levan.Levana é um polissacarídeo extracelular, biologicamente ativo, não tóxico, contendo em sua estrutura apenas frutose. A maximização da produção de levana, por via fermentativa, pela linhagem de Zymomonas mobilis ZAG-12, foi estudada utilizando-se um planejamento fatorial de dois níveis 2(4-1, variando-se as concentrações iniciais de sacarose (150, 200 e 250 g.L-1 , extrato de levedura (2.0, 3.5 e 5.0 g.L-1, temperatura (20, 25 e 30ºC e agitação (50, 75 e 100 rpm. As fermentações foram desenvolvidas por processos descontínuos em frascos Pyrex roscados, de 500 mL, contendo 300 mL de meio a base de sacarose, por 72 horas. No início e ao final do processo, foram dosados: biomassa, etanol, levana e sacarose como açúcares redutores totais. A análise dos dados mostra que o aumento da produção de levana

The anti-obesity effects of the dietary combination of fermented red ginseng with levan in high fat diet mouse model.

Science.gov (United States)

Oh, Jin sun; Lee, Seung Ri; Hwang, Keum Taek; Ji, Geun Eog

2014-04-01

In this study, to evaluate the anti-obesity effects of fermented red ginseng (FG), levan (L), and their combination (FGL), we investigated their effects on the weights of body, liver and white adipose tissue, lipid profiles, and biomarkers for insulin resistance in high fat diet (HFD)-induced obese C57BL/6J male mice. Furthermore, the levels of leptin in the serum were measured. FG (150 mg/kg/d), L (100 mg/kg/d), and FGL (150 mg/kg/d of FG plus 100 mg/kg/d of L) were administered orally to mice daily for 11 weeks. After 11 weeks feeding, FGL showed significantly lower body weight and fat mass with decreasing food efficiency ratio than the HFD control mice. In addition, the FGL group was significantly lower in the levels of total cholesterol and fasting blood glucose and score of the homeostatic model assessment of insulin resistance. Furthermore, FGL decreased serum leptin levels compared to the HFD control group. Taken together, FGL showed a significant anti-obesity effect in HFD-induced obese mice and prevent insulin and leptin resistance. FGL may be potentially useful for the prevention of obesity. Copyright © 2013 John Wiley & Sons, Ltd.

The Production, Purification and Properties of the Biopolymer Levan Produced by the Bacterium Erwinia Herbicola

Science.gov (United States)

1989-08-01

after comparison with ATCC 11142 Acetobacter pasteurianus. ATCC 15953 Microbacterium 2 laevanlformans. and QMB 1624 Bacillus coagulans (B, gub^jlu...is produced by several bacteria, including Brwjnja herbicola. Streptococcus salivarius. Pseudomonas prunicola. Bacillus subtilis. and Actinomvcetes...J, i X I i rtfi ii i IT PTT-n T~^L^^^^ r1 •» ■ ■ 11 ■ ■ ■ i >■ 111 I’I I’.VIT fi-H-rtfi 1 -f ’ •■» i | i r , , , Levan from Bacillus

Effects of levan-type fructan on growth performance, nutrient digestibility, diarrhoea scores, faecal shedding of total lactic acid bacteria and coliform bacteria, and faecal gas emission in weaning pigs.

Science.gov (United States)

Lei, Xin Jian; Kim, Yong Min; Park, Jae Hong; Baek, Dong Heon; Nyachoti, Charles Martin; Kim, In Ho

2018-03-01

The use of antibiotics as growth promoters in feed has been fully or partially banned in several countries. The objective of this study was to evaluate effects of levan-type fructan on growth performance, nutrient digestibility, faecal shedding of lactic acid bacteria and coliform bacteria, diarrhoea scores, and faecal gas emission in weaning pigs. A total of 144 weaning pigs [(Yorkshire × Landrace) × Duroc] were randomly allocated to four diets: corn-soybean meal-based diets supplemented with 0, 0.1, 0.5, or 1.0 g kg -1 levan-type fructan during this 42-day experiment. During days 0 to 21 and 0 to 42, average daily gain and average daily feed intake were linearly increased (P bacteria counts were linearly increased (P = 0.001). The results indicate that dietary supplementation with increasing levan-type fructan enhanced growth performance, improved nutrient digestibility, and increased faecal lactic acid bacteria counts in weaning pigs linearly. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Emulsion polymerization with high energy radiation

International Nuclear Information System (INIS)

Stannett, V.T.; Stahel, E.P.

1992-01-01

High energy radiation, particularly that of cobalt-60 or caesium-137 gamma-rays, provides in principle an ideal initiator for emulsion polymerization. The high free radical yields from the radiolysis of the aqueous phase combined with the high kinetic chain lengths associated with emulsion polymerization lead to a highly effective utilization of the radiation. There are other important advantages compared with the use of chemical initiators such as potassium persulfate. These are outlined in the chapter, together with some attendant disadvantages. Radiation-induced initiation is temperature independent, and low temperature polymerizations can be conducted with ease. Monomers that mainly terminate their growing chains by chain transfer to monomer give higher molecular weights at lower temperatures. Industrially, vinyl acetate is an important example of such a monomer, and it has been studied using radiation initiation. Both laboratory and pilot plant studies have been carried out and reported. The results are summarized in this chapter. Styrene is the classical example of a material that under a number of conditions closely obeys the so-called ideal Smith-Ewart kinetics. It has been found that under similar conditions but substituting radiation for potassium persulfate as the initiator, ideal kinetics were closely followed. Most of the conventional and some non-standard vinyl and diene monomers have been studied to some extent with radiation-initiated polymerizations in emulsion. To conserve space however, this chapter presents and discusses the results obtained only with styrene and vinyl acetate, both in laboratory and pilot plant investigations. Other monomers and special situations are referenced either directly or to the other available reviews. (orig.)

Purification, cloning, characterization, and N-glycosylation analysis of a novel β-fructosidase from Aspergillus oryzae FS4 synthesizing levan- and neolevan-type fructooligosaccharides.

Directory of Open Access Journals (Sweden)

Li Xu

Full Text Available β-Fructosidases are a widespread group of enzymes that catalyze the hydrolysis of terminal fructosyl units from various substrates. These enzymes also exhibit transglycosylation activity when they function with high concentrations of sucrose, which is used to synthesize fructooligosaccharides (FOS in the food industry. A β-fructosidase (BfrA with high transglycosylation activity was purified from Aspergillus oryzae FS4 as a monomeric glycoprotein. Compared with the most extensively studied Aspergillus spp. fructosidases that synthesize inulin-type β-(2-1-linked FOS, BfrA has unique transfructosylating property of synthesizing levan- and neolevan-type β-(2-6-linked FOS. The coding sequence (bfrAFS4, 1.86 kb of BfrA was amplified and expressed in Escherichia coli and Pichia pastoris. Both native and recombinant proteins showed transfructosylation and hydrolyzation activities with broad substrate specificity. These proteins could hydrolyze the following linkages: Glc α-1, 2-β Fru; Glc α-1, 3-α Fru; and Glc α-1, 5-β Fru. Compared with the unglycosylated E. coli-expressed BfrA (E.BfrA, the N-glycosylated native (N.BfrA and the P. pastoris-expressed BfrA (P.BfrA were highly stable at a wide pH range (pH 4 to 11, and significantly more thermostable at temperatures up to 50°C with a maximum activity at 55°C. Using sucrose as substrate, the Km and kcat values for total activity were 37.19±5.28 mM and 1.0016±0.039×104 s-1 for N.BfrA. Moreover, 10 of 13 putative N-glycosylation sites were glycosylated on N.BfrA, and N-glycosylation was essential for enzyme thermal stability and optima activity. Thus, BfrA has demonstrated as a well-characterized A. oryzae fructosidase with unique transfructosylating capability of synthesizing levan- and neolevan-type FOS.

Plasma polymerized high energy density dielectric films for capacitors

Science.gov (United States)

Yamagishi, F. G.

1983-01-01

High energy density polymeric dielectric films were prepared by plasma polymerization of a variety of gaseous monomers. This technique gives thin, reproducible, pinhole free, conformable, adherent, and insoluble coatings and overcomes the processing problems found in the preparation of thin films with bulk polymers. Thus, devices are prepared completely in a vacuum environment. The plasma polymerized films prepared all showed dielectric strengths of greater than 1000 kV/cm and in some cases values of greater than 4000 kV/cm were observed. The dielectric loss of all films was generally less than 1% at frequencies below 10 kHz, but this value increased at higher frequencies. All films were self healing. The dielectric strength was a function of the polymerization technique, whereas the dielectric constant varied with the structure of the starting material. Because of the thin films used (thickness in the submicron range) surface smoothness of the metal electrodes was found to be critical in obtaining high dielectric strengths. High dielectric strength graft copolymers were also prepared. Plasma polymerized ethane was found to be thermally stable up to 150 C in the presence of air and 250 C in the absence of air. No glass transitions were observed for this material.

Radiation-induced polymerization of glass-forming systems. VII. Polymerization in supercooled state under high pressure

International Nuclear Information System (INIS)

Kaetsu, I.; Yoshii, F.; Watanabe, Y.

1978-01-01

Radiation-induced polymerization of glass-forming monomers such as 2-hydroxyethyl methacrylate and glycidyl methacrylate under high pressure was studied. The glass transition temperature of these monomers was heightened by increased pressure. The temperature dependence of polymerizability showed a characteristic relation, similar to those in supercooled-phase polymerization under normal pressure, that had a maximum at T/sub ν/ which shifted to higher levels of temperature as well as to T/sub g/ under high pressure. Polymerizability in the supercooled state also increased under increased pressure

Preparation of Biocomposites using Sawdust and Lignosulfonate with a Culturе Liquid of Levan Producer Azotobacter vinelandii as a Bonding Agent

Directory of Open Access Journals (Sweden)

Victor V. Revin

2016-02-01

Full Text Available The possibility of preparing molding-bioengineered materials, such as woodchip boards (WCB, from sawdust using technical lignosulfonate (LGS, a wood waste product, and a culture liquid (CL of levan microbial polysaccharide producer by Azotobacter vinelandii D-08 is explored in this article. The parameters of the derived materials are comparable to those of traditional materials made from toxic phenol-formaldehyde resins. The various physical and mechanical characteristics of the materials depend on the quantity of the bonding agent used for the preparation. Adding a culture liquid increases the humidity resistance of the molding materials. Using electron microscopy and X-ray micro-tomography, it is clear that the structure of woodchip boards become more homogeneous without microcracks with the addition of CL. The strength of the best samples prepared was approximately 24 to 29 MPa with a density of 1170 to 1255 kg/m3 and a swell on wetting of 6.7%. During hot pressing, noticeable changes were observed by Fourier transform infrared spectroscopy (FTIR at frequencies typical of LGS sulfonic-acid groups, levan fructose fragments, and skeletal vibrations of a syringal/guaiacyl core in lignin and of C-H groups of hemicelluloses. This indicates the involvement of these functional groups in the process of binding wood particles with hot pressing.

High-voltage polymeric insulated cables

Energy Technology Data Exchange (ETDEWEB)

Ross, A

1987-01-01

Reviews developments in high-voltage (here defined as 25 kV, 66 kV and 132 kV) polymeric insulated cables in the UK over the period 1979-1986, with particular reference to the experience of the Eastern Electricity Board. Outlines the background to the adoption of XPLE-insulated solid cable, and the design, testing, terminations, jointing and costs of 25 kV, 66 kV and 132 kV cables.

Simultaneous measurement of polymerization stress and curing kinetics for photo-polymerized composites with high filler contents.

Science.gov (United States)

Wang, Zhengzhi; Landis, Forrest A; Giuseppetti, Anthony A M; Lin-Gibson, Sheng; Chiang, Martin Y M

2014-12-01

Photopolymerized composites are used in a broad range of applications with their performance largely directed by reaction kinetics and contraction accompanying polymerization. The present study was to demonstrate an instrument capable of simultaneously collecting multiple kinetics parameters for a wide range of photopolymerizable systems: degree of conversion (DC), reaction exotherm, and polymerization stress (PS). Our system consisted of a cantilever beam-based instrument (tensometer) that has been optimized to capture a large range of stress generated by lightly-filled to highly-filled composites. The sample configuration allows the tensometer to be coupled to a fast near infrared (NIR) spectrometer collecting spectra in transmission mode. Using our instrument design, simultaneous measurements of PS and DC are performed, for the first time, on a commercial composite with ≈80% (by mass) silica particle fillers. The in situ NIR spectrometer collects more than 10 spectra per second, allowing for thorough characterization of reaction kinetics. With increased instrument sensitivity coupled with the ability to collect real time reaction kinetics information, we show that the external constraint imposed by the cantilever beam during polymerization could affect the rate of cure and final degree of polymerization. The present simultaneous measurement technique is expected to provide new insights into kinetics and property relationships for photopolymerized composites with high filler content such as dental restorative composites. Published by Elsevier Ltd.

Radiation polymerization of acrylamide with super-high molecular weight in inverse emulsion

International Nuclear Information System (INIS)

Ye Qiang; Ge Xuewu; Xu Xiangling; Zhang Zhicheng

1998-01-01

The inverse emulsion polymerization of acrylamide has been studied with γ-ray initiation. Polyacrylamide with super high molecular weight over ten million (11 x 10 6 ), which is very important in application as flocculant, is obtained. In this work, some methods are taken to enhance the molecular weight as follows: (1) In order to prepare soluble polyacrylamide with super high molecular weight, the better conditions are: the emulsifier content is about 2% and the monomer concentration is about 20%∼24% in the composition of monomer emulsion, and the absorbed dose is about 500∼600 Gy. (2) Initiating with high dose rate and polymerizing with low dose rate can not only enhance the molecular weight of product, but also curtail the polymerizing time. (3) Stopping radiation when the conversion gets to about 10% and post-polymerizing outside the radiation source until the conversion gets to 82% can obtain polyacrylamide with super high molecular weight, and shorten the irradiation time as well

Highly efficient reversible addition-fragmentation chain-transfer polymerization in ethanol/water via flow chemistry

Energy Technology Data Exchange (ETDEWEB)

Ye, Piaoran [Case Western Reserve Univ., Cleveland, OH (United States); Cao, Peng -Fei [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Su, Zhe [Case Western Reserve Univ., Cleveland, OH (United States); Advincula, Rigoberto [Case Western Reserve Univ., Cleveland, OH (United States)

2017-03-23

Here, utilization of a flow reactor under high pressure allows highly efficient polymer synthesis via reversible addition–fragmentation chain-transfer (RAFT) polymerization in an aqueous system. Compared with the batch reaction, the flow reactor allows the RAFT polymerization to be performed in a high-efficiency manner at the same temperature. The adjustable pressure of the system allows further elevation of the reaction temperature and hence faster polymerization. Other reaction parameters, such as flow rate and initiator concentration, were also well studied to tune the monomer conversion and the molar mass dispersity (Ð) of the obtained polymers. Gel permeation chromatography, nuclear magnetic resonance (NMR), and Fourier transform infrared spectroscopies (FTIR) were utilized to monitor the polymerization process. With the initiator concentration of 0.15 mmol L^–1, polymerization of poly(ethylene glycol) methyl ethermethacrylate with monomer conversion of 52% at 100 °C under 73 bar can be achieved within 40 min with narrow molar mass dispersity (D) Ð (<1.25). The strategy developed here provides a method to produce well-defined polymers via RAFT polymerization with high efficiency in a continuous manner.

Highly efficient and selective pressure-assisted photon-induced polymerization of styrene

Energy Technology Data Exchange (ETDEWEB)

Guan, Jiwen [Department of Physics and Astronomy, University of Western Ontario, London, Ontario N6A 3K7 (Canada); Song, Yang, E-mail: yang.song@uwo.ca [Department of Physics and Astronomy, University of Western Ontario, London, Ontario N6A 3K7 (Canada); Department of Chemistry, University of Western Ontario, London, Ontario N6A 5B7 (Canada)

2016-06-07

The polymerization process of condensed styrene to produce polystyrene as an industrially important polymeric material was investigated using a novel approach by combining external compression with ultraviolet radiation. The reaction evolution was monitored as a function of time and the reaction products were characterized by in situ Fourier transform infrared spectroscopy. By optimizing the loading pressures, we observed highly efficient and selective production of polystyrene of different tacticities. Specifically, at relatively low loading pressures, infrared spectra suggest that styrene monomers transform to amorphous atactic polystyrene (APS) with minor crystalline isotactic polystyrene. In contrast, APS was found to be the sole product when polymerization occurs at relatively higher loading pressures. The time-dependent reaction profiles allow the examination of the polymerization kinetics by analyzing the rate constant and activation volume as a function of pressure. As a result, an optimized pressure condition, which allows a barrierless reaction to proceed, was identified and attributed to the very desirable reaction yield and kinetics. Finally, the photoinitiated reaction mechanism and the growth geometry of the polymer chains were investigated from the energy diagram of styrene and by the topology analysis of the crystal styrene. This study shows strong promise to produce functional polymeric materials in a highly efficient and controlled manner.

A Self-Reporting Photocatalyst for Online Fluorescence Monitoring of High Throughput RAFT Polymerization.

Science.gov (United States)

Yeow, Jonathan; Joshi, Sanket; Chapman, Robert; Boyer, Cyrille Andre Jean Marie

2018-04-25

Translating controlled/living radical polymerization (CLRP) from batch to the high throughput production of polymer libraries presents several challenges in terms of both polymer synthesis and characterization. Although recently there have been significant advances in the field of low volume, high throughput CLRP, techniques able to simultaneously monitor multiple polymerizations in an "online" manner have not yet been developed. Here, we report our discovery that 5,10,15,20-tetraphenyl-21H,23H-porphine zinc (ZnTPP) is a self-reporting photocatalyst that can mediate PET-RAFT polymerization as well as report on monomer conversion via changes in its fluorescence properties. This enables the use of a microplate reader to conduct high throughput "online" monitoring of PET-RAFT polymerizations performed directly in 384-well, low volume microtiter plates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly durable and unidirectionally stooped polymeric nanohairs for gecko-like dry adhesive

International Nuclear Information System (INIS)

Im, Hyeon Seong; Kwon, Ki Yoon; Kim, Jong Uk; Kim, Tae-il; Kim, Kwang Su; Yi, Hoon; Jeong, Hoon Eui; Yoo, Pil J; Pang, Changhyun

2015-01-01

Gecko-like dry adhesive using high aspect ratio polymeric nanohairs has insuperable limitations, although it has huge potential in many applications. Repeated harsh contacts on a target substrate lead to physical collapse of nanohairs and significant degradation of the adhesion property, because the polymeric nanohairs are quite fragile due to poor mechanical robustness. Herein, we demonstrate a highly robust gecko-like dry adhesive with unidirectionally stooped polymeric nanohairs (diameter 100 nm) with a high aspect ratio (∼9) using an ultrathin metal coating. 100 cycles of repeated adhesion tests with 1 N preloading force did not significantly degrade adhesion or cause collapse of nanohairs. We believe that this approach allows gecko-like dry adhesive to be utilized in many related applications and diverse industry interests. (paper)

Radiation chemistry of polymeric system

International Nuclear Information System (INIS)

Machi, Sueo; Ishigaki, Isao

1978-01-01

Among wide application of radiation in the field of polymer chemistry, practices of polymerization, graft polymerization, bridging, etc. are introduced hereinafter. As for the radiation sources of radiation polymerization, in addition to the 60 Co-γ ray with long permeation distance which has been usually applied, electron beam accelerators with high energy, large current and high reliability have come to be produced, and the liquid phase polymerization by electron beam has attracted attention industrially. Concerning polymerizing reactions, explanations were given to electron beam polymerization under high dose rate, the polymerization in supercooling state or under high pressure, and emulsifying polymerization. As for radiation bridging, radiation is applied for the bridging of hydrogel, acceleration of bridging and improvement of radiation resistance. It is also utilized for reforming membranes by graft polymerization, and synthesis of polymers for medical use. Application of fixed enzymes in the medical field has been investigated by fixing various enzymes by low temperature γ-ray polymerization with glassy monomers such as HEMA. (Kobatake, H.)

A New Route for High-Purity Organic Materials: High-Pressure-Ramp-Induced Ultrafast Polymerization of 2-(Hydroxyethyl)Methacrylate

Science.gov (United States)

Evlyukhin, E.; Museur, L.; Traore, M.; Perruchot, C.; Zerr, A.; Kanaev, A.

2015-12-01

The synthesis of highly biocompatible polymers is important for modern biotechnologies and medicine. Here, we report a unique process based on a two-step high-pressure ramp (HPR) for the ultrafast and efficient bulk polymerization of 2-(hydroxyethyl)methacrylate (HEMA) at room temperature without photo- and thermal activation or addition of initiator. The HEMA monomers are first activated during the compression step but their reactivity is hindered by the dense glass-like environment. The rapid polymerization occurs in only the second step upon decompression to the liquid state. The conversion yield was found to exceed 90% in the recovered samples. The gel permeation chromatography evidences the overriding role of HEMA2•• biradicals in the polymerization mechanism. The HPR process extends the application field of HP-induced polymerization, beyond the family of crystallized monomers considered up today. It is also an appealing alternative to typical photo- or thermal activation, allowing the efficient synthesis of highly pure organic materials.

Preparation of high surface area and high conductivity polyaniline nanoparticles using chemical oxidation polymerization technique

Science.gov (United States)

Budi, S.; Yusmaniar; Juliana, A.; Cahyana, U.; Purwanto, A.; Imaduddin, A.; Handoko, E.

2018-03-01

In this work, polyaniline nanoparticles were synthesized using a chemical oxidation polymerization technique. The ammonium peroxydisulfate (APS)/aniline ratio, APS dropping time, and polymerization temperature were optimized to increase the surface area and conductivity of the polyaniline.The Fourier-transform infrared (FTIR) spectrum confirmed the formation of emeraldine salt polyaniline. X-ray diffraction (XRD) patterns indicated that amorphous and crystalline phases of the polyaniline were formed with crystallinity less than 40%. Scanning electron microscope (SEM) micrographs showed that the finest nanoparticles with uniform size distribution were obtained at the polymerization temperature of 0°C. A surface area analyzer (SAA) showed that the highest Brunauer-Emmett-Teller surface area (SBET ) of 42.14 m2/gwas obtained from an APS/aniline ratio of 0.75 with a dropping time of 0 s at a polymerization temperature of 0°C. A four-point probe measurement conducted at 75–300K indicated relatively high conductivity of the semiconductor characteristic of the polyaniline.

Highly Defined Multiblock Copolypeptoids: Pushing the Limits of Living Nucleophilic Ring-Opening Polymerization

KAUST Repository

Fetsch, Corinna

2012-06-05

Advanced macromolecular engineering requires excellent control over the polymerization reaction. Living polymerization methods are notoriously sensitive to impurities, which makes a practical realization of such control very challenging. Reversible-deactivation radical polymerization methods are typically more robust, but have other limitations. Here, we demonstrate by repeated (ge;10 times) chain extension the extraordinary robustness of the living nucleophilic ring-opening polymerization of N-substituted glycine N-carboxyanhydrides, which yields polypeptoids. We observe essentially quantitative end-group fidelity under experimental conditions that are comparatively easily managed. This is employed to synthesize a pentablock quinquiespolymer with high definition. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Defined Multiblock Copolypeptoids: Pushing the Limits of Living Nucleophilic Ring-Opening Polymerization

KAUST Repository

Fetsch, Corinna; Luxenhofer, Robert

2012-01-01

Advanced macromolecular engineering requires excellent control over the polymerization reaction. Living polymerization methods are notoriously sensitive to impurities, which makes a practical realization of such control very challenging. Reversible-deactivation radical polymerization methods are typically more robust, but have other limitations. Here, we demonstrate by repeated (ge;10 times) chain extension the extraordinary robustness of the living nucleophilic ring-opening polymerization of N-substituted glycine N-carboxyanhydrides, which yields polypeptoids. We observe essentially quantitative end-group fidelity under experimental conditions that are comparatively easily managed. This is employed to synthesize a pentablock quinquiespolymer with high definition. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

STUDIES ON HIGH SOLID CONTENT AND STABLE EMULSIFIER—FREE EMULSION POLYMERIZATION

Institute of Scientific and Technical Information of China (English)

TangGuangliang; HaoGuangjie; 等

1998-01-01

In this article,AHPS(3-allyloxy-2-hydroxy-1-propanesulfonate salt) was synthesized to use in emulsifier-free emulsion polymerization of BA/BMA/MMA system for high solid content latexes.Storage stability,flow behavior of the latexes,morphology of the obtained latex particles,dynamic viscoelastic behavior,tensile strength and water resistance properties of the resulted copolymers were investigated.The experimental results show that with the addition of AHPS,stability of the emulsion is greatly improved that there appears no apparent precipitation during the polymerization and storage at room temperature for 6 months and at -10℃ for four months.Flow of the latexes follows the Bingham body laws,diameter of the latex particles is about 0.6μm,of which is larger than that of by conventional emulsion polymerization(0.12μm).In addition,not only water resistance of the copolymers obtained by emulsifier-free emulstion polymerization is greatly improved,but also tensile strength is obviously enhanced.

Crosslinking polymerization of tetraethylene glycol dimethacrylate under high pressure

Energy Technology Data Exchange (ETDEWEB)

Kaminski, K; Paluch, M; Ziolo, J [Institute of Physics, Silesian University, Uniwersytecka 4, 40-007 Katowice (Poland); Bogoslovov, R; Roland, C M [Chemistry Division, Code 6120, Naval Research Laboratory, Washington DC 20375-5342 (United States)], E-mail: kaminski@us.edu.pl

2008-07-15

The polymerization reaction of tetraethylene glycol dimethacrylate was induced by application of high pressure. Broadband dielectric spectroscopy was employed to investigate dielectric properties of the produced polymers. Additionally swelling experiment was performed to determine the degree of crossliniking of the polymers.

Elastic Modulus at High Frequency of Polymerically Stabilized Suspensions

NARCIS (Netherlands)

Nommensen, P.A.; Duits, Michael H.G.; van den Ende, Henricus T.M.; Mellema, J.

2000-01-01

The elastic moduli of polymerically stabilized suspensions consisting of colloidal silica particles coated with endgrafted PDMS (Mn = 80 000) in heptane, were measured as a function of concentration. And the elastic modulus at high frequency G'.. was quantitatively described by model calculations

Highly Branched Bio-Based Unsaturated Polyesters by Enzymatic Polymerization

Directory of Open Access Journals (Sweden)

Hiep Dinh Nguyen

2016-10-01

Full Text Available A one-pot, enzyme-catalyzed bulk polymerization method for direct production of highly branched polyesters has been developed as an alternative to currently used industrial procedures. Bio-based feed components in the form of glycerol, pentaerythritol, azelaic acid, and tall oil fatty acid (TOFA were polymerized using an immobilized Candida antarctica lipase B (CALB and the potential for an enzymatic synthesis of alkyds was investigated. The developed method enables the use of both glycerol and also pentaerythritol (for the first time as the alcohol source and was found to be very robust. This allows simple variations in the molar mass and structure of the polyester without premature gelation, thus enabling easy tailoring of the branched polyester structure. The postpolymerization crosslinking of the polyesters illustrates their potential as binders in alkyds. The formed films had good UV stability, very high water contact angles of up to 141° and a glass transition temperature that could be controlled through the feed composition.

Radiation induced emulsion polymerization

International Nuclear Information System (INIS)

Stannett, V.T.; Stahel, E.P.

1990-01-01

High energy radiation is particularly favored for the initiation of emulsion polymerization. The yield of free radicals, for example, from the radiolysis of the aqueous phase, is high; G(radical) values of 5-7. In addition, the rather special kinetics associated with emulsion polymerization lead, in general, to very large kinetic chain lengths, even with 'non-ideal' monomers such as vinyl acetate. Together, high polymerization rates at low doses become possible. There are some important advantages of radiation polymerization compared with chemical initiators, such as potassium persulfate. Perhaps the most important among them is the temperature independence of the initiation step. This makes low temperature polymerization very accessible. With monomers such as vinyl acetate, where chain termination to monomer is predominant, low temperatures lead to often highly desirable higher molecular weights. With styrene, the classical ideally behaved monomer, there are the advantages such as, for example, the feasibility of using cationic monomers. These and some attendant disadvantages are discussed in detail, including pilot plant studies

Highly Branched Bio-Based Unsaturated Polyesters by Enzymatic Polymerization

DEFF Research Database (Denmark)

Nguyen, Hiep Dinh; Löf, David; Hvilsted, Søren

2016-01-01

A one-pot, enzyme-catalyzed bulk polymerization method for direct production of highly branched polyesters has been developed as an alternative to currently used industrial procedures. Bio-based feed components in the form of glycerol, pentaerythritol, azelaic acid, and tall oil fatty acid (TOFA)...... stability, very high water contact angles of up to 141° and a glass transition temperature that could be controlled through the feed composition....

Carboxyl-Functionalized Polymeric Microspheres Prepared by One-Stage Photoinitiated RAFT Dispersion Polymerization

Directory of Open Access Journals (Sweden)

Jianbo Tan

2017-12-01

Full Text Available Herein, we report a photoinitiated reversible addition-fragmentation chain transfer (RAFT dispersion copolymerization of methyl methacrylate (MMA and methyl methacrylic (MAA for the preparation of highly monodisperse carboxyl-functionalized polymeric microspheres. High rates of polymerization were observed, with more than 90% particle yields being achieved within 3 h of UV irradiation. Effects of reaction parameters (e.g., MAA concentration, RAFT agent concentration, photoinitiator concentration, and solvent composition were studied in detail, and highly monodisperse polymeric microspheres were obtained in most cases. Finally, silver (Ag composite microspheres were prepared by in situ reduction of AgNO3 using the carboxyl-functionalized polymeric microspheres as the template. The obtained Ag composite microspheres were able to catalyze the reduction of methylene blue (MB with NaBH4 as a reductant.

Highly reflective polymeric substrates functionalized utilizing atomic layer deposition

Science.gov (United States)

Zuzuarregui, Ana; Coto, Borja; Rodríguez, Jorge; Gregorczyk, Keith E.; Ruiz de Gopegui, Unai; Barriga, Javier; Knez, Mato

2015-08-01

Reflective surfaces are one of the key elements of solar plants to concentrate energy in the receivers of solar thermal electricity plants. Polymeric substrates are being considered as an alternative to the widely used glass mirrors due to their intrinsic and processing advantages, but optimizing both the reflectance and the physical stability of polymeric mirrors still poses technological difficulties. In this work, polymeric surfaces have been functionalized with ceramic thin-films by atomic layer deposition. The characterization and optimization of the parameters involved in the process resulted in surfaces with a reflection index of 97%, turning polymers into a real alternative to glass substrates. The solution we present here can be easily applied in further technological areas where seemingly incompatible combinations of polymeric substrates and ceramic coatings occur.

Highly reflective polymeric substrates functionalized utilizing atomic layer deposition

Energy Technology Data Exchange (ETDEWEB)

Zuzuarregui, Ana, E-mail: a.zuzuarregui@nanogune.eu; Gregorczyk, Keith E. [CIC Nanogune Consolider, de Tolosa Hiribidea 76, 20018 San Sebastián (Spain); Coto, Borja; Ruiz de Gopegui, Unai; Barriga, Javier [IK4-Tekniker, Iñaki Goenaga 5, 20600 Eibar (Spain); Rodríguez, Jorge [Torresol Energy (SENER Group), Avda. de Zugazarte 61, 48930 Las Arenas (Spain); Knez, Mato [CIC Nanogune Consolider, de Tolosa Hiribidea 76, 20018 San Sebastián (Spain); IKERBASQUE Basque Foundation for Science, Maria Diaz de Haro 3, 48013 Bilbao (Spain)

2015-08-10

Reflective surfaces are one of the key elements of solar plants to concentrate energy in the receivers of solar thermal electricity plants. Polymeric substrates are being considered as an alternative to the widely used glass mirrors due to their intrinsic and processing advantages, but optimizing both the reflectance and the physical stability of polymeric mirrors still poses technological difficulties. In this work, polymeric surfaces have been functionalized with ceramic thin-films by atomic layer deposition. The characterization and optimization of the parameters involved in the process resulted in surfaces with a reflection index of 97%, turning polymers into a real alternative to glass substrates. The solution we present here can be easily applied in further technological areas where seemingly incompatible combinations of polymeric substrates and ceramic coatings occur.

Highly reflective polymeric substrates functionalized utilizing atomic layer deposition

International Nuclear Information System (INIS)

Zuzuarregui, Ana; Gregorczyk, Keith E.; Coto, Borja; Ruiz de Gopegui, Unai; Barriga, Javier; Rodríguez, Jorge; Knez, Mato

2015-01-01

Reflective surfaces are one of the key elements of solar plants to concentrate energy in the receivers of solar thermal electricity plants. Polymeric substrates are being considered as an alternative to the widely used glass mirrors due to their intrinsic and processing advantages, but optimizing both the reflectance and the physical stability of polymeric mirrors still poses technological difficulties. In this work, polymeric surfaces have been functionalized with ceramic thin-films by atomic layer deposition. The characterization and optimization of the parameters involved in the process resulted in surfaces with a reflection index of 97%, turning polymers into a real alternative to glass substrates. The solution we present here can be easily applied in further technological areas where seemingly incompatible combinations of polymeric substrates and ceramic coatings occur

Influence of carbon source and the fermentation process on levan production by Zymomonas mobilis analyzed by the surface response method Influência da fonte de carbono e do processo fermentativo na produção de levana por Zymomonas mobilis analisada pela metodologia de superfície de resposta

Directory of Open Access Journals (Sweden)

Raquel Renan Jorge Borsari

2006-09-01

Full Text Available The aim of this study is to assess sugar cane juice and sucrose as substrates, the batch and fed batch processes and their interaction in the levan production using a complete factorial design. Zymomonas mobilis was cultivated in different sugar cane juice and sucrose concentrations in two fermentation processes at 25 °C for 20 h. A complete factorial design (2³ was used to analyze the effects of the type and concentration of the substrate, as well as the batch and fed batch processes. A complete second factorial design (2² was used to observe the importance of sugar cane juice. The results indicated that the batch process improved the levan production reaching 40.14 g/L. The addition of sugar cane juice was not statistically significant for levan formation, however sugar cane juice stimulated biomass, sorbitol and ethanol production. The best medium for levan production was 150 g/L sucrose in batch.O presente estudo avaliou caldo de cana de açúcar e sacarose como substratos e os processos batelada e batelada alimentada e suas interações na produção de levana. Zymomonas mobilis foi cultivada em diferentes concentrações de caldo de cana de açúcar e sacarose nos dois processos fermentativos a 25 °C por 20 h. Foi utilizado um delineamento fatorial completo (23 para analisar os efeitos do tipo e concentração de substratos e processos batelada e batelada alimentada. Um segundo delineamento fatorial completo (22 foi usado para confirmar a importância do caldo de cana de açúcar. Os resultados indicam que o processo batelada foi o melhor para a produção de levana, atingindo 40,14 g/L em 150 g/L de sacarose. A adição de caldo de cana de açúcar não foi estatisticamente significativa para formação de levana, porém o caldo estimulou a produção de biomassa, sorbitol e etanol.

Synthesis and characterization of pulsed polymerized poly(3,4-ethylenedioxythiophene) electrodes for high-performance electrochemical capacitors

International Nuclear Information System (INIS)

Pandey, G.P.; Rastogi, A.C.

2013-01-01

Poly(3,4-ethylenedioxythiophene) (PEDOT) is electrochemically prepared as a film on flexible thin graphite substrate by short galvanic pulse method in organic media. For comparative studies, PEDOT films are also prepared by potentiostatic polymerization method. The nucleation and growth mechanism for PEDOT film polymerized by short current pulses is presented with morphological and structural studies. The growth of PEDOT is continuous during the pulse off period as confirmed by the deposited mass of PEDOT by these two different methods. The SEM studies of pulse polymerized PEDOT films with different pulse on time show the features of highly porous and ridge like structures which help in rapid migration of dopant ClO 4 − ions during the charge and discharge processes. The X-ray photoelectron spectroscopy (XPS) studies confirm that in the pulse polymerized PEDOT films polymer chains are fully conjugated with the dopant ClO 4 − ions. The electrochemical characterization of PEDOT films show that pulse polymerized PEDOT films exhibited high specific capacitance (126.5 F g −1 ) with an improved energy density and rate kinetics as comparison to the potentiostatically deposited PEDOT films (100 F g −1 ) in aqueous electrolyte.

Highly Active N,O Zinc Guanidine Catalysts for the Ring-Opening Polymerization of Lactide.

Science.gov (United States)

Schäfer, Pascal M; Fuchs, Martin; Ohligschläger, Andreas; Rittinghaus, Ruth; McKeown, Paul; Akin, Enver; Schmidt, Maximilian; Hoffmann, Alexander; Liauw, Marcel A; Jones, Matthew D; Herres-Pawlis, Sonja

2017-09-22

New zinc guanidine complexes with N,O donor functionalities were prepared, characterized by X-Ray crystallography, and examined for their catalytic activity in the solvent-free ring-opening polymerization (ROP) of technical-grade rac-lactide at 150 °C. All complexes showed a high activity. The fastest complex [ZnCl 2 (DMEGasme)] (C1) produced colorless poly(lactide) (PLA) after 90 min with a conversion of 52 % and high molar masses (M w =69 100, polydispersity=1.4). The complexes were tested with different monomer-to-initiator ratios to determine the rate constant k p . Furthermore, a polymerization with the most active complex C1 was monitored by in situ Raman spectroscopy. Overall, conversion of up to 90 % can be obtained. End-group analysis was performed to clarify the mechanism. All four complexes combine robustness against impurities in the lactide with high polymerization rates, and they represent the fastest robust lactide ROP catalysts to date, opening new avenues to a sustainable ROP catalyst family for industrial use. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymerization Using Phosphazene Bases

KAUST Repository

Zhao, Junpeng

2015-09-01

In the recent rise of metal-free polymerization techniques, organic phosphazene superbases have shown their remarkable strength as promoter/catalyst for the anionic polymerization of various types of monomers. Generally, the complexation of phosphazene base with the counterion (proton or lithium cation) significantly improves the nucleophilicity of the initiator/chain end resulting in highly enhanced polymerization rates, as compared with conventional metalbased initiating systems. In this chapter, the general features of phosphazenepromoted/catalyzed polymerizations and the applications in macromolecular engineering (synthesis of functionalized polymers, block copolymers, and macromolecular architectures) are discussed with challenges and perspectives being pointed out.

Isolation and characterization of inulin with a high degree of polymerization from roots of Stevia rebaudiana (Bert.) Bertoni.

Science.gov (United States)

Lopes, Sheila M S; Krausová, Gabriela; Rada, Vojtěch; Gonçalves, José E; Gonçalves, Regina A C; de Oliveira, Arildo J B

2015-06-26

The polysaccharide inulin has great importance in the food and pharmaceutical industries. The degree of polymerization (DP) of inulin influences important properties, such as, solubility, thermal stability, sweetness power and prebiotic activity. Molecules with a high degree of polymerization are obtained through physical techniques for enrichment of the inulin chains because they are not commonly obtained from plants extract. Gas chromatography/Mass Spectrometry and (1)H Nuclear Magnetic Resonance analysis showed that inulin from Stevia rebaudiana roots has a degree of polymerization (DPn 28) higher than the value of DPn 12-15 for inulins from other plant species. Furthermore, the methodology of freeze/thaw to enrich the chains allowed us to increase the DP, similarly to other methodologies used for the enrichment of inulin chains. The prebiotic assays confirm that inulin from S. rebaudiana has a high DP. The combined use of these molecules with low degree of polymerization fructans seems to be advantageous to prolong the prebiotic effect in the colon. Our results suggest that S. rebaudiana roots are a promising source of high degree polymerization inulins. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electrochemical energy storage by polyaniline nanofibers: high gravity assisted oxidative polymerization vs. rapid mixing chemical oxidative polymerization.

Science.gov (United States)

Zhao, Yibo; Wei, Huige; Arowo, Moses; Yan, Xingru; Wu, Wei; Chen, Jianfeng; Wang, Yiran; Guo, Zhanhu

2015-01-14

Polyaniline (PANI) nanofibers prepared by high gravity chemical oxidative polymerization in a rotating packed bed (RPB) have demonstrated a much higher specific capacitance of 667.6 F g(-1) than 375.9 F g(-1) of the nanofibers produced by a stirred tank reactor (STR) at a gravimetric current of 10 A g(-1). Meanwhile, the cycling stability of the electrode is 62.2 and 65.9% for the nanofibers from RPB and STR after 500 cycles, respectively.

Reaction of Acetylenedicarboxylic Acid Made Easy: High-Pressure Route for Polymerization

DEFF Research Database (Denmark)

Delori, Amit; Hutchison, Ian B.; Bull, Craig L.

2018-01-01

A breakthrough has been achieved in improving the efficiency of solid-state polymerization of acetylenedicarboxylic acid (ADCA). Traditional solid-state polymerization of ADCA is marked by long exposure times of γ-radiation (>10 days) and very low yields (around 5.5%). We have been able to perform...... a reaction to an n = 8 oligomer, as confirmed by matrix-assisted laser desorption/ionization-time of flight, in less than 2 min by employing ∼6 GPa of pressure. We have determined the crystal structure of ADCA on increasing pressure to (5.2 GPa) to provide insight into the process of polymerization...... with Pixel calculations supporting our evaluation of the polymerization process....

Influence of CO2 on ultrasound-induced polymerizations in high-pressure fluids

NARCIS (Netherlands)

Kuijpers, M.W.A.; Jacobs, L.J.M.; Kemmere, M.F.; Keurentjes, J.T.F.

2005-01-01

A strong viscosity increase upon polymerization hinders cavitation and subsequent radical formation during an ultrasound-induced bulk polymerization. Ultrasound-induced radical polymerizations of methyl methacrylate (MMA) have been performed in CO2-expanded MMA, as well as in bulk MMA. For this

Rational designed mutagenesis of levansucrase from Bacillus licheniformis 8-37-0-1 for product specificity study.

Science.gov (United States)

He, Chunjuan; Yang, Yirui; Zhao, Renfei; Qu, Jingyao; Jin, Lan; Lu, Lili; Xu, Li; Xiao, Min

2018-04-01

Levansucrases, which belong to the glycoside hydrolase family 68 (GH68), synthesize β (2-6)-linked fructan levan with sucrose as substrate. We described the use of a levansucrase (Bl_SacB) from Bacillus licheniformis 8-37-0-1 for catalysis of fructosyl transfer to obtain high levan yield previously. In the present study, six variants (Y246A, N251A, K372A, R369A, R369S, and R369K) were constructed through sequence alignment and structural analysis to explore the synthesis mechanism of Bl_SacB. The selected residues were predicted to localize to the substrate-entering channel of the active cavity and close to or remote from the catalytic triad. The products of these variants ranged from homopolymers levan to fructo-oligosaccharides (FOSs). The primary FOSs were identified through MS and NMR analyses as neolevan-type neokestose [β-D-Fru-(2-6)-α-D-Glc-(1-2)-β-D-Fru], levan-type 6-kestose [β-D-Fru-(2-6)-β-D-Fru-(2-1)-α-D-Glc], and inulin-type 1-kestose [β-D-Fru-(2-1)-β-D-Fru-(2-1)-α-D-Glc]. The mutation at Tyr 246 located remote from the catalytic triad led to the production of short-chain oligosaccharides with degree of polymerization (DP) of up to 25. The replaced Arg 369 located close to the catalytic triad resulted in either elimination of polysaccharide synthesis or complete change in the dominant linkage of the products. The Michaelis constants (K m ) of Y246A, N251A, K372A, and R369K were found to be similar to that of the wild type (WT). However, the turnover number (k cat ) and the value of transfructosylation versus hydrolysis activity of the six variants decreased compared with those of the WT. Hence, the residues located on the surface of the substrate-entering channel of Bl_SacB can be critical in product linkage type and/or elongation mechanism.

Compression Behavior of High Performance Polymeric Fibers

National Research Council Canada - National Science Library

Kumar, Satish

2003-01-01

Hydrogen bonding has proven to be effective in improving the compressive strength of rigid-rod polymeric fibers without resulting in a decrease in tensile strength while covalent crosslinking results in brittle fibers...

Synthesis of polystyrene with high melting temperature through BDE/CuCl catalyzed polymerization

Institute of Scientific and Technical Information of China (English)

WAN; Xiaolong

2001-01-01

［1］Ewen, J. A., Novel method for plastic production, Science (in Chinese), 1997, 9: 34.［2］Brintzinger, H. H., Fischer, D., Waymouth, R. M. et al., Stereospecific olefin polymerization with chiral metallocene catalysts, Angewandte Chemie International Edition in English, 1995, 34(11): 1143.［3］Matyjaszewski, K., Atom transfer radical polymerization, role of various components and reaction conditions, Polym. Prep., 1997, 38(2): 736.［4］Wang, J. S., Matyjaszewski, K., Controlled/"living" radical polymerization, atom transfer radical polymerization in the presence of transition-metal complex, J. Am. Soc., 1995, 117: 5614.［5］Wang, J. S., Matyjaszewski, K., Controlled/"living" radical polymerization, halogen atom transfer radical polymerization promoted by a Cu(I)/Cu(II) redox process, Macromolecules, 1995, 28: 7901.［6］Koto, M., Kamigaito, M., Sawamoto, M. et al., Polymerization of methyl methacrylate with the carbon tetrachloride/dichloro-tris(triphenyphosphine) ruthenium(II)/methylaluminum bis(2,6-di-tert-butylphenoxide) initiating system: possible of living radical polymerization, Macromolecules, 1995, 28: 1721.［7］Ando, T., Kato, M., Living radical polymerization of methyl methacrylate with Ruthenium complex: formation of polymers with controlled molecular weights and very narrow distributions, Macromolecules, 1996, 29: 1070.［8］Granel, C., Dubios, P., Jerome, R. et al., Controlled radical polymerization of methacrylic monomers in the presence of a bis(ortho-chelated) arylnickel(II) complex and different activated alkyl halides, Macromolecules, 1996, 29: 8576.［9］Granel, C., Moineau, G., Lecome, P. et al., (Meth)acrylates pseudo-living radical polymerization in the presence of transition metal complexes: the kharasch reaction revisited, Polym. Prep., 1997, 38(1): 450.［10］Ando, T., Kamigaito, M., Sawamoto, M., Iron(II) chloride complex for living radical polymerization of methyl methacrylate, Macromolecules, 1997, 30: 4507.［11�

Nanoporous Polymeric Grating-Based Biosensors

KAUST Repository

Gao, Tieyu; Hsiao, Vincent; Zheng, Yue Bing; Huang, Tony Jun

2012-01-01

We demonstrate the utilization of an interferometrically created nanoporous polymeric gratings as a platform for biosensing applications. Aminopropyltriethoxysilane (APTES)-functionalized nanoporous polymeric gratings was fabricated by combining holographic interference patterning and APTES-functionalization of pre-polymer syrup. The successful detection of multiple biomolecules indicates that the biofunctionalized nanoporous polymeric gratings can act as biosensing platforms which are label-free, inexpensive, and applicable as high-throughput assays. Copyright © 2010 by ASME.

Nanoporous Polymeric Grating-Based Biosensors

KAUST Repository

Gao, Tieyu

2012-05-02

We demonstrate the utilization of an interferometrically created nanoporous polymeric gratings as a platform for biosensing applications. Aminopropyltriethoxysilane (APTES)-functionalized nanoporous polymeric gratings was fabricated by combining holographic interference patterning and APTES-functionalization of pre-polymer syrup. The successful detection of multiple biomolecules indicates that the biofunctionalized nanoporous polymeric gratings can act as biosensing platforms which are label-free, inexpensive, and applicable as high-throughput assays. Copyright © 2010 by ASME.

Packaging based on polymeric materials

Directory of Open Access Journals (Sweden)

Jovanović Slobodan M.

2005-01-01

Full Text Available In the past two years the consumption of common in the developed countries world wide (high tonnage polymers for packaging has approached a value of 50 wt.%. In the same period more than 50% of the packaging units on the world market were made of polymeric materials despite the fact that polymeric materials present 17 wt.% of all packaging materials. The basic properties of polymeric materials and their environmental and economical advantages, providing them such a position among packaging materials, are presented in this article. Recycling methods, as well as the development trends of polymeric packaging materials are also presented.

Fabrication of high-capacity polyelectrolyte brush-grafted porous AAO-silica composite membrane via RAFT polymerization.

Science.gov (United States)

Song, Cunfeng; Wang, Meijie; Liu, Xin; Wang, He; Chen, Xiaoling; Dai, Lizong

2017-09-01

Surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization has been utilized to fabricate high-capacity strong anion-exchange (AEX) membrane for the separation of protein. By means of RAFT polymerization, quaternized poly(3-(methacrylamidomethyl)-pyridine) brushes formed 3-dimensional nanolayers on the surface of porous anodic aluminum oxide (AAO)-silica composite membrane. The surface properties of the membranes were analyzed by SEM, water contact angle, ATR-FTIR, XPS and TGA. To investigate the adsorption performance, the new AEX membranes were applied to recover a model protein, ovalbumin (OVA). High adsorption capacities of 95.8mg/g membranes (static) and 65.3mg/g membranes (dynamic) were obtained at ambient temperature. In the further studies, up to 90% of the adsorbed OVA was efficiently eluted by using phosphate buffer-1M NaCl as elution medium. The successful separation of OVA with high purity from a mixture protein solution was also achieved by using the AEX membranes. The present study demonstrated that under mild reaction condition, RAFT polymerization can be used to fabricate ion-exchange membrane which has many remarkable features, such as high capacity and selectivity, easy elution and so on. Copyright © 2017. Published by Elsevier B.V.

Antibiotic polymeric nanoparticles for biofilm-associated infection therapy.

Science.gov (United States)

Cheow, Wean Sin; Hadinoto, Kunn

2014-01-01

Polymeric nanoparticles are highly attractive as drug delivery vehicles due to their high structural integrity, stability during storage, ease of preparation and functionalization, and controlled release capability. Similarly, lipid-polymer hybrid nanoparticles, which retain the benefits of polymeric nanoparticles plus the enhanced biocompatibility and prolonged circulation time owed to the lipids, have recently emerged as a superior alternative to polymeric nanoparticles. Drug nanoparticle complex prepared by electrostatic interaction of oppositely charged drug and polyelectrolytes represents another type of polymeric nanoparticle. This chapter details the preparation, characterization, and antibiofilm efficacy testing of antibiotic-loaded polymeric and hybrid nanoparticles and antibiotic nanoparticle complex.

Radiation sterilization of polymeric implant materials

International Nuclear Information System (INIS)

Bruck, S.D.; Mueller, E.P.

1988-01-01

High-energy irradiation sterilization of medical devices and implants composed of polymeric biomaterials that are in contact with tissue and/or blood, may adversely affect their long-term mechanical and/or biological performance (tissue and/or blood compatibility). Since many polymeric implants may contain trace quantities of catalysts and/or other additives, the effect of high-energy radiation on these additives, and possible synergistic effects with the polymer chains under the influence of high-energy radiation, must be considered. It is essential to indicate whether polymeric implants are used in short-term (acute) or long-term (chronic) applications. Relatively small changes in their physicochemical, mechanical, and biological properties may be tolerable in the short term, whereas similar changes may lead to catastrophic failures in long-term applications. Therefore, polymeric implants which are to be sterilized by high-energy irradiation should be carefully evaluated for long-term property changes which may be induced by the radiation

Feed Fermentation with Reuteran- and Levan-Producing Lactobacillus reuteri Reduces Colonization of Weanling Pigs by Enterotoxigenic Escherichia coli.

Science.gov (United States)

Yang, Yan; Galle, Sandra; Le, Minh Hong Anh; Zijlstra, Ruurd T; Gänzle, Michael G

2015-09-01

This study determined the effect of feed fermentation with Lactobacillus reuteri on growth performance and the abundance of enterotoxigenic Escherichia coli (ETEC) in weanling piglets. L. reuteri strains produce reuteran or levan, exopolysaccharides that inhibit ETEC adhesion to the mucosa, and feed fermentation was conducted under conditions supporting exopolysaccharide formation and under conditions not supporting exopolysaccharide formation. Diets were chosen to assess the impact of organic acids and the impact of viable L. reuteri bacteria. Fecal samples were taken throughout 3 weeks of feeding; at the end of the 21-day feeding period, animals were euthanized to sample the gut digesta. The feed intake was reduced in pigs fed diets containing exopolysaccharides; however, feed efficiencies did not differ among the diets. Quantification of L. reuteri by quantitative PCR (qPCR) detected the two strains used for feed fermentation throughout the intestinal tract. Quantification of E. coli and ETEC virulence factors by qPCR demonstrated that fermented diets containing reuteran significantly (P reuteri reduced the level of colonization of weaning piglets with ETEC, and feed fermentation supplied concentrations of reuteran that may specifically contribute to the effect on ETEC. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

High-speed organocatalytic polymerization of a renewable methylene butyrolactone by a phosphazene superbase

KAUST Repository

Schmitt, Meghan L.; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene You Xian

2014-01-01

The organic phosphazene superbase, 1-tert-butyl-4,4,4-tris(dimethylamino)- 2,2-bis[tris(dimethylamino)phosphoranylid-enamino]-2λ5, 4λ5-catenadi(phosphazene) (t-Bu-P4), is found to directly initiate high-speed polymerization of the biomass-derived renewable γ-methyl-α-methylene-γ-butyrolactone (MMBL), in contrast to other polymerization systems using t-Bu-P4 which typically require addition of an organic acid or a nucleophile as a co-initiating component. This MMBL polymerization by t-Bu-P4 alone is extremely rapid; even with a low t-Bu-P4 loading of 0.1 mol% or 0.02 mol%, quantitative monomer conversion is achieved in 20 s or 1 min, respectively, affording medium to high molecular weight PMMBL bioplastics in a catalytic fashion. The combined experimental and theoretical/computational studies have yielded mechanisms of chain initiation through abstraction of a proton from a monomer by t-Bu-P 4, essentially barrier-less chain propagation through rapid conjugate addition of the enolate anion stabilized by the nano-size cation [t-Bu-P 4H]+ to the monomer, and chain termination through chain transfer to the monomer which generates a saturated termination chain end and the [t-Bu-P4H]+-stabilized anionic active species that starts a new chain. This journal is © the Partner Organisations 2014.

Click polymerization for the synthesis of reduction-responsive polymeric prodrug

Science.gov (United States)

Zhang, Xiaojin; Wang, Hongquan; Dai, Yu

2018-05-01

Click polymerization is a powerful polymerization technique for the construction of new macromolecules with well-defined structures and multifaceted functionalities. Here, we synthesize reduction-responsive polymeric prodrug PEG- b-(PSS- g-MTX)- b-PEG containing disulfide bonds and pendant methotrexate (MTX) via two-step click polymerization followed by conjugating MTX to pendant hydroxyl. MTX content in polymeric prodrug is 13.5%. Polymeric prodrug is able to form polymeric micelles by self-assembly in aqueous solution. Polymeric micelles are spherical nanoparticles with tens of nanometers in size. Of note, polymeric micelles are reduction-responsive due to disulfide bonds in the backbone of PEG- b-(PSS- g-MTX)- b-PEG and could release pendant drugs in the presence of the reducing agents such as dl-dithiothreitol (DTT).

High performance nature of biodegradable polymeric nanocomposites for oil-well drilling fluids

Directory of Open Access Journals (Sweden)

Tarek M. Madkour

2016-06-01

Full Text Available Multi-walled carbon nanotube (MWCNT and graphene nanoplatelet reinforced thermoplastic poly(lactic acid (PLA biodegradable nanocomposites were designed and prepared using solution casting techniques. The prepared biodegradable polymers are expected to provide an environmentally friendly alternative to petroleum-based polymers. Both nanocomposite systems exhibited better thermal stability and improved mechanical performance over the unreinforced polymer exhibiting excellent strength and degradability. The addition of graphene nanofiller in varied amounts was aimed to enhance the thermal and mechanical properties of the nanocomposites even further and incorporate the outstanding characteristics of graphene nanoplatelets into the nanocomposites. The polymeric nanocomposites showed also superior advantages for oil drilling relevances, automotive lubricating purposes, membrane technology and food packaging. Scanning electron microscopy images indicated a homogeneous dispersion of the nanofiller within the polymeric matrix at low filler loadings and a cluster formation at higher loadings that could be responsible for the polymeric matrix movement restrictions. The enthalpy of mixing (the polymer and the nanofiller measured could explain the cause of the repulsive interactions between the nanoparticles and the polymeric chains, which created an additional excluded volume that the polymeric segments were restricted to occupy, thus forcing the conformational characteristics of the polymeric chains to deviate away from those of the bulk chains. The prepared polymeric nano composites (poly lactic acid carbon nano tube and poly lactic acid graphene nanoplatelets were utilized in the formulation of oil-base mud as a viscosifier. The rheological, filtration properties and electrical stability of the oil based mud formulation with the new polymeric nanocomposite were studied and the result compared to the oil-based mud formulation with commercial viscosifier.

Pulsed-laser polymerization in compartmentalized liquids. 1. Polymerization in vesicles

NARCIS (Netherlands)

Jung, M.; Casteren, van I.A.; Monteiro, M.J.; Herk, van A.M.; German, A.L.

2000-01-01

Polymerization in vesicles is a novel type of polymerization in heterogeneous media, leading to parachute-like vesicle-polymer hybrid morphologies. To explore the kinetics of vesicle polymerizations and to learn more about the actual locus of polymerization we applied the pulsed-laser polymerization

Characterization behavior of some polymeric composite ion exchangers

International Nuclear Information System (INIS)

El-Zahhar, A.A; Ahdel-Aziz, H.M.; Siyam, T.

2005-01-01

Polymeric composite resins were prepared by template polymerization process in aqueous solution. Thermogravimetric analysis (TGA), differential thermal analysis (DTA) and The X-ray diffraction patterns (XRD) were performed to evaluate the physico chemical properties of the different polymeric composite resins. The TGA and DTA clarify high thermal stability of prepared polymeric composite resins. XRD of prepared polymeric composite shows that there is crystalline structure of some resins while other are amorphous one

Ring-opening polymerization of 19-electron [2]cobaltocenophanes: a route to high-molecular-weight, water-soluble polycobaltocenium polyelectrolytes.

Science.gov (United States)

Mayer, Ulrich F J; Gilroy, Joe B; O'Hare, Dermot; Manners, Ian

2009-08-05

Water-soluble, high-molecular-weight polycobaltocenium polyelectrolytes have been prepared by ring-opening polymerization (ROP) techniques. Anionic polymerization of a strained 19-electron dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium chloride resulted in the formation of oligomers with up to nine repeat units. Thermal ROP of dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium nitrate resulted in the formation of high-molecular-weight polycobaltocenium nitrate, a redox-active cobalt-containing polyelectrolyte.

High power light emitting diode (LED) arrays versus halogen light polymerization of oral biomaterials: Barcol hardness, compressive strength and radiometric properties.

Science.gov (United States)

Mills, Robin W; Uhl, Alexander; Blackwell, Gordon B; Jandt, Klaus D

2002-07-01

The clinical performance of light polymerized dental composites is greatly influenced by the quality of the light curing unit (LCU) used. Commonly used halogen LCUs have some specific drawbacks such as decreasing light output with time. This may result in a low degree of monomer conversion of the composites with negative clinical implications. Previous studies have shown that blue light emitting diode (LED) LCUs have the potential to polymerize dental composites without having the drawbacks of halogen LCUs. Since these studies were carried out LED technology has advanced significantly and commercial LED LCUs are now becoming available. This study investigates the Barcol hardness as a function of depth, and the compressive strength of dental composites that had been polymerized for 40 or 20s with two high power LED LCU prototypes, a commercial LED LCU, and a commercial halogen LCU. In addition the radiometric properties of the LCUs were characterized. The two high power prototype LED LCUs and the halogen LCU showed a satisfactory and similar hardness-depth performance whereas the hardness of the materials polymerized with the commercial LED LCU rapidly decreased with sample depth and reduced polymerization time (20 s). There were statistically significant differences in the overall compressive strengths of composites polymerized with different LCUs at the 95% significance level (p = 0.0016) with the two high power LED LCU prototypes and the halogen LCU forming a statistically homogenous group. In conclusion, LED LCU polymerization technology can reach the performance level of halogen LCUs. One of the first commercial LED LCUs however lacked the power reserves of the high power LED LCU prototypes.

Thermal polymerization of Moringa oleifera oil

International Nuclear Information System (INIS)

Melo, Tania M.S.; Novack, Katia M.; Leandro, Cristiano

2011-01-01

It is increasingly clear both for society and the scientific community, that is necessary to find alternatives to reduce the use of polymeric materials because of their damage to the environment. One way to minimize the environmental problems related to the use of polymers is try to make them quickly degradable. In this study it was obtained a material with polymeric appearance derived from heating of the vegetable oil extracted from seeds of Moringa oleifera. The resulting product is an interesting alternative to obtain polymeric materials that may have biodegradable characteristics, coming from a renewable source and low cost. Moringa oil can be used since it has a high content of unsaturated fatty acids, and its main constituent oleic acid. All samples were characterized by FTIR, NMR and GPC. It was obtained a polymeric material, malleable, high viscosity, with some elasticity, low crystallinity and no unpleasant odor. (author)

In-situ polymerization of polyaniline on the surface of graphene oxide for high electrochemical capacitance

International Nuclear Information System (INIS)

Li, Xinlu; Zhong, Qineng; Zhang, Xinlin; Li, Tongtao; Huang, Jiamu

2015-01-01

Conducting polymer polyaniline (PANI) was in-situ polymerized on the surface of graphene oxide (GO) to form PANI encapsulating GO nanocomposites. The morphology and microstructure were examined by scanning electron microscopy, X-ray diffraction and N 2 absorption/desorption analysis. Electrochemical properties were tested by cyclic voltammetry, galvanostatic charge/discharge cycles and electrochemical impedance spectroscopy. Experimental results showed that ethanol assisted the dispersion of GO in water and facilitated the diffusion of polymer monomers on GO. GO as a support material can provide sufficient reaction sites for the deposition of aniline to form the film-like GO/PANI composites. Capacitive performance illustrated that the in-situ polymerization of PANI on GO was effective in improving the specific capacitance and cycling stability. - Highlights: • GO/PANI nanocomposites were achieved by in-situ polymerization. • PANI was uniformly coated on the surface of GO with addition of ethanol. • GO/PANI show high specific capacitance and cycling stability

In situ synthesis of molecularly imprinted nanoparticles in porous support membranes using high-viscosity polymerization solvents.

Science.gov (United States)

Renkecz, Tibor; László, Krisztina; Horváth, Viola

2012-06-01

There is a growing need in membrane separations for novel membrane materials providing selective retention. Molecularly imprinted polymers (MIPs) are promising candidates for membrane functionalization. In this work, a novel approach is described to prepare composite membrane adsorbers incorporating molecularly imprinted microparticles or nanoparticles into commercially available macroporous filtration membranes. The polymerization is carried out in highly viscous polymerization solvents, and the particles are formed in situ in the pores of the support membrane. MIP particle composite membranes selective for terbutylazine were prepared and characterized by scanning electron microscopy and N₂ porosimetry. By varying the polymerization solvent microparticles or nanoparticles with diameters ranging from several hundred nanometers to 1 µm could be embedded into the support. The permeability of the membranes was in the range of 1000 to 20,000 Lm⁻²  hr⁻¹  bar⁻¹. The imprinted composite membranes showed high MIP/NIP (nonimprinted polymer) selectivity for the template in organic media both in equilibrium-rebinding measurements and in filtration experiments. The solid phase extraction of a mixture of the template, its analogs, and a nonrelated compound demonstrated MIP/NIP selectivity and substance selectivity of the new molecularly imprinted membrane. The synthesis technique offers a potential for the cost-effective production of selective membrane adsorbers with high capacity and high throughput. Copyright © 2012 John Wiley & Sons, Ltd.

Preparation of interconnected highly porous polymeric structures by a replication and freeze-drying process

NARCIS (Netherlands)

Hou, Q.; Grijpma, Dirk W.; Feijen, Jan

2003-01-01

Three-dimensional degradable porous polymeric structures with high porosities (93-98%) and well-interconnected pore networks have been prepared by freeze-drying polymer solutions in the presence of a leachable template followed by leaching of the template. Templates of the pore network were prepared

Gamma Radiation-Induced Template Polymerization Technique

International Nuclear Information System (INIS)

Siyam, T.

2005-01-01

Gamma radiation induced copolymerization of acrylamide sodiumacrylate (AM-AANa) in the presence and absence of the polymer additive was studied at low monomer concentration(1.4M/l). The results showed that the exponents of the dose rate for the polymerization rate was found to be 1.3 and 1.4 in the absence and in the presence of the polymer additive respectively. The molecular weight of the formed polymer increased by addition of the polymer to the system. In the presence of the polymer the comonomers polymerize on the added polymer. In the absence of the added polymer the comonomers polymerize according to the copolymerization process at the initial stage of the copolymerization. While at high conversion the residual comonomers polymerize on the formed macromolecular chains of the produced polymer. These studies showed that the copolymerization in the presence of added polymer is completely template copolymerization while in the absence of the polymer the copolymerization process is only template process with a high conversion

Electron beam induced graft-polymerization of methyl methacrylate onto polyethylene films at high dose rates

International Nuclear Information System (INIS)

Mori, Koji; Koshiishi, Kenji; Masuhara, Ken-ichi

1991-01-01

Electron beam induced graft-polymerization by the mutual irradiation technique of methyl methacrylate on the surface of low density polyethylene films (LD) and high density polyethylene films (HD) was investigated at high dose rates over 10 Mrad per second. Graft-polymerization mechanisms were discussed on the basis of O 2 permeability, tensile strength, elongation at break, and surface tension of the grafted films. As the degree of grafting increased, the O 2 permeability of LD decreased, while that of HD little changed at the grafting up to 4 ∼ 5 %. This indicates that the grafting occurred in the amorphous regions for LD and occurred in the amorphous regions in the neighborhood of crystalline regions for HD. For HD, when the degree of the grafting surpassed 4 ∼ 5 %, the O 2 permeability, tensile strength, elongation at break, and surface tension decreased with an increase in the degree of grafting. It was assumed that rapid grafting in the amorphous regions in the neighborhood of crystalline regions caused the increase in local temperature by the heat of polymerization, and the viscosity of polyethylene in the amorphous regions decreased with an increase in temperature. As a result, the graft chains, which formed micro domain structure, condensed in the amorphous regions and the domain increased in size. (author)

Pentafluorosulfanyl Substituents in Polymerization Catalysis.

Science.gov (United States)

Kenyon, Philip; Mecking, Stefan

2017-10-04

Highly electron-withdrawing pentafluorosulfanyl groups were probed as substituents in an organometallic catalyst. In Ni(II) salicylaldiminato complexes as an example case, these highly electron-withdrawing substituents allow for polymerization of ethylene to higher molecular weights with reduced branching due to significant reductions in β-hydrogen elimination. Combined with the excellent functional group tolerance of neutral Ni(II) complexes, this suppression of β-hydrogen elimination allows for the direct polymerization of ethylene in water to nanocrystal dispersions of disentangled, ultrahigh-molecular-weight linear polyethylene.

Highly water-absorbing silk yarn with interpenetrating network via in situ polymerization.

Science.gov (United States)

Lee, Ka I; Wang, Xiaowen; Guo, Xia; Yung, Ka-Fu; Fei, Bin

2017-02-01

Silk was modified via in situ polymerization of two monomers acrylamide and sodium acrylate by swelling in an effective LiBr dissolution system. Swelling of natural silks in LiBr solutions of low concentration was clearly observed under optical microscope, and their conformational changes were revealed by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. Dissolution tests and FTIR spectra of these modified silks suggested the presence of interpenetrating network of polyacrylamide and poly(sodium acrylate) in the silk yarns. These modified silks exhibited superior water absorption to that of raw silk and greatly improved mechanical properties in both dry and wet states. These novel modified silks also showed low cytotoxicity towards skin keratinocytes, having potential applications in biomedical textiles. This modification method by in situ polymerization after swelling in LiBr provides a new route to highly enhance the properties and performance of silk for various applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Polymeric media for tritium fixation

International Nuclear Information System (INIS)

Franz, J.A.; Burger, L.L.

1975-01-01

The synthesis and leach testing of several polymeric media for tritium fixation are presented. Tritiated bakelite, poly(acrylonitrile) and polystyrene successfully fixed tritium. Tritium leach rates at the tracer level appear to be negligible. Advantages and disadvantages of the processes are discussed, and further bench-scale investigations underway are reported. Rough cost estimates are presented for the different media and are compared with alternate approaches such as deep-well injection and long-term tank storage. Polymeric media costs are high compared to deep-well storage and are of the same order of magnitude per liter of water as for isotopic enrichment. With this limitation, polymeric media can be economically feasible only for highly concentrated tritiated wastes. It is recommended that the bakelite and polystyrene processes be examined on a larger scale to permit more accurate cost analysis and process design. (auth)

High-pressure synthesis of CuBa2Ca3Cu4O10+δ superconductor from precursors prepared by a polymerized complex method

International Nuclear Information System (INIS)

Aoba, Tomoya; Bizen, Takeshi; Suzuki, Tsuneo; Nakayama, Tadachika; Suematsu, Hisayuki; Niihara, Koichi; Katsumata, Tetsuhiro; Inaguma, Yoshiyuki

2011-01-01

Samples of a CuBa 2 Ca 3 Cu 4 O 10+ δ superconductor were synthesized under a high pressure of 5 GPa at 1100-1200degC for 30 min using precursors produced by solid-state reaction and polymerized complex methods. Compared with the precursors prepared by the solid-state reaction method, the precursors produced by the polymerized complex method have low grain sizes. The superconductive transition temperature of the samples prepared using precursors made by the polymerized complex method was found to be 113 K. The volume fractions of the superconducting phase in the samples prepared using precursors made by the solid-state reaction and polymerized complex methods were 49 and 36%, respectively. From these results, precursors made by the polymerized complex method can be used in the high-pressure synthesis of superconductors similarly to those made by the solid-state reaction method. (author)

Phosphasalen indium complexes showing high rates and isoselectivities in rac-lactide polymerizations

Energy Technology Data Exchange (ETDEWEB)

Myers, Dominic; White, Andrew J.P. [Department of Chemistry, Imperial College London (United Kingdom); Forsyth, Craig M. [School of Chemistry, Monash University, Clayton, VIC (Australia); Bown, Mark [CSIRO Manufacturing, Bayview Avenue, Clayton, VIC (Australia); Williams, Charlotte K. [Department of Chemistry, Oxford University (United Kingdom)

2017-05-02

Polylactide (PLA) is the leading bioderived polymer produced commercially by the metal-catalyzed ring-opening polymerization of lactide. Control over tacticity to produce stereoblock PLA, from rac-lactide improves thermal properties but is an outstanding challenge. Here, phosphasalen indium catalysts feature high rates (30±3 m{sup -1} min{sup -1}, THF, 298 K), high control, low loadings (0.2 mol %), and isoselectivity (P{sub i}=0.92, THF, 258 K). Furthermore, the phosphasalen indium catalysts do not require any chiral additives. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Secreted osteopontin is highly polymerized in human airways and fragmented in asthmatic airway secretions.

Directory of Open Access Journals (Sweden)

Mehrdad Arjomandi

Full Text Available Osteopontin (OPN is a member of the small integrin-binding ligand N-linked glycoprotein (SIBLING family and a cytokine with diverse biologic roles. OPN undergoes extensive post-translational modifications, including polymerization and proteolytic fragmentation, which alters its biologic activity. Recent studies suggest that OPN may contribute to the pathogenesis of asthma.To determine whether secreted OPN (sOPN is polymerized in human airways and whether it is qualitatively different in asthma, we used immunoblotting to examine sOPN in bronchoalveolar lavage (BAL fluid samples from 12 healthy and 21 asthmatic subjects (and in sputum samples from 27 healthy and 21 asthmatic subjects. All asthmatic subjects had mild to moderate asthma and abstained from corticosteroids during the study. Furthermore, we examined the relationship between airway sOPN and cellular inflammation.We found that sOPN in BAL fluid and sputum exists in polymeric, monomeric, and cleaved forms, with most of it in polymeric form. Compared to healthy subjects, asthmatic subjects had proportionately less polymeric sOPN and more monomeric and cleaved sOPN. Polymeric sOPN in BAL fluid was associated with increased alveolar macrophage counts in airways in all subjects.These results suggest that sOPN in human airways (1 undergoes extensive post-translational modification by polymerization and proteolytic fragmentation, (2 is more fragmented and less polymerized in subjects with mild to moderate asthma, and (3 may contribute to recruitment or survival of alveolar macrophages.

RAFT Aqueous Dispersion Polymerization of N-(2-(Methacryloyloxy)ethyl)pyrrolidone: A Convenient Low Viscosity Route to High Molecular Weight Water-Soluble Copolymers.

Science.gov (United States)

Cunningham, Victoria J; Derry, Matthew J; Fielding, Lee A; Musa, Osama M; Armes, Steven P

2016-06-28

RAFT solution polymerization of N -(2-(methacryoyloxy)ethyl)pyrrolidone (NMEP) in ethanol at 70 °C was conducted to produce a series of PNMEP homopolymers with mean degrees of polymerization (DP) varying from 31 to 467. Turbidimetry was used to assess their inverse temperature solubility behavior in dilute aqueous solution, with an LCST of approximately 55 °C being observed in the high molecular weight limit. Then a poly(glycerol monomethacylate) (PGMA) macro-CTA with a mean DP of 63 was chain-extended with NMEP using a RAFT aqueous dispersion polymerization formulation at 70 °C. The target PNMEP DP was systematically varied from 100 up to 6000 to generate a series of PGMA 63 -PNMEP x diblock copolymers. High conversions (≥92%) could be achieved when targeting up to x = 5000. GPC analysis confirmed high blocking efficiencies and a linear evolution in M n with increasing PNMEP DP. A gradual increase in M w / M n was also observed when targeting higher DPs. However, this problem could be minimized ( M w / M n RAFT aqueous dispersion polymerization of NMEP was approximately four times faster than the RAFT solution polymerization of NMEP in ethanol when targeting the same DP in each case. This is perhaps surprising because both 1 H NMR and SAXS studies indicate that the core-forming PNMEP chains remain relatively solvated at 70 °C in the latter formulation. Moreover, dissolution of the initial PGMA 63 -PNMEP x particles occurs on cooling from 70 to 20 °C as the PNMEP block passes through its LCST. Hence this RAFT aqueous dispersion polymerization formulation offers an efficient route to a high molecular weight water-soluble polymer in a rather convenient low-viscosity form. Finally, the relatively expensive PGMA macro-CTA was replaced with a poly(methacrylic acid) (PMAA) macro-CTA. High conversions were also achieved for PMAA 85 -PNMEP x diblock copolymers prepared via RAFT aqueous dispersion polymerization for x ≤ 4000. Again, better control was achieved when

IMMOBILIZATION OF FLAVIN ON HIGHLY POROUS POLYMERIC DISKS - 3 ROUTES TO A CATALYTICALLY ACTIVE MEMBRANE

NARCIS (Netherlands)

SCHOO, HFM; CHALLA, G; ROWATT, B; SHERRINGTON, DC

Disks obtained by polymerization of high internal phase emulsions (Polyhipe) had completely open pore structures and were used as a carrier material for the immobilisation of 10-ethyl-isoalloxazine ('flavin'). Three methods for immobilization are described: (1) direct modification of

Radical-Mediated Enzymatic Polymerizations

Science.gov (United States)

Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

2016-01-01

Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

Highly active self-immobilized FI-Zr catalysts in a PCP framework for ethylene polymerization.

Science.gov (United States)

Li, He; Xu, Bo; He, Jianghao; Liu, Xiaoming; Gao, Wei; Mu, Ying

2015-12-04

A series of zirconium-based porous coordination polymers (PCPs) containing FI catalysts in the frameworks have been developed and studied as catalysts for ethylene polymerization. These PCPs exhibit good catalytic activities and long life times, producing polyethylenes with high molecular weights and bimodal molecular weight distribution in the form of particles.

Mechanochemical Ring-Opening Polymerization of Lactide: Liquid-Assisted Grinding for the Green Synthesis of Poly(lactic acid) with High Molecular Weight.

Science.gov (United States)

Ohn, Nuri; Shin, Jihoon; Kim, Sung Sik; Kim, Jeung Gon

2017-09-22

Mechanochemical polymerization of lactide is carried out by using ball milling. Mechanical energy from collisions between the balls and the vessel efficiently promotes an organic-base-mediated metal- and solvent-free solid-state polymerization. Investigation of the parameters of the ball-milling synthesis revealed that the degree of lactide ring-opening polymerization could be modulated by the ball-milling time, vibration frequency, mass of the ball media, and liquid-assisted grinding. Liquid-assisted grinding was found to be an especially important factor for achieving a high degree of mechanochemical polymerization. Although polymer-chain scission from the strong collision energy prevented mechanical-force-driven high-molecular-weight polymer synthesis, the addition of only a small amount of liquid enabled sufficient energy dissipation and poly(lactic acid) was thereby obtained with a molecular weight of over 1×10 5  g mol -1 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymeric bicontinuous microemulsions

DEFF Research Database (Denmark)

Bates, F.S.; Maurer, W.W.; Lipic, P.M.

1997-01-01

High molecular weight block copolymers can be viewed as macromolecular surfactants when blended with thermodynamically incompatible homopolymers. This Letter describes the formation of polymeric bicontinuous microemulsions in nurtures containing a model diblock copolymer and two homopolymers. Alt...

Experimental study of living free radical polymerization using trifunctional initiator and polymerization mediated by nitroxide

International Nuclear Information System (INIS)

Galhardo, Eduardo; Lona, Liliane M.F.

2009-01-01

Controlled free radical polymerization or living free radical polymerization has received increasing attention as a technique for the production of polymers with microstructure highly controlled. In particular, narrow molecular weight distributions are obtained with polydispersity very close to one. In this research it was investigate the controlled polymerization mediated by nitroxide, using a cyclic trifunctional peroxide. As long as we know, there are only publications in literature dealing with NMRP using mono- and bi-functional initiators. It was believed that the trifunctional peroxide can increase the rate of polymerization, since more free radicals are generated, if compared with initiators with lower functionality. Furthermore, the fact of the initiator be cyclic means that branches are not generated in the chains, which theoretically prevents an increase in polydispersity of the polymer. The effect of the dissociation constant of the trifunctional initiator in the velocity of the reaction was analyzed. (author)

Thermodynamic Presynthetic Considerations for Ring-Opening Polymerization.

Science.gov (United States)

Olsén, Peter; Odelius, Karin; Albertsson, Ann-Christine

2016-03-14

The need for polymers for high-end applications, coupled with the desire to mimic nature's macromolecular machinery fuels the development of innovative synthetic strategies every year. The recently acquired macromolecular-synthetic tools increase the precision and enable the synthesis of polymers with high control and low dispersity. However, regardless of the specificity, the polymerization behavior is highly dependent on the monomeric structure. This is particularly true for the ring-opening polymerization of lactones, in which the ring size and degree of substitution highly influence the polymer formation properties. In other words, there are two important factors to contemplate when considering the particular polymerization behavior of a specific monomer: catalytic specificity and thermodynamic equilibrium behavior. This perspective focuses on the latter and undertakes a holistic approach among the different lactones with regard to the equilibrium thermodynamic polymerization behavior and its relation to polymer synthesis. This is summarized in a monomeric overview diagram that acts as a presynthetic directional cursor for synthesizing highly specific macromolecules; the means by which monomer equilibrium conversion relates to starting temperature, concentration, ring size, degree of substitution, and its implications for polymerization behavior are discussed. These discussions emphasize the importance of considering not only the catalytic system but also the monomer size and structure relations to thermodynamic equilibrium behavior. The thermodynamic equilibrium behavior relation with a monomer structure offers an additional layer of complexity to our molecular toolbox and, if it is harnessed accordingly, enables a powerful route to both monomer formation and intentional macromolecular design.

Plasma polymerization by Softplasma

DEFF Research Database (Denmark)

Jiang, J.; Wu, Zhenning; Benter, Maike

2008-01-01

, external electrode, and electrodeless microwave or high frequency reactors. [3] Softplasma™ is an internal electrode plasma setup powered by low frequenc~ gower supply. It was developed in late 90s for surface treatment of silicone rubber. [ ]- 5] It is a low pressure, low electron density, 3D homogenous......In the late 19th century, the first depositions - known today as plasma polymers, were reported. In the last century, more and more research has been put into plasma polymers. Many different deposition systems have been developed. [1, 2] Shi F. F. broadly classified them into internal electrode...... plasma. In this study, we are presenting the surface modification"pf polymers by plasma polymerization using Softplasma™. Softplasma™ can be used for two major types of polymerization: polymerization of vinyl monomers, where plasma acts as initiator; chemical vapour deposition, where plasma acts...

High temperature initiator-free RAFT polymerization of methyl methacrylate in a microwave reactor

NARCIS (Netherlands)

Paulus, R.M.; Becer, C.R.; Hoogenboom, R.; Schubert, U.S.

2009-01-01

The reversible additionfragmentation chain transfer (RAFT) polymerization of methyl methacrylate (MMA) was investigated under microwave irradiation. At first, a comparison was made between microwave and thermal heating for the RAFT polymerization of MMA with azobis(isobutyronitrile) (AIBN) as

Elektroaktive polymerer

DEFF Research Database (Denmark)

West, K.

Traditionelt tænker vi på polymerer (plastik) som elektrisk isolerende materialer - det som er udenpå ledningerne. I dag kender vi imidlertid også polymerer med intrinsisk elektrisk ledningsevne, og plast er på vej ind i anvendelser, der tidligereudelukkende var baseret på metaller og uorganiske...... halvledere. Hertil kommer, at en del af de ledende polymerer kan stimuleres til at skifte mellem en ledende og en halvledende tilstand, hvorved de ændret både form og farve. I foredraget gives der enrække eksempler på anvendelse af polymerer som elektriske komponenter - rækkende fra polymer elektronik over...

Syringyl Methacrylate, a Hardwood Lignin-Based Monomer for High-Tg Polymeric Materials.

Science.gov (United States)

Holmberg, Angela L; Reno, Kaleigh H; Nguyen, Ngoc A; Wool, Richard P; Epps, Thomas H

2016-05-17

As viable precursors to a diverse array of macromolecules, biomass-derived compounds must impart wide-ranging and precisely controllable properties to polymers. Herein, we report the synthesis and subsequent reversible addition-fragmentation chain-transfer polymerization of a new monomer, syringyl methacrylate (SM, 2,6-dimethoxyphenyl methacrylate), that can facilitate widespread property manipulations in macromolecules. Homopolymers and heteropolymers synthesized from SM and related monomers have broadly tunable and highly controllable glass transition temperatures ranging from 114 to 205 °C and zero-shear viscosities ranging from ∼0.2 kPa·s to ∼17,000 kPa·s at 220 °C, with consistent thermal stabilities. The tailorability of these properties is facilitated by the controlled polymerization kinetics of SM and the fact that one vs two o -methoxy groups negligibly affect monomer reactivity. Moreover, syringol, the precursor to SM, is an abundant component of depolymerized hardwood (e.g., oak) and graminaceous (e.g., switchgrass) lignins, making SM a potentially sustainable and low-cost candidate for tailoring macromolecular properties.

Radiation-induced graft polymerization of amphiphilic monomers with different polymerization characteristics onto hydrophobic polysilane

Energy Technology Data Exchange (ETDEWEB)

Tanaka, Hidenori; Iwasaki, Isao; Kunai, Yuichiro [Research Reactor Institute, Kyoto University, Asashironishi 2-1010, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan); Sato, Nobuhiro, E-mail: sato-n@rri.kyoto-u.ac.j [Research Reactor Institute, Kyoto University, Asashironishi 2-1010, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan); Matsuyama, Tomochika [Research Reactor Institute, Kyoto University, Asashironishi 2-1010, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan)

2011-08-15

The structures of poly(methyl-n-propylsilane) (PMPrS) amphiphilically modified through {gamma}-ray-induced graft polymerization were investigated with {sup 1}H NMR measurement. By the use of methyl methacrylate (MMA) or diethyl fumarate (DEF) as monomers for the graft polymerization, grafting yield rose with increasing total absorption dose and monomer concentrations, but decreased with increasing dose rate. This result means that grafting yield of modified PMPrS can be controlled by changing irradiation conditions. However, the number of PMMA or PDEF graft chains per PMPrS chain was estimated to be less than 1.0 by analysis of {sup 1}H NMR spectra, and this value was lower than that we had expected. To improve graft density, maleic anhydride (MAH), which is known as a non-homopolymerizable monomer in radical polymerization, was used as a monomer for grafting. As a result, high density grafting (one MAH unit for 4.2 silicon atoms) was attained. It demonstrates that the structure of {gamma}-ray-modified polysilane strongly depends on the polymerization characteristics of grafted monomers.

Effect of oxyfluorinated multi-walled carbon nanotube additives on positive temperature coefficient/negative temperature coefficient behavior in high-density polyethylene polymeric switches

International Nuclear Information System (INIS)

Bai, Byong Chol; Kang, Seok Chang; Im, Ji Sun; Lee, Se Hyun; Lee, Young-Seak

2011-01-01

Graphical abstract: The electrical properties of MWCNT-filled HDPE polymeric switches and their effect on oxyfluorination. Highlights: → Oxyfluorinated MWCNTs were used to reduce the PTC/NTC phenomenon in MWCNT-filled HDPE polymeric switches. → Electron mobility is difficult in MWCNT particles when the number of oxygen functional groups (C-O, C=O) increases by oxyfluorination. → A mechanism of improved electrical properties of oxyfluorinated MWCNT-filled HDPE polymeric switches was suggested. -- Abstract: Multi-walled carbon nanotubes (MWCNTs) were embedded into high-density polyethylene (HDPE) to improve the electrical properties of HDPE polymeric switches. The MWCNT surfaces were modified by oxyfluorination to improve their positive temperature coefficient (PTC) and negative temperature coefficient (NTC) behaviors in HDPE polymeric switches. HDPE polymeric switches exhibit poor electron mobility between MWCNT particles when the number of oxygen functional groups is increased by oxyfluorination. Thus, the PTC intensity of HDPE polymeric switches was increased by the destruction of the electrical conductivity network. The oxyfluorination of MWCNTs also leads to weak NTC behavior in the MWCNT-filled HDPE polymeric switches. This result is attributed to the reduction of the mutual attraction between the MWCNT particles at the melting temperature of HDPE, which results from a decrease in the surface free energy of the C-F bond in MWCNT particles.

Polymerization of polyethers initiated by irradiation with high power pulsed electron beams

International Nuclear Information System (INIS)

Gerber, V.D.; Tolkachev, V.S.; Chmukh, V.N.

1982-01-01

Air oxygen effect on thin-layer polymerization of polyethers, initiated by irradiation with powerful pulse electron beams is studied using the method of IR-spectrophotometry. The analysis of experimental data has shown that in polyether surface layer polymerization is suppressed by oxygen, concentration of which in the layer remains stable at the expense of diffusion from air during two consequent irradiation pulses

Schlenk Techniques for Anionic Polymerization

KAUST Repository

Ratkanthwar, Kedar; Zhao, Junpeng; Zhang, Hefeng; Hadjichristidis, Nikolaos; Mays, Jimmy

2015-01-01

Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands

An easily regenerable enzyme reactor prepared from polymerized high internal phase emulsions

International Nuclear Information System (INIS)

Ruan, Guihua; Wu, Zhenwei; Huang, Yipeng; Wei, Meiping; Su, Rihui; Du, Fuyou

2016-01-01

A large-scale high-efficient enzyme reactor based on polymerized high internal phase emulsion monolith (polyHIPE) was prepared. First, a porous cross-linked polyHIPE monolith was prepared by in-situ thermal polymerization of a high internal phase emulsion containing styrene, divinylbenzene and polyglutaraldehyde. The enzyme of TPCK-Trypsin was then immobilized on the monolithic polyHIPE. The performance of the resultant enzyme reactor was assessed according to the conversion ability of N_α-benzoyl-L-arginine ethyl ester to N_α-benzoyl-L-arginine, and the protein digestibility of bovine serum albumin (BSA) and cytochrome (Cyt-C). The results showed that the prepared enzyme reactor exhibited high enzyme immobilization efficiency and fast and easy-control protein digestibility. BSA and Cyt-C could be digested in 10 min with sequence coverage of 59% and 78%, respectively. The peptides and residual protein could be easily rinsed out from reactor and the reactor could be regenerated easily with 4 M HCl without any structure destruction. Properties of multiple interconnected chambers with good permeability, fast digestion facility and easily reproducibility indicated that the polyHIPE enzyme reactor was a good selector potentially applied in proteomics and catalysis areas. - Graphical abstract: Schematic illustration of preparation of hypercrosslinking polyHIPE immobilized enzyme reactor for on-column protein digestion. - Highlights: • A reactor was prepared and used for enzyme immobilization and continuous on-column protein digestion. • The new polyHIPE IMER was quite suit for protein digestion with good properties. • On-column digestion revealed that the IMER was easy regenerated by HCl without any structure destruction.

An easily regenerable enzyme reactor prepared from polymerized high internal phase emulsions

Energy Technology Data Exchange (ETDEWEB)

Ruan, Guihua, E-mail: guihuaruan@hotmail.com [Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guangxi 541004 (China); Guangxi Collaborative Innovation Center for Water Pollution Control and Water Safety in Karst Area, Guilin University of Technology, Guilin 541004 (China); Wu, Zhenwei; Huang, Yipeng; Wei, Meiping; Su, Rihui [Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guangxi 541004 (China); Du, Fuyou, E-mail: dufu2005@126.com [Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guangxi 541004 (China); Guangxi Collaborative Innovation Center for Water Pollution Control and Water Safety in Karst Area, Guilin University of Technology, Guilin 541004 (China)

2016-04-22

A large-scale high-efficient enzyme reactor based on polymerized high internal phase emulsion monolith (polyHIPE) was prepared. First, a porous cross-linked polyHIPE monolith was prepared by in-situ thermal polymerization of a high internal phase emulsion containing styrene, divinylbenzene and polyglutaraldehyde. The enzyme of TPCK-Trypsin was then immobilized on the monolithic polyHIPE. The performance of the resultant enzyme reactor was assessed according to the conversion ability of N{sub α}-benzoyl-L-arginine ethyl ester to N{sub α}-benzoyl-L-arginine, and the protein digestibility of bovine serum albumin (BSA) and cytochrome (Cyt-C). The results showed that the prepared enzyme reactor exhibited high enzyme immobilization efficiency and fast and easy-control protein digestibility. BSA and Cyt-C could be digested in 10 min with sequence coverage of 59% and 78%, respectively. The peptides and residual protein could be easily rinsed out from reactor and the reactor could be regenerated easily with 4 M HCl without any structure destruction. Properties of multiple interconnected chambers with good permeability, fast digestion facility and easily reproducibility indicated that the polyHIPE enzyme reactor was a good selector potentially applied in proteomics and catalysis areas. - Graphical abstract: Schematic illustration of preparation of hypercrosslinking polyHIPE immobilized enzyme reactor for on-column protein digestion. - Highlights: • A reactor was prepared and used for enzyme immobilization and continuous on-column protein digestion. • The new polyHIPE IMER was quite suit for protein digestion with good properties. • On-column digestion revealed that the IMER was easy regenerated by HCl without any structure destruction.

Self-Propagating Frontal Polymerization in Water at Ambient Pressure

Science.gov (United States)

Olten, Nesrin; Kraigsley, Alison; Ronney, Paul D.

2003-01-01

Advances in polymer chemistry have led to the development of monomers and initiation agents that enable propagating free-radical polymerization fronts to exist. These fronts are driven by the exothermicity of the polymerization reaction and the transport of heat from the polymerized product to the reactant monomer/solvent/initiator solution. The thermal energy transported to the reactant solution causes the initiator to decompose, yielding free radicals, which start the free radical polymerization process as discussed in recent reviews. The use of polymerization processes based on propagating fronts has numerous applications. Perhaps the most important of these is that it enables rapid curing of polymers without external heating since the polymerization process itself provides the high temperatures necessary to initiate and sustain polymerization. This process also enables more uniform curing of arbitrarily thick samples since it does not rely on heat transfer from an external source, which will necessarily cause the temperature history of the sample to vary with distance from the surface according to a diffusion-like process. Frontal polymerization also enables filling and sealing of structures having cavities of arbitrary shape without having to externally heat the structure. Water at atmospheric pressure is most convenient solvent to employ and the most important for practical applications (because of the cost and environmental issues associated with DMSO and other solvents). Nevertheless, to our knowledge, steady, self-propagating polymerization fronts have not been reported in water at atmospheric pressure. Currently, polymerization fronts require a high boiling point solvent (either water at high pressures or an alternative solvent such as dimethyl sulfoxide (DMSO) (boiling point 189 C at atmospheric pressure.) Early work on frontal polymerization, employed pressures up to 5000 atm in order to avoid boiling of the monomer/solvent/initiator solution. High

Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

KAUST Repository

Thomas, Renee M.

2010-11-24

A highly active enantiopure bimetallic cobalt complex was explored for the enantioselective polymerization of a variety of monosubstituted epoxides. The polymerizations were optimized for high rates and stereoselectivity, with s-factors (kfast/kslow) for most epoxides exceeding 50 and some exceeding 300, well above the threshold for preparative utility of enantiopure epoxides and isotactic polyethers. Values for mm triads of the resulting polymers are typically greater than 95%, with some even surpassing 98%. In addition, the use of a racemic catalyst allowed the preparation of isotactic polyethers in quantitative yields. The thermal properties of these isotactic polyethers are presented, with many polymers exhibiting high T m values. This is the first report of the rapid synthesis of a broad range of highly isotactic polyethers via the enantioselective polymerization of racemic epoxides. © 2010 American Chemical Society.

Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

KAUST Repository

Thomas, Renee M.; Widger, Peter C. B.; Ahmed, Syud M.; Jeske, Ryan C.; Hirahata, Wataru; Lobkovsky, Emil B.; Coates, Geoffrey W.

2010-01-01

A highly active enantiopure bimetallic cobalt complex was explored for the enantioselective polymerization of a variety of monosubstituted epoxides. The polymerizations were optimized for high rates and stereoselectivity, with s-factors (kfast/kslow) for most epoxides exceeding 50 and some exceeding 300, well above the threshold for preparative utility of enantiopure epoxides and isotactic polyethers. Values for mm triads of the resulting polymers are typically greater than 95%, with some even surpassing 98%. In addition, the use of a racemic catalyst allowed the preparation of isotactic polyethers in quantitative yields. The thermal properties of these isotactic polyethers are presented, with many polymers exhibiting high T m values. This is the first report of the rapid synthesis of a broad range of highly isotactic polyethers via the enantioselective polymerization of racemic epoxides. © 2010 American Chemical Society.

The tempered polymerization of human neuroserpin.

Directory of Open Access Journals (Sweden)

Rosina Noto

Full Text Available Neuroserpin, a member of the serpin protein superfamily, is an inhibitor of proteolytic activity that is involved in pathologies such as ischemia, Alzheimer's disease, and Familial Encephalopathy with Neuroserpin Inclusion Bodies (FENIB. The latter belongs to a class of conformational diseases, known as serpinopathies, which are related to the aberrant polymerization of serpin mutants. Neuroserpin is known to polymerize, even in its wild type form, under thermal stress. Here, we study the mechanism of neuroserpin polymerization over a wide range of temperatures by different techniques. Our experiments show how the onset of polymerization is dependent on the formation of an intermediate monomeric conformer, which then associates with a native monomer to yield a dimeric species. After the formation of small polymers, the aggregation proceeds via monomer addition as well as polymer-polymer association. No further secondary mechanism takes place up to very high temperatures, thus resulting in the formation of neuroserpin linear polymeric chains. Most interesting, the overall aggregation is tuned by the co-occurrence of monomer inactivation (i.e. the formation of latent neuroserpin and by a mechanism of fragmentation. The polymerization kinetics exhibit a unique modulation of the average mass and size of polymers, which might suggest synchronization among the different processes involved. Thus, fragmentation would control and temper the aggregation process, instead of enhancing it, as typically observed (e.g. for amyloid fibrillation.

Accelerated Combinatorial High Throughput Star Polymer Synthesis via a Rapid One-Pot Sequential Aqueous RAFT (rosa-RAFT) Polymerization Scheme.

Science.gov (United States)

Cosson, Steffen; Danial, Maarten; Saint-Amans, Julien Rosselgong; Cooper-White, Justin J

2017-04-01

Advanced polymerization methodologies, such as reversible addition-fragmentation transfer (RAFT), allow unprecedented control over star polymer composition, topology, and functionality. However, using RAFT to produce high throughput (HTP) combinatorial star polymer libraries remains, to date, impracticable due to several technical limitations. Herein, the methodology "rapid one-pot sequential aqueous RAFT" or "rosa-RAFT," in which well-defined homo-, copolymer, and mikto-arm star polymers can be prepared in very low to medium reaction volumes (50 µL to 2 mL) via an "arm-first" approach in air within minutes, is reported. Due to the high conversion of a variety of acrylamide/acrylate monomers achieved during each successive short reaction step (each taking 3 min), the requirement for intermediary purification is avoided, drastically facilitating and accelerating the star synthesis process. The presented methodology enables RAFT to be applied to HTP polymeric bio/nanomaterials discovery pipelines, in which hundreds of complex polymeric formulations can be rapidly produced, screened, and scaled up for assessment in a wide range of applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Functional polypeptides obtained by living ring opening polymerizations of N-carboxyanhydrides

NARCIS (Netherlands)

Habraken, G.J.M.

2011-01-01

N-Carboxyanhydride ring opening polymerization (NCA ROP) is a method to prepare polypeptides with a high degree of polymerization in large quantities. The living polymerization technique of NCA ROP gave the opportunity to synthesize many polymer architectures with well-defined blocks and copolymers

A model of frontal polymerization using complex initiation

Directory of Open Access Journals (Sweden)

P. M. Goldfeder

1999-01-01

Full Text Available Frontal polymerization is a process in which a spatially localized reaction zone propagates into a monomer, converting it into a polymer. In the simplest case of free-radical polymerization, a mixture of monomer and initiator is placed in a test tube. A reaction is then initiated at one end of the tube. Over time, a self-sustained thermal wave, in which chemical conversion occurs, is produced. This phenomenon is possible because of the highly exothermic nature of the polymerization reactions.

High-energy radiation monitoring based on radio-fluorogenic co-polymerization. I : Small volume in situ probe

NARCIS (Netherlands)

Warman, J.M.; De Haas, M.P.; Luthjens, L.

2009-01-01

A method of radiation dosimetry is described which is based on the radiation-induced initiation of polymerization of a bulk monomer (e.g. methyl methacrylate) containing a small concentration (about 100 ppm) of a compound which is non-fluorescent but which becomes highly fluorescent when it is

Preparation of highly absorbing polymeric hydrogels by radiation processing: mechanical and physical properties

International Nuclear Information System (INIS)

Dragusin, M.

1994-01-01

Some highly absorbing polymeric hydrogels such as acrylic polymers were produced by radiation processing with gamma sources Co-60 of 10,000 Ci, 3 kGy/h and an electron beam accelerator of 3 - 6 MeV, 0.3 - 3 kGy/s. For practical purposes, such as different applications in agriculture, etc, we studied the physical properties of residual monomers by refractometric and polarographic methods and the mechanical properties (gel strength) with devices made in our laboratory. (Author)

A flexible, robust and antifouling asymmetric membrane based on ultra-long ceramic/polymeric fibers for high-efficiency separation of oil/water emulsions.

Science.gov (United States)

Wang, Kui; Yiming, Wubulikasimu; Saththasivam, Jayaprakash; Liu, Zhaoyang

2017-07-06

Polymeric and ceramic asymmetric membranes have dominated commercial membranes for water treatment. However, polymeric membranes are prone to becoming fouled, while ceramic membranes are mechanically fragile. Here, we report a novel concept to develop asymmetric membranes based on ultra-long ceramic/polymeric fibers, with the combined merits of good mechanical stability, excellent fouling resistance and high oil/water selectivity, in order to meet the stringent requirements for practical oil/water separation. The ultra-long dimensions of ceramic nanofibers/polymeric microfibers endow this novel membrane with mechanical flexibility and robustness, due to the integrated and intertwined structure. This membrane is capable of separating oil/water emulsions with high oil-separation efficiency (99.9%), thanks to its nanoporous selective layer made of ceramic nanofibers. Further, this membrane also displays superior antifouling properties due to its underwater superoleophobicity and ultra-low oil adhesion of the ceramic-based selective layer. This membrane exhibits high water permeation flux (6.8 × 10 4 L m -2 h -1 bar -1 ) at low operation pressures, which is attributed to its 3-dimensional (3D) interconnected fiber-based structure throughout the membrane. In addition, the facile fabrication process and inexpensive materials required for this membrane suggest its significant potential for industrial applications.

Twin screw extruders as polymerization reactors for a free radical homo polymerization

NARCIS (Netherlands)

Ganzeveld, K.J.; Janssen, L.P.B.M.

The bulk polymerization of n-butylmethacrylate was investigated in a counter-rotating twin screw extruder. It appeared that the gel effect, occurring with bulk polymerizations, affected the polymerization progress very strongly. Due to this effect the conversion of the reaction is independent of the

Emulsifier-free emulsion polymerization produces highly charged, monodisperse particles for near infrared photonic crystals.

Science.gov (United States)

Reese, Chad E; Asher, Sanford A

2002-04-01

We have developed emulsifier-free, emulsion polymerization recipes for the synthesis of highly charged, monodisperse latex particles of diameters between 500 and 1100 nm. These latexes consist of poly[styrene-(co-2-hydroxyethyl methacrylate)] spherical particles whose surfaces are functionalized with sulfate and carboxylic acid groups. These highly charged, monodisperse particles readily self-assemble into robust, three-dimensionally ordered crystalline colloidal array photonic crystals that Bragg diffract light in the near infrared spectral region. By altering the particle number density, the diffraction wavelength can be tuned from approximately 1000 to approximately 4000 nm.

Mechanocatalytic polymerization and cross-linking in a polymeric matrix

NARCIS (Netherlands)

Jakobs, R.T.M.; Ma, Shuang; Sijbesma, R.P.

2013-01-01

A latent olefin metathesis catalyst, bearing two polymeric NHC ligands, was embedded in a semicrystalline polymer matrix containing cyclic olefins. The catalyst was activated by straining the solid material under compression, resulting in polymerization and cross-linking reactions of the monomers in

Various aspects of ultrasound assisted emulsion polymerization process.

Science.gov (United States)

Korkut, Ibrahim; Bayramoglu, Mahmut

2014-07-01

In this paper, the effects of ultrasonic (US) power, pulse ratio, probe area and recipe composition were investigated on two process responses namely, monomer (methyl methacrylate, MMA) conversion and electrical energy consumption per mass of product polymer (PMMA). Pulsed mode US is more suitable than continuous mode US for emulsion polymerization. The probe (tip) area has little effect on the yield of polymerization when comparing 19 and 13 mm probes, 13 mm probe performing slightly better for high conversion levels. Meanwhile, large probe area is beneficial for high conversion efficiency of electric energy to US energy as well as for high radical generation yield per energy consumed. The conversion increased slightly and electrical energy consumption decreased substantially by using a recipe with high SDS and monomer concentrations. Conclusions presented in this paper may be useful for scale-up of US assisted emulsion polymerization. Copyright © 2014 Elsevier B.V. All rights reserved.

Surfactant-Free RAFT Emulsion Polymerization of Styrene Using Thermoresponsive macroRAFT Agents: Towards Smart Well-Defined Block Copolymers with High Molecular Weights

Directory of Open Access Journals (Sweden)

Steffen Eggers

2017-12-01

Full Text Available The combination of reversible addition–fragmentation chain transfer (RAFT and emulsion polymerization has recently attracted much attention as a synthetic tool for high-molecular-weight block copolymers and their micellar nano-objects. Up to recently, though, the use of thermoresponsive polymers as both macroRAFT agents and latex stabilizers was impossible in aqueous media due to their hydrophobicity at the usually high polymerization temperatures. In this work, we present a straightforward surfactant-free RAFT emulsion polymerization to obtain thermoresponsive styrenic block copolymers with molecular weights of around 100 kDa and their well-defined latexes. The stability of the aqueous latexes is achieved by adding 20 vol % of the cosolvent 1,4-dioxane (DOX, increasing the phase transition temperature (PTT of the used thermoresponsive poly(N-acryloylpyrrolidine (PAPy macroRAFT agents above the polymerization temperature. Furthermore, this cosolvent approach is combined with the use of poly(N,N-dimethylacrylamide-block-poly(N-acryloylpiperidine-co-N-acryloylpyrrolidine (PDMA-b-P(APi-co-APy as the macroRAFT agent owning a short stabilizing PDMA end block and a widely adjustable PTT of the P(APi-co-APy block in between 4 and 47 °C. The temperature-induced collapse of the latter under emulsion polymerization conditions leads to the formation of RAFT nanoreactors, which allows for a very fast chain growth of the polystyrene (PS block. In dynamic light scattering (DLS, as well as cryo-transmission electron microscopy (cryoTEM, moreover, all created latexes indeed reveal a high (temperature stability and a reversible collapse of the thermoresponsive coronal block upon heating. Hence, this paper pioneers a versatile way towards amphiphilic thermoresponsive high-molecular-weight block copolymers and their nano-objects with tailored corona switchability.

Direct surface PEGylation of nanodiamond via RAFT polymerization

International Nuclear Information System (INIS)

Shi, Yingge; Liu, Meiying; Wang, Ke; Huang, Hongye; Wan, Qing; Tao, Lei; Fu, Lihua; Zhang, Xiaoyong; Wei, Yen

2015-01-01

Graphical abstract: In this paper, we describe an efficient, practical and novel method to modify ND via direct immobilization of chain transfer agent for RAFT polymerization. - Highlights: • Surface PEGylation of ND via RAFT polymerization. • ND with high water dispersibility and excellent biocompatibility. • Controlled living polymerization. - Abstract: Nanodiamond (ND) is a novel class of carbon nanomaterials, which has been extensively investigated for biomedical applications because of its small size, high surface area and excellent biocompatibility. However, the biomedical applications of unmodified ND are still largely restricted because of their poor dispersibility in both aqueous and organic medium. In this work, we reported a novel strategy for the surface modification of ND via reversible addition fragmentation chain transfer (RAFT) polymerization. For preparation of the PEGylated ND (pPEGMA-ND), chain transfer agent (CTA) was immobilized onto ND through reaction between the hydroxyl group of ND and the carboxyl group of CTA, which was used as the initiator for surface-initiated RAFT polymerization. The successful preparation of pPEGMA-ND was characterized by nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectra and thermal gravimetric analysis in detail. Results demonstrated that pPEGMA-ND exhibited enhanced water dispersibility and desirable biocompatibility, making it promising for biomedical applications.

Direct surface PEGylation of nanodiamond via RAFT polymerization

Energy Technology Data Exchange (ETDEWEB)

Shi, Yingge [Department of Chemistry and Jiangxi Provincial Key Laboratory of New Energy Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Liu, Meiying [Department of Chemistry and Jiangxi Provincial Key Laboratory of New Energy Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wang, Ke [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China); Huang, Hongye; Wan, Qing [Department of Chemistry and Jiangxi Provincial Key Laboratory of New Energy Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Tao, Lei [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China); Fu, Lihua [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry and Jiangxi Provincial Key Laboratory of New Energy Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China)

2015-12-01

Graphical abstract: In this paper, we describe an efficient, practical and novel method to modify ND via direct immobilization of chain transfer agent for RAFT polymerization. - Highlights: • Surface PEGylation of ND via RAFT polymerization. • ND with high water dispersibility and excellent biocompatibility. • Controlled living polymerization. - Abstract: Nanodiamond (ND) is a novel class of carbon nanomaterials, which has been extensively investigated for biomedical applications because of its small size, high surface area and excellent biocompatibility. However, the biomedical applications of unmodified ND are still largely restricted because of their poor dispersibility in both aqueous and organic medium. In this work, we reported a novel strategy for the surface modification of ND via reversible addition fragmentation chain transfer (RAFT) polymerization. For preparation of the PEGylated ND (pPEGMA-ND), chain transfer agent (CTA) was immobilized onto ND through reaction between the hydroxyl group of ND and the carboxyl group of CTA, which was used as the initiator for surface-initiated RAFT polymerization. The successful preparation of pPEGMA-ND was characterized by nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectra and thermal gravimetric analysis in detail. Results demonstrated that pPEGMA-ND exhibited enhanced water dispersibility and desirable biocompatibility, making it promising for biomedical applications.

UV laser engraving of high temperature polymeric materials

International Nuclear Information System (INIS)

Martinez, D.; Laude, L.D.; Kolev, K.; Hanus, F.

1999-01-01

Among emerging technologies, those associated with laser sources as surface processing tools are quite promising. In the present work, a UV pulsed (excimer) laser source is experimented for engraving (or ablating) polymeric materials based on three high temperature polymers: polyethylene terephtalate (PET), polyethersulfone (PES) and polyphenylene sulfide (PPS). The ablation phenomenon is demonstrated on all these polymers and evaluated by stylus profilometry upon varying the laser fluence at impact. For each polymer, results give evidence for three characteristic quantities: an ablation threshold E sub 0, a maximum ablation depth per pulse z sub 0 and an initial rate of ablation α, just above threshold. A simple ablation model is presented which describes correctly the observed behaviours and associates closely the above quantities to the polymer formulation, thus providing for the first time a rational basis to polymer ablation. The model may be extended to parent plastic materials whenever containing the same polymers. It may also be used to predict the behaviours of other polymers when subjected to excimer laser irradiation

Chelating polymeric membranes

KAUST Repository

Peinemann, Klaus-Viktor; Villalobos Vazquez de la Parra, Luis Francisco; Hilke, Roland

2015-01-01

microporous chelating polymeric membrane. Embodiments include, but are not limited to, microporous chelating polymeric membranes, device comprising the membranes, and methods of using and making the same.

Fluorescent polymeric nanocomposite films generated by surface-mediated photoinitiation of polymerization

International Nuclear Information System (INIS)

Avens, Heather J.; Chang, Erin L.; May, Allison M.; Berron, Brad J.; Seedorf, Gregory J.; Balasubramaniam, Vivek; Bowman, Christopher N.

2011-01-01

Incorporation of nanoparticles (NPs) into polymer films represents a valuable strategy for achieving a variety of desirable physical, optical, mechanical, and electrical attributes. Here, we describe and characterize the creation of highly fluorescent polymer films by entrapment of fluorescent NPs into polymer matrices through surface-mediated eosin photoinitiation reactions. Performing surface-mediated polymerizations with NPs combines the benefits of a covalently anchored film with the unique material properties afforded by NPs. The effects of monomer type, crosslinker content, NP size, and NP surface chemistry were investigated to determine their impact on the relative amount of NPs entrapped in the surface-bound films. The density of entrapped NPs was increased up to 6-fold by decreasing the NP diameter. Increasing the crosslinking agent concentration enabled a greater than 2-fold increase in the amount of NPs entrapped. Additionally, the monomer chemistry played a significant role as poly(ethylene glycol) diacrylate (PEGDA)-based monomer formulations entrapped a 10-fold higher density of carboxy-functionalized NPs than did acrylamide/bisacrylamide formulations, though the latter formulations ultimately immobilized more fluorophores by generating thicker films. In the context of a polymerization-based microarray biodetection platform, these findings enabled tailoring of the monomer and NP selection to yield a 200-fold improvement in sensitivity from 31 (±1) to 0.16 (±0.01) biotinylated target molecules per square micron. Similarly, in polymerization-based cell staining applications, appropriate monomer and NP selection enabled facile visualization of microscale, sub-cellular features. Careful consideration of monomer and NP selection is critical to achieve the desired properties in applications that employ surface-mediated polymerization to entrap NPs.

One-Pot Synthesis of Charged Amphiphilic Diblock and Triblock Copolymers Via High-Throughput Cu(0-Mediated Polymerization

Directory of Open Access Journals (Sweden)

Lenny Voorhaar

2017-07-01

Full Text Available Block copolymers containing functionalized monomers, for example those containing charged groups, can be used for many purposes, one of which is the design of polymeric supramolecular materials based on electrostatic interactions. In this paper the synthesis of diblock copolymers and ABA-triblock copolymers containing poly(n-butyl acrylate as a first or middle block and poly(2-(dimethylaminoethyl acrylate, poly(1-ethoxyethyl acrylate and poly(1-ethoxyethyl-2-carboxyethyl acrylate as second or outer blocks, resulting in block copolymers that can contain positive or negative charges, is reported. The polymerizations were performed and optimized via one-pot sequential monomer addition reactions via Cu(0-mediated polymerization using an automated parallel synthesizer. Different initiators, monomer concentrations and polymerization times were tested. While a bromide-containing initiator led to the best results for most monomers, when polymerizing 2-(dimethylaminoethyl acrylate the use of a chloride-containing initiator was necessary. Due to the slower polymerization using this initiator, a longer polymerization time was needed before addition of the second monomer. Using the optimized conditions, the diblock and triblock copolymers could be synthesized with good control over molecular weight and dispersities around 1.1 were obtained.

Synthesis of polyphenylacetylene by radiation-induced polymerization in deoxycholic acid clathrate

International Nuclear Information System (INIS)

Cataldo, Franco; Strazzulla, Giovanni; Iglesias-Groth, Susana

2009-01-01

Phenylacetylene was polymerized as inclusion compound (clathrate) inside deoxycholic acid (DOCA) crystals. The polymerization was initiated by γ radiation and a total dose of 320 kGy was employed. The resulting polyphenylacetylene (PPA) was isolated by dissolution of deoxycholic acid in boiling ethanol. PPA high polymer was accompanied by a series of phenylacetylene oligomers, which were detected by liquid chromatographic analysis (HPLC). PPA was characterized by electronic absorption spectroscopy and by FT-IR spectroscopy in comparison to a reference PPA prepared by a stereospecific catalyst. The microstructure of PPA from inclusion polymerization was highly trans type, similar to that observed on PPA prepared by bulk radiolysis. No optical activity was detected by polarimetry on PPA prepared by inclusion polymerization. The host-guest complex PPA/DOCA was studied by differential thermal analysis (DTA) and by thermogravimetry (TGA). DTA provided evidences of the host-guest complex formation from the shift of the melting point of DOCA while the TGA confirmed the identity - in terms of thermal behaviour - of the PPA from inclusion polymerization with that from stereospecific polymerization

Monte Carlo simulation of non-linear free radical polymerization using a percolation kinetic gelation model (I): free radical homo polymerization

International Nuclear Information System (INIS)

Ghiass, M.; Dabir, B.; Nikazar, M.; Rey, A.D.; Mirzadeh, H.

2001-01-01

A kinetic gelation model that incorporates the kinetics of free radical homo polymerization is implemented to determine the effects of kinetics on polymerization statistics and microstructures. The simulation is performed on a simple cubic lattice that has 100 sites in each direction. A new algorithm for random selecting of the next step in a self-avoiding random walk and very efficient mechanisms of mobility of components are introduced to improve the generality of the predictions by removing commonly accruing deficiencies due to early trapping of radicals. A first order kinetics is considered for decomposition of initiator that enables us to consider the effect of temperature on polymerization reaction. Better understanding of microstructural evolution during polymerization and providing a framework to produce a realistic system of highly packed random chains within polymer network are among the benefits of model

Application of mercapto-silica polymerized high internal phase emulsions for the solid-phase extraction and preconcentration of trace lead(II).

Science.gov (United States)

Su, Rihui; Ruan, Guihua; Chen, Zhengyi; Du, Fuyou; Li, Jianping

2015-12-01

A new class of solid-phase extraction column prepared with grafted mercapto-silica polymerized high internal phase emulsion particles was used for the preconcentration of trace lead. First, mercapto-silica polymerized high internal phase emulsion particles were synthesized by using high internal phase emulsion polymerization and carefully assembled in a polyethylene syringe column. The influences of various parameters including adsorption pH value, adsorption and desorption solvents, flow rate of the adsorption and desorption procedure were optimized, respectively, and the suitable uploading sample volumes, adsorption capacity, and reusability of solid phase extraction column were also investigated. Under the optimum conditions, Pb(2+) could be preconcentrated quantitatively over a wide pH range (2.0-5.0). In the presence of foreign ions, such as Na(+) , K(+) , Ca(2+) , Zn(2+) , Mg(2+) , Cu(2+) , Fe(2+) , Cd(2+) , Cl(-) and NO3 (-) , Pb(2+) could be recovered successfully. The prepared solid-phase extraction column performed with high stability and desirable durability, which allowed more than 100 replicate extractions without measurable changes of performance. The feasibility of the developed method was further validated by the extraction of Pb(2+) in rice samples. At three spiked levels of 40.0, 200 and 800 μg/kg, the average recoveries for Pb(2+) in rice samples ranged from 87.3 to 105.2%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Silicon dioxide obtained by Polymeric Precursor Method

International Nuclear Information System (INIS)

Oliveira, C.T.; Granado, S.R.; Lopes, S.A.; Cavalheiro, A.A.

2011-01-01

The Polymeric Precursor Method is able for obtaining several oxide material types with high surface area even obtained in particle form. Several MO 2 oxide types such as titanium, silicon and zirconium ones can be obtained by this methodology. In this work, the synthesis of silicon oxide was monitored by thermal analysis, XRD and surface area analysis in order to demonstrate the influence of the several synthesis and calcining parameters. Surface area values as higher as 370m2/g and increasing in the micropore volume nm were obtained when the material was synthesized by using ethylene glycol as polymerizing agent. XRD analysis showed that the material is amorphous when calcinated at 600°C in despite of the time of calcining, but the material morphology is strongly influenced by the polymeric resin composition. Using Glycerol as polymerizing agent, the pore size increase and the surface area goes down with the increasing in decomposition time, when compared to ethylene glycol. (author)

Pressure-induced polymerization of P(CN){sub 3}

Energy Technology Data Exchange (ETDEWEB)

Gou, Huiyang, E-mail: hgou@ciw.edu, E-mail: tstrobel@ciw.edu; Kim, Duck Young; Strobel, Timothy A., E-mail: hgou@ciw.edu, E-mail: tstrobel@ciw.edu [Geophysical Laboratory, Carnegie Institution of Washington, 5251 Broad Branch Road, NW, Washington, DC 20015 (United States); Yonke, Brendan L. [NRC Postdoctoral Associate, Naval Research Laboratory, 4555 Overlook Ave., SW, Washington, DC 20375 (United States); Epshteyn, Albert [Naval Research Laboratory, 4555 Overlook Ave., SW, Washington, DC 20375 (United States); Smith, Jesse S. [High Pressure Collaborative Access Team, Geophysical Laboratory, Carnegie Institution of Washington, Argonne, Illinois 60439 (United States)

2015-05-21

Motivated to explore the formation of novel extended carbon-nitrogen solids via well-defined molecular precursor pathways, we studied the chemical reactivity of highly pure phosphorous tricyanide, P(CN){sub 3}, under conditions of high pressure at room temperature. Raman and infrared (IR) spectroscopic measurements reveal a series of phase transformations below 10 GPa, and several low-frequency vibrational modes are reported for the first time. Synchrotron powder X-ray diffraction measurements taken during compression show that molecular P(CN){sub 3} is highly compressible, with a bulk modulus of 10.0 ± 0.3 GPa, and polymerizes into an amorphous solid above ∼10.0 GPa. Raman and IR spectra, together with first-principles molecular-dynamics simulations, show that the amorphization transition is associated with polymerization of the cyanide groups into CN bonds with predominantly sp{sup 2} character, similar to known carbon nitrides, resulting in a novel phosphorous carbon nitride (PCN) polymeric phase, which is recoverable to ambient pressure.

In situ polymerization of monomers for polyphenylquinoxaline/graphite

Science.gov (United States)

Serafini, T. T.; Delvigs, P.; Vannucci, R. D.

1973-01-01

Methods currently used to prepare fiber reinforced, high temperature resistant polyphenylquinoxaline (PPQ) composites employ extremely viscous, low solids content solutions of high molecular weight PPQ polymers. An improved approach, described in this report, consists of impregnating the fiber with a solution of the appropriate monomers instead of a solution of previously synthesized high molecular weight polymer. Polymerization of the monomers occurs in situ on the fiber during the solvent removal and curing stages. The in situ polymerization approach greatly simplifies the fabrication of PPQ graphite fiber composites. The use of low viscosity monomeric type solutions facilitates fiber wetting, permits a high solids content, and eliminates the need for prior polymer synthesis.

Modeling of free radical polymerization up to high conversion. II. Development of a mathematical model.

NARCIS (Netherlands)

Tefera shibeshe, N.; Tefera, N.; Weickert, G.; Westerterp, K.R.

1997-01-01

In free radical polymerization diffusion-controlled processes take place simultaneously to the normal chemical reactions. Despite extensive efforts to model such processes a consistent model for the design of a polymerization reactor has not yet been established. In this article a semiempirical

Fabrication, Physicochemical Characterization, and Performance Evaluation of Biodegradable Polymeric Microneedle Patch System for Enhanced Transcutaneous Flux of High Molecular Weight Therapeutics.

Science.gov (United States)

Shah, Viral; Choudhury, Bijaya Krushna

2017-11-01

A revolutionary paradigm shift is being observed currently, towards the use of therapeutic biologics for disease management. The present research was focused on designing an efficient dosage form for transdermal delivery of α-choriogonadotropin (high molecular weight biologic), through biodegradable polymeric microneedles. Polyvinylpyrrolidone-based biodegradable microneedle arrays loaded with high molecular weight polypeptide, α-choriogonadotropin, were fabricated for its systemic delivery via transdermal route. Varied process and formulation parameters were optimized for fabricating microneedle array, which in turn was expected to temporally rupture the stratum corneum layer of the skin, acting as a major barrier to drug delivery through transdermal route. The developed polymeric microneedles were optimized on the basis of quality attributes like mechanical strength, axial strength, insertion ratio, and insertion force analysis. The optimized polymeric microneedle arrays were characterized for in vitro drug release studies, ex vivo drug permeation studies, skin resealing studies, and in vivo pharmacokinetic studies. Results depicted that fabricated polymeric microneedle arrays with mechanical strength of above 5 N and good insertion ratio exhibited similar systemic bioavailability of α-choriogonadotropin in comparison to marketed subcutaneous injection formulation of α-choriogonadotropin. Thus, it was ultimately concluded that the designed drug delivery system can serve as an efficient tool for systemic delivery of therapeutic biologics, with an added benefit of overcoming the limitations of parenteral delivery, achieving better patient acceptability and compliance.

High fluorescence emission silver nano particles coated with poly (styrene-g-soybean oil) graft copolymers: Antibacterial activity and polymerization kinetics.

Science.gov (United States)

Hazer, Baki; Kalaycı, Özlem A

2017-05-01

Autoxidation of poly unsaturated fatty acids makes negative effect on foods. In this work, this negative effect was turned to a great advantage using autoxidized soybean oil as a macroperoxide nanocomposite initiator containing silver nano particles in free radical polymerization of vinyl monomers. The synthesis of soybean oil macro peroxide was carried out by exposing soybean oil to air oxygen with the presence of silver nanoparticles (Ag NPs) at room temperature. Autoxidized soybean oil macroperoxide containing silver nanoparticles (Agsbox) successfully initiated the free radical polymerization of styrene in order to obtain Polystyrene (PS)-g-soybean oil graft copolymer containing Ag NPs. Both autoxidized soybean oil and PS-g-sbox with Ag NPs showed a surface plasmon resonance and high fluorescence emission. Overall rate constant (K) of styrene polymerization initiated by autoxidized soybean oil macroperoxide with Ag NPs was found to be K=1.95.10 -4 Lmol -1 s -1 at 95°C. Antibacterial efficiency was observed in the PS-g-soybean oil graft copolymer film samples containing Ag NPs. 1 H NMR and GPC techniques were used for the structural analysis of the fractionated polymeric oils. Copyright © 2016 Elsevier B.V. All rights reserved.

Radiation-induced in-source polymerization of acrylonitrile in urea canal complex

International Nuclear Information System (INIS)

Yoshii, Fumio; Abe, Toshihiko; Kobayashi, Yasushi.

1975-01-01

Effect of reaction conditions on the radiation-induced in-source polymerization of acrylonitrile in urea canal complex and the properties of obtained polyacrylonitriles were investigated. The results were discussed in comparison with previously reported of the post-polymerization experiments. 1) Rate of polymerization and viscosity (eta sub(sp)/C) were the highest when the molar ratio of acrylonitrile to urea in canal complex was unity. Similar results were also obtained in the post-polymerization. However, eta sub(sp)/C exhibited different behavior on polymerization time in comparison with post-polymerization. 2) The initial rate (Rsub(p)) of polymerization is proportional to the dose rate (I) at low dose rate, but at high dose rates (above 2x10 5 r/hr) makes Rsub(p) proportional to Isup(0.5). 3) Molecular weight distribution become broader with increasing polymerization time and is broad as compared with those obtained by the post-polymerization. G-value of initiation of polymerization decreased with increasing polymerization time. These value was larger than the that obtained in the post-polymerization. 4) The stereoregularity of the polyacrylonitriles was independent of the molar ratio of acrylonitrile to urea in the canal complex and conversion. 5) The appearance of the polyacrylonitriles observed by the scanning electron microscope changed from curled string to extended one as the polymerization proceed. 6) Infrared spectrum revealed the ketenimine and cyclization structure in the polyacrylonitriles obtained below -100 0 C. The content of these abnormal structures increased with increasing conversion. (auth.)

Intrinsic Levanase Activity of Bacillus subtilis 168 Levansucrase (SacB.

Directory of Open Access Journals (Sweden)

Luz Méndez-Lorenzo

Full Text Available Levansucrase catalyzes the synthesis of fructose polymers through the transfer of fructosyl units from sucrose to a growing fructan chain. Levanase activity of Bacillus subtilis levansucrase has been described since the very first publications dealing with the mechanism of levan synthesis. However, there is a lack of qualitative and quantitative evidence regarding the importance of the intrinsic levan hydrolysis of B. subtilis levansucrase and its role in the levan synthesis process. Particularly, little attention has been paid to the long-term hydrolysis products, including its participation in the final levan molecules distribution. Here, we explored the hydrolytic and transferase activity of the B. subtilis levansucrase (SacB when levans produced by the same enzyme are used as substrate. We found that levan is hydrolyzed through a first order exo-type mechanism, which is limited to a conversion extent of around 30% when all polymer molecules reach a structure no longer suitable to SacB hydrolysis. To characterize the reaction, Isothermal Titration Calorimetry (ITC was employed and the evolution of the hydrolysis products profile followed by HPLC, GPC and HPAEC-PAD. The ITC measurements revealed a second step, taking place at the end of the reaction, most probably resulting from disproportionation of accumulated fructo-oligosaccharides. As levanase, levansucrase may use levan as substrate and, through a fructosyl-enzyme complex, behave as a hydrolytic enzyme or as a transferase, as demonstrated when glucose and fructose are added as acceptors. These reactions result in a wide variety of oligosaccharides that are also suitable acceptors for fructo-oligosaccharide synthesis. Moreover, we demonstrate that SacB in the presence of levan and glucose, through blastose and sucrose synthesis, results in the same fructooligosaccharides profile as that observed in sucrose reactions. We conclude that SacB has an intrinsic levanase activity that

Synthesis and Evaluation of Molecularly Imprinted Polymeric Microspheres for Chloramphenicol by Aqueous Suspension Polymerization as a High Performance Liquid Chromatography Stationary Phase

International Nuclear Information System (INIS)

Zhang, Yan; Lei, Jiandu

2013-01-01

Molecularly imprinted microsphere for chloramphenicol (CAP) with high adsorption capacity and excellent selectivity is prepared by aqueous suspension polymerization, in which chloramphenicol is used as template molecule and ethyl acetate as porogen. The CAP-imprinted microspheres are used as high performance liquid chromatography (HPLC) stationary phase and packed into stainless steel column (150 mm Χ 4.6 mm i. d.) for selective separation of chloramphenicol. HPLC analysis suggests that chloramphenicol can be distinguished from not only its structural analogs but also other broad-spectrum antibiotic such as erythromycin and tetracycline. In addition, the binding experiments of CAP-imprinted microspheres are carried out in ethanol/water (1:4, V:V), the results indicate that the maximum apparent static binding capacity of molecularly imprinted microspheres is up to 66.64 mg g -1 according to scatchard model

Polymeric micelles for drug targeting.

Science.gov (United States)

Mahmud, Abdullah; Xiong, Xiao-Bing; Aliabadi, Hamidreza Montazeri; Lavasanifar, Afsaneh

2007-11-01

Polymeric micelles are nano-delivery systems formed through self-assembly of amphiphilic block copolymers in an aqueous environment. The nanoscopic dimension, stealth properties induced by the hydrophilic polymeric brush on the micellar surface, capacity for stabilized encapsulation of hydrophobic drugs offered by the hydrophobic and rigid micellar core, and finally a possibility for the chemical manipulation of the core/shell structure have made polymeric micelles one of the most promising carriers for drug targeting. To date, three generations of polymeric micellar delivery systems, i.e. polymeric micelles for passive, active and multifunctional drug targeting, have arisen from research efforts, with each subsequent generation displaying greater specificity for the diseased tissue and/or targeting efficiency. The present manuscript aims to review the research efforts made for the development of each generation and provide an assessment on the overall success of polymeric micellar delivery system in drug targeting. The emphasis is placed on the design and development of ligand modified, stimuli responsive and multifunctional polymeric micelles for drug targeting.

Phosphazene-promoted anionic polymerization

KAUST Repository

Zhao, Junpeng

2014-01-01

In the recent surge of metal-free polymerization techniques, phosphazene bases have shown their remarkable potential as organic promoters/catalysts for the anionic polymerization of various types of monomers. By complexation with the counterion (e.g. proton or lithium cation), phosphazene base significantly improve the nucleophilicity of the initiator/chain-end resulting in rapid and usually controlled anionic/quasi-anionic polymerization. In this review, we will introduce the general mechanism, i.e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

Plasma-polymerized alkaline anion-exchange membrane: Synthesis and structure characterization

International Nuclear Information System (INIS)

Hu Jue; Meng Yuedong; Zhang Chengxu; Fang Shidong

2011-01-01

After-glow discharge plasma polymerization was developed for alkaline anion-exchange membranes synthesis using vinylbenzyl chloride as monomer. X-ray photoelectron spectroscopy and attenuated total reflection Fourier transform infrared spectroscopy were used to characterize the chemical structure properties of plasma-polymerized membranes. Ion-exchange capacities of quaternized poly(vinylbenzyl chloride) (QPVBC) membranes were measured to evaluate their capability of hydroxyl ion transport. A mechanism of plasma polymerization using VBC as monomer that accounts for the competitive effects of free radicals polymerization and plasma ablation in the plasma polymerization process was proposed. Our results indicate that plasma discharge power influences the contents of functional groups and the structure of the plasma polymer membranes, which attribute to the coactions of polymerization and ablation. The properties of uniform morphology, good adhesion to the substrate, high thermal stability and satisfying anion conduction level suggest the potential application of QPVBC membrane deposited at discharge power of 20 W in alkaline direct methanol fuel cells.

Highly Enhanced Fluorescence of CdSeTe Quantum Dots Coated with Polyanilines via In-Situ Polymerization and Cell Imaging Application.

Science.gov (United States)

Xue, Jingjing; Chen, Xinyi; Liu, Shanglin; Zheng, Fenfen; He, Li; Li, Lingling; Zhu, Jun-Jie

2015-09-02

The polyaniline (PAN)-coated CdSeTe quantum dots (QDs) were prepared by in situ polymerization of aniline on the surface of CdSeTe QDs. The PAN-coated CdSeTe QDs has a tremendously enhanced fluorescence (∼40 times) and improved biocompatibility compared to the uncoated CdSeTe QDs. The fluorescence intensity of the PAN-coated CdSeTe QDs can be adjusted by controlling the construction parameters of the PAN shell. The kinetics of the in situ controllable polymerization process was studied by varying the temperature, and the apparent activation energy of polymerization was estimated. With the same method, a series of the PAN derivatives were also tested to coat the CdSeTe QDs in this study. All the QDs showed a significant enhancement of the fluorescence intensity and better biocompatibility. The significantly enhanced fluorescence can provide highly amplified signal for luminescence-based cell imaging.

Conducting Polymeric Materials

DEFF Research Database (Denmark)

Hvilsted, Søren

2016-01-01

The overall objective of this collection is to provide the most recent developments within the various areas of conducting polymeric materials. The conductivity of polymeric materials is caused by electrically charged particles, ions, protons and electrons. Materials in which electrons...

High-temperature nanoporous ceramic monolith prepared from a polymeric bicontinuous microemulsion template.

Science.gov (United States)

Jones, Brad H; Lodge, Timothy P

2009-02-11

Nanoporous ceramic with a unique pore structure was derived from an all-hydrocarbon polymeric bicontinuous microemulsion (BmuE). The BmuE was designed to allow facile removal of one phase, resulting in a nanoporous polymer monolith with BmuE-like structure. The pores were filled with a commercially available, polymeric precursor to nonoxide, Si-based ceramics. Pyrolysis resulted in a monolith of nanoporous ceramic, stable to at least 1000 degrees C, with a BmuE-like pore structure. The pore structure is disordered and 3-D continuous. Microscopy and gas sorption measurements suggest a well-defined pore size distribution spanning roughly 60-100 nm, sizes previously unattainable through related techniques.

In situ polymerization of highly dispersed polypyrrole on reduced graphite oxide for dopamine detection.

Science.gov (United States)

Qian, Tao; Yu, Chenfei; Wu, Shishan; Shen, Jian

2013-12-15

A composite consisting of reduced graphite oxide and highly dispersed polypyrrole nanospheres was synthesized by a straightforward technique, by in situ chemical oxidative polymerization. The novel polypyrrole nanospheres can prevent the aggregation of reduced graphite oxide sheets by electrostatic repulsive interaction, and enhance their electrochemical properties in the nano-molar measurement of dopamine in biological systems with a linear range of 1-8000 nM and a detection limit as low as 0.3 nM. © 2013 Elsevier B.V. All rights reserved.

Silicon and aluminum doping effects on the microstructure and properties of polymeric amorphous carbon films

Energy Technology Data Exchange (ETDEWEB)

Liu, Xiaoqiang, E-mail: lxq_suse@sina.com [Material Corrosion and Protection Key Laboratory of Sichuan province, Sichuan University of Science and Engineering, Zigong 643000 (China); Hao, Junying, E-mail: jyhao@licp.cas.cn [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Xie, Yuntao [Material Corrosion and Protection Key Laboratory of Sichuan province, Sichuan University of Science and Engineering, Zigong 643000 (China)

2016-08-30

Highlights: • Evolution of nanostructure and properties of the polymeric amorphous carbon films were firstly studied. • Si doping enhanced polymerization of the hydrocarbon chains and Al doping resulted in increase in the ordered carbon clusters of polymeric amorphous carbon films. • Soft polymeric amorphous carbon films exhibited an unconventional frictional behaviors with a superior wear resistance. • The mechanical and vacuum tribological properties of the polymeric amorphous carbon films were significantly improved by Si and Al co-doping. - Abstract: Polymeric amorphous carbon films were prepared by radio frequency (R.F. 13.56 MHz) magnetron sputtering deposition. The microstructure evolution of the deposited polymeric films induced by silicon (Si) and aluminum(Al) doping were scrutinized through infrared spectroscopy, multi-wavelength Raman spectroscopy, scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). The comparative results show that Si doping can enhance polymerization and Al doping results in an increase in the ordered carbon clusters. Si and Al co-doping into polymeric films leads to the formation of an unusual dual nanostructure consisting of cross-linked polymer-like hydrocarbon chains and fullerene-like carbon clusters. The super-high elasticity and super-low friction coefficients (<0.002) under a high vacuum were obtained through Si and Al co-doping into the films. Unconventionally, the co-doped polymeric films exhibited a superior wear resistance even though they were very soft. The relationship between the microstructure and properties of the polymeric amorphous carbon films with different elements doping are also discussed in detail.

Optical Properties of the Self-Assembling Polymeric Colloidal Systems

Directory of Open Access Journals (Sweden)

Alexandra Mocanu

2013-01-01

Full Text Available In the last decade, optical materials have gained much interest due to the high number of possible applications involving path or intensity control and filtering of light. The continuous emerging technology in the field of electrooptical devices or medical applications allowed the development of new innovative cost effective processes to obtain optical materials suited for future applications such as hybrid/polymeric solar cells, lasers, polymeric optical fibers, and chemo- and biosensing devices. Considering the above, the aim of this review is to present recent studies in the field of photonic crystals involving the use of polymeric materials.

Smart polymeric materials in forms of fiber and film

International Nuclear Information System (INIS)

Sugo, Takanobu

1998-01-01

Chemical grafting: graft polymerization is a powerful technology to append novel functionality to base fibers, clothes, felts, films and others, while maintaining their original properties. As shown in Figure 1, while a gardener may use a pair of shears to cut the branch, to cut the molecular branch of a polymeric material, one can utilize the radiation energy. Effective utilization of the radiation energy can proceed to a novel reaction that is impossible for other conventional methods and develop a new material bearing outstanding functions. This technology is named radiation-induced graft polymerization (RIGP). In this article, the present research and development of novel functional polymeric materials by radiation-induced graft polymerization is described. The felt of intertwined fibers has been widely used as a filter to remove particles from air but not toxic gaseous compounds. However, by RIGP, one can transform the felt into a high functional filter that will absorb the toxic gaseous compounds while removing particles simultaneously. As a result, the RIGP technology, which is impossible by conventional technology, has enabled the development of a novel functional material that produce highly pure air. Commercialization of this filter for applications in a semiconductor manufacturing facility and as an air purifier is under process. Moreover, this filter can also be used to produce highly purified water by removing toxic heavy metals. Commercially available polyethylene films are also been transform into conductive separators by RIGP to increase the lifetime of a battery by more than five-fold. (J.P.N)

Applied bioactive polymeric materials

CERN Document Server

Carraher, Charles; Foster, Van

1988-01-01

The biological and biomedical applications of polymeric materials have increased greatly in the past few years. This book will detail some, but not all, of these recent developments. There would not be enough space in this book to cover, even lightly, all of the major advances that have occurred. Some earlier books and summaries are available by two of this book's Editors (Gebelein & Carraher) and these should be consul ted for additional information. The books are: "Bioactive Polymeric Systems" (Plenum, 1985); "Polymeric Materials In Medication" (Plenum, 1985); "Biological Acti vi ties of Polymers" (American Chemical Society, 1982). Of these three, "Bioacti ve Polymeric Systems" should be the most useful to a person who is new to this field because it only contains review articles written at an introductory level. The present book primarily consists of recent research results and applications, with only a few review or summary articles. Bioactive polymeric materials have existed from the creation of life...

Optical Fiber Sensors Based on Polymeric Sensitive Coatings

Directory of Open Access Journals (Sweden)

Pedro J. Rivero

2018-03-01

Full Text Available Polymer technology is one of the fastest growing fields of contemporary research due to the possibility of using a wide variety of synthetic chemical routes for obtaining a polymeric network with a well-defined structure, resulting in materials with outstanding macroscopic properties. Surface engineering techniques based on the implementation of polymeric structures can be used as an interesting tool for the design of materials with functional properties. In this sense, the use of fabrication techniques for the design of nanostructured polymeric coatings is showing an important growth due to the intrinsic advantages of controlling the structure at a nanoscale level because physical, chemical, or optical properties can be considerably improved in comparison with the bulk materials. In addition, the presence of these sensitive polymeric coatings on optical fiber is a hot topic in the scientific community for its implementation in different market niches because a wide variety of parameters can be perfectly measured with a high selectivity, sensitivity, and fast response time. In this work, the two main roles that a polymeric sensitive matrix can play on an optical fiber for sensing applications are evaluated. In a first section, the polymers are used as a solid support for the immobilization of specific sensitive element, whereas in the second section the polymeric matrix is used as the chemical transducer itself. Additionally, potential applications of the optical fiber sensors in fields as diverse as biology, chemistry, engineering, environmental, industry or medicine will be presented in concordance with these two main roles of the polymeric sensitive matrices.

Polymerization of Methyl Methacrylate with Samarocene Complex Supported on Mesoporous Silica

Institute of Scientific and Technical Information of China (English)

无

2001-01-01

Samarocene complex was supported on a series of mesoporous silica with various pore sizes. Polymerization of methyl methacrylate (MMA) by these catalysts provide highly syndiotactic PMMAs with higher molecular weights compared with those obtained by solution polymerization with homogeneous catalyst system.

"Click" i polymerer 2

DEFF Research Database (Denmark)

Hvilsted, Søren

2012-01-01

"Click"-reaktioner til fremstilling af ledende polymerer med funktionelle håndtag og bipolymermaterialer......"Click"-reaktioner til fremstilling af ledende polymerer med funktionelle håndtag og bipolymermaterialer...

Survey and research on precision polymerization polymeric materials; Seimitsu jugo kobunshi zairyo ni kansuru chosa kenkyu

Energy Technology Data Exchange (ETDEWEB)

NONE

1996-03-01

Survey and research on the precision control of primary structure of polymeric materials and the precision evaluation technology have been conducted to develop advanced polymeric materials. It is proposed that the three basic processes of polymer synthesis, i.e., addition, condensation, and biomimesis, in forming the precision polymerization skeleton are to be covered through a centralized joint research effort with participation of industry, academia, and the government institute and under the leadership of researchers from academic institutions as the team leaders. For the study of technology trends, international conferences held in UK, Germany, and Hawaii are introduced, and domestic meetings, i.e., Annual Polymer Congress and Polymer Conference, are summarized. In addition, Precision Polymerization Forum and International Workshop on Precision Polymerization were held. The basic studies include a quantum-chemical elucidation of the elementary process in polymerization reaction, time-resolved analysis of polymerization process and polymer properties, synthesis of polymers with controlled microstructures by coordination polymerization using metal complexes, synthesis of polymer with controlled microstructures by precision polycondensation, molecular recognition in catalyst-reaction site, and synthesis of imprinting polymers. 246 refs., 117 figs., 14 tabs.

13C Kinetic isotopic effect of polymerization on monomers with multiple bond

International Nuclear Information System (INIS)

Berman, E.L.; Polyakov, V.B.; Makovetskij, K.L.; Golenko, T.G.; Galimov, Eh.M.; AN SSSR, Moscow. Inst. Organicheskoj Khimii; AN SSSR, Moscow. Inst. Geokhimii i Analiticheskoj Khimii)

1988-01-01

13 C kinetic isotopic effect (KIE) of anionic and radical polymerization and metathesis reaction of monomers with multiple bonds are studied and correlation between the found KIE values of polymerization and the structure of transition state is established. 13 C KIE of polymerization reactions are investigated using monomers with natural content of the isotope. Polymerization was carried out using high-vacuum equipment: radical polymerization of methyl acrylate (MA) and vinyl acetate in benzene solution under the effect of benzoyl peroxide (60 deg C); anionic polymerization of MA, initiated by potassium butyl cellosolvolate, was realized in mass at 25 deg C; cyclopentene metathesis reaction was conducted in benzene under the effect of initiating system WCl 6 - (C 3 H 5 ) 2 Si(CH 3 ) 2 at -30 deg C; phenylacetylene polymers were prepared by polymerization in benzene solution at 20 deg C under the effect of WCl 6 . It is ascertained that 13 C KIE of radical and anionic polymerization of olefins and cycloolefin metathesis constitutes 2.0 -2.4%. Polymerization of compound with ternary bond is accompanied by a lower value of 13 C KIE (<1%), which is explained by double bond of reacting bond in transition state

X-ray initiated polymerization of wood impregnants

Energy Technology Data Exchange (ETDEWEB)

Cleland, Marshall R.; Galloway, Richard A. [IBA Industrial, Inc., Edgewood, NY (United States); Berejka, Anthony J. [Ionicorp, Huntington, NY 11743 (United States)], E-mail: berejka@msn.com; Montoney, Daniel [Strathmore Products, Syracuse, NY (United States); Driscoll, Mark; Smith, Leonard; Scott Larsen, L. [State University of New York, SUNY-ESF, Syracuse, NY (United States)

2009-07-15

X-rays, derived from a high energy, high-current electron beam (EB), initiated in-situ polymerization of a unique class of monomers that were found to penetrate the cell walls of wood. X-rays initiated an auto-catalytic acrylic polymerization and penetrated through thick pieces of wood. The final cured product having the polymerizate, a polymer, both in the wood cell lumens and in the cell walls is called wood impregnated with a wood-polymer penetrant (WPP). The controlled lower dose rate of X-rays overcame disproportionation encountered when using higher dose-rate electron beam initiation. With X-rays, the in-situ polymerization took place in one exposure of modest dose. With EB, multiple passes were needed to avoid excessive heat build-up and monomer volatilization. Having entered the cell walls of the wood and then being polymerized within the cell walls, these radiation-cured unique monomers imparted outstanding dimensional stability upon exposure of the impregnated wood to humidity cycling. The preferred monomer system was also chemically modified prior to impregnation with agents that would remain in the wood and prevent the growth of fungi and other microbials. This technique differs from historic uses of monomers that merely filled the lumens of the wood (historic wood-polymer composites), which are only suitable for indoor use. The WPP impregnated wood that was either X-ray cured or EB cured demonstrated enhanced structural properties, dimensional stability, and decay resistance.

X-ray initiated polymerization of wood impregnants

International Nuclear Information System (INIS)

Cleland, Marshall R.; Galloway, Richard A.; Berejka, Anthony J.; Montoney, Daniel; Driscoll, Mark; Smith, Leonard; Scott Larsen, L.

2009-01-01

X-rays, derived from a high energy, high-current electron beam (EB), initiated in-situ polymerization of a unique class of monomers that were found to penetrate the cell walls of wood. X-rays initiated an auto-catalytic acrylic polymerization and penetrated through thick pieces of wood. The final cured product having the polymerizate, a polymer, both in the wood cell lumens and in the cell walls is called wood impregnated with a wood-polymer penetrant (WPP). The controlled lower dose rate of X-rays overcame disproportionation encountered when using higher dose-rate electron beam initiation. With X-rays, the in-situ polymerization took place in one exposure of modest dose. With EB, multiple passes were needed to avoid excessive heat build-up and monomer volatilization. Having entered the cell walls of the wood and then being polymerized within the cell walls, these radiation-cured unique monomers imparted outstanding dimensional stability upon exposure of the impregnated wood to humidity cycling. The preferred monomer system was also chemically modified prior to impregnation with agents that would remain in the wood and prevent the growth of fungi and other microbials. This technique differs from historic uses of monomers that merely filled the lumens of the wood (historic wood-polymer composites), which are only suitable for indoor use. The WPP impregnated wood that was either X-ray cured or EB cured demonstrated enhanced structural properties, dimensional stability, and decay resistance.

High monomer content batch microemulsion polymerization of butyl acrylate initiated with gamma ray

Energy Technology Data Exchange (ETDEWEB)

Chen Jun [Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026 (China)]. E-mail: chjun04@mail.ustc.edu.cn; Zhang Zhicheng [Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026 (China)]. E-mail: zczhang@ustc.edu.cn

2007-05-15

Radiation polymerization of butyl acrylate was performed in a microemulsion stabilized with a mixture of sodium of 12-acryloxy-9-octadecenoic acid and sodium dodecyl sulfate in a weight ratio of 2 at room temperature. BA content in microemulsion can be successfully improved up to 40 wt% with low surfactant concentration (lower than 10 wt%). The resulted stable, translucent microlatex contain particles with average diameter from 28.1 to 38.1 nm with different monomer content. Particle size depends on the dose rate and surfactant concentration. Effects of monomer content and dose rate on the maximum polymerization rate are discussed.

Study of radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. VIII. Polymerization of styrene and methyl methacrylate adsorbed on aerosil

International Nuclear Information System (INIS)

Fukano, K.; Kageyama, E.

1976-01-01

Aerosol is silica having a purity which is very high compared with that of silica gel and having, unlike silica gel, no micropores. To investigate the effects of impurities and micropores on the radiation-induced polymerization of styrene and methyl methacrylate adsorbed on silica gel, the radiation-induced polymerization of styrene and methyl methacrylate adsorbed on Aerosil was carried out. The results of both the styrene--Aerosil 300 system and the methyl methacrylate--Aerosil 300 system were similar to those of the styrene-silica gel and methyl methacrylate-silica gel systems, respectively. This suggests that in the radiation-induced polymerization of both styrene--silica gel and methyl methacrylate--silica gel systems the impurities and the presence of micropores have almost no effect on the reaction mechanism. The effect of aluminum as an impurity was investigated on the styrene--Aerosil MOX 170 system. It was found that aluminum accelerated the cationic polymerization

Kinetic advantages of using microwaves in the emulsion polymerization of MMA

Energy Technology Data Exchange (ETDEWEB)

Costa, C. [Departamento de Engenharia Quimica, Universidade Federal de Santa Catarina, Campus Universitario, CEP: 88040-900, Florianopolis, SC (Brazil); Santos, A.F.; Fortuny, M. [Programa de Mestrado em Engenharia de Processos, Universidade Tiradentes, Instituto de Tecnologia e Pesquisa, Av. Murilo Dantas, 300, CEP: 49032-490, Aracaju, SE (Brazil); Araujo, P.H.H. [Departamento de Engenharia Quimica, Universidade Federal de Santa Catarina, Campus Universitario, CEP: 88040-900, Florianopolis, SC (Brazil); Sayer, C. [Departamento de Engenharia Quimica, Universidade Federal de Santa Catarina, Campus Universitario, CEP: 88040-900, Florianopolis, SC (Brazil)], E-mail: csayer@enq.ufsc.br

2009-03-01

Microwave irradiation has been an interesting alternative for heating systems and several chemical reactions. In polymerization processes, microwaves can enhance reaction rates or improve specific characteristics of the formed polymer. In this work, the use of microwave irradiation in emulsion polymerization reactions has been studied, using a commercial microwave reactor, which is able to perform syntheses under controlled conditions of temperature and power. Methyl methacrylate emulsion polymerization reactions were faster, resulting in smaller polymer particles, in comparison to the conventional heating method (reactions in a jacketed reactor). Different effects were observed in the emulsion polymerization of butyl acrylate. To study the effect of high power microwave irradiation upon the emulsion polymerization, a pulsed irradiation strategy was developed, in which the samples were repeatedly heated within short intervals of time (about 27 s) at the maximum microwave power. A significant reduction of the total time of irradiation was observed in reactions carried out under the pulsed scheme, showing the kinetic advantages of using microwaves in emulsion polymerization processes.

Synthesis of magnetic polymeric microspheres

Energy Technology Data Exchange (ETDEWEB)

Gervald, A Yu; Gritskova, Inessa A; Prokopov, Nikolai I [M.V. Lomonosov Moscow State Academy of Fine Chemical Technology, Moscow (Russian Federation)

2010-05-13

The key types of magnetic polymeric microspheres are considered. Methods of synthesis of different types of magnetic nanoparticles and of preparation of stable magnetic fluids on their basis are outlined. The overview of the methods for the manufacture of magnetic polymeric microspheres is presented. The effect of the synthesis conditions on the characteristics of magnetic polymeric microspheres such as the diameter and the particle size distribution and the content of magnetic material is discussed by particular examples. The application fields of magnetic polymeric microspheres are briefly surveyed.

Synthesis of magnetic polymeric microspheres

International Nuclear Information System (INIS)

Gervald, A Yu; Gritskova, Inessa A; Prokopov, Nikolai I

2010-01-01

The key types of magnetic polymeric microspheres are considered. Methods of synthesis of different types of magnetic nanoparticles and of preparation of stable magnetic fluids on their basis are outlined. The overview of the methods for the manufacture of magnetic polymeric microspheres is presented. The effect of the synthesis conditions on the characteristics of magnetic polymeric microspheres such as the diameter and the particle size distribution and the content of magnetic material is discussed by particular examples. The application fields of magnetic polymeric microspheres are briefly surveyed.

Novel polymer coatings based on plasma polymerized 2-methoxyethyl acrylate

DEFF Research Database (Denmark)

Wu, Zhenning; Jiang, Juan; Benter, Maike

2008-01-01

plasma system[4]. The system named SoftPlasma™ is equipped with unique three-phase pulsed AC voltage. Low energy plasma polymerization has almost no thermal load for sensitive polymer materials[5]. Plasma polymerized coatings are highly cross-linked, pin-hole free and provide hydrophilic or hydrophobic...... properties[4-6]. We have exploited these possibilities and prepared plasma polymerized 2-methoxyethyl acrylate (PPMEA) coatings on various polymer substrates. The PPMEA coatings were optimized using various plasma polymerization conditions and characterized by X-ray photoelectron spectroscopy......, Fouriertransform infrared spectroscopy, Atomic force spectroscopy and Water contact-angle measurements. The microstructures ofPPMEA coatings with different thicknesses were also studied. For practical applications in mind, the coating stability was tested in different media (air, water, acetone, phosphate...

NATO Advanced Study Institute on Ring-opening Metathesis Polymerization of Olefins and Polymerization of Alkynes

CERN Document Server

1998-01-01

The first NATO Advanced Study Institute on Olefin Metathesis and Polymerization Catalysts was held on September 10-22, 1989 in Akcay, Turkey. Based on the fundamental research of RRSchrock, RGrubbs and K.B.Wagener in the field of ring opening metathesis polymerization (ROMP), acyclic diene metathesis (ADMET) and alkyne polymerization, these areas gained growing interest within the last years. Therefore the second NATO-ASI held on metathesis reactions was on Ring Opening Metathesis Po­ lymerization of Olefins and Polymerization of Alkynes on September 3-16, 1995 in Akcay, Turkey. The course joined inorganic, organic and polymer chemists to exchange their knowledge in this field. This volume contains the main and short lectures held in Akcay. To include ADMET reactions better into the title of this volume we changed it into: Metathesis Polymerization of Olefins and Alkyne Polymerization. This volume is addressed to research scientists, but also to those who start to work in the area of olefin metathesis and al...

Recent advances on polymeric membranes for membrane reactors

KAUST Repository

Buonomenna, M. G.

2012-06-24

Membrane reactors are generally applied in high temperature reactions (>400 °C). In the field of fine chemical synthesis, however, much milder conditions are generally applicable and polymeric membranes were applied without their damage. The successful use of membranes in membrane reactors is primary the result of two developments concerning: (i) membrane materials and (ii) membrane structures. The selection of a suited material and preparation technique depends on the application the membrane is to be used in. In this chapter a review of up to date literature about polymers and configuration catalyst/ membranes used in some recent polymeric membrane reactors is given. The new emerging concept of polymeric microcapsules as catalytic microreactors has been proposed. © 2012 Bentham Science Publishers. All rights reserved.

Reactive surfactants in heterophase polymerization

NARCIS (Netherlands)

Guyot, A.; Tauer, K.; Asua, J.M.; Es, van J.J.G.S.; Gauthier, C.; Hellgren, A.C.; Sherrington, D.C.; Montoya-Goni, A.; Sjöberg, M.; Sindt, O.; Vidal, F.F.M.; Unzue, M.; Schoonbrood, H.A.S.; Schipper, E.T.W.M.; Lacroix-Desmazes, P.

1999-01-01

This paper summarizes the work carried out during 3 years in a Network of the program "Human Capital and Mobility" of the European Union CHRX 93-0159 entitled "Reactive surfactants in heterophase polymerization for high performance polymers". A series of about 25 original papers will be published in

RAFT polymerization mediated bioconjugation strategies

OpenAIRE

Bulmuş, Volga

2011-01-01

This review aims to highlight the use of RAFT polymerization in the synthesis of polymer bioconjugates. It covers two main bioconjugation strategies using the RAFT process: (i) post-polymerization bioconjugations using pre-synthesized reactive polymers, and (ii) bioconjugations via in situ polymerization using biomolecule-modified monomers or chain transfer agents. © 2011 The Royal Society of Chemistry.

Polymerization of methyl methacrylate by diphenylamido bis (methylcyclopentadienyl) ytterbium complex

Institute of Scientific and Technical Information of China (English)

WANG, Yao-Rong(王耀荣); SHEN, Qi(沈琪); MA, Jia-Le(马家乐); ZHAO, Qun(赵群)

2000-01-01

Methyl methacrylate (MMA) was effectively polymerized by diphenylamido bis(methyicyclopentadienyl) ytterbium complex (MeCp)2YbNPh2(THF). Tne reaction can be carried out over a range of polymerization temperature from - 40℃ to 40℃ and gives the polyMMA with high molecular weights.The initiation mechanism was demonstrated by diphenylamidoterminated methyl methacrylate oligomer.

Optical investigations of various polymeric materials used in dental technology

Science.gov (United States)

Negrutiu, Meda Lavinia; Sinescu, Cosmin; Topala, Florin Ionel; Ionita, Ciprian; Goguta, Luciana; Marcauteanu, Corina; Rominu, Mihai; Podoleanu, Adrian Gh.

2011-10-01

Dental prosthetic restorations have to satisfy high stress as well as aesthetic requirements. In order to avoid deficiencies of dental prostheses, several alternative systems and procedures were imagined, directly related to the material used and also to the manufacturing technology. Increasing the biomechanical comportment of polymeric materials implies fiber reinforcing. The different fibers reinforcing products made very difficult the evaluation of their performances and biomechanical properties analysis. There are several known methods which are used to assess the quality of dental prostheses, but most are invasive. These lead to the destruction of the samples and often no conclusion could be drawn in the investigated areas of interest. Using a time domain en-face OCT system, we have recently demonstrated real time thorough evaluation of quality of various dental treatments. The aim of this study was to assess the quality of various polymeric materials used in dental technology and to validate the en face OCT imagistic evaluation of polymeric dental prostheses by using scanning electron microscopy (SEM) and microcomputer tomography (μCT). SEM investigations evidenced the nonlinear aspect of the interface between the polymeric material and the fiber reinforcement and materials defects in some samples. The results obtained by microCT revealed also some defects inside the polymeric materials and at the interfaces with the fiber reinforcement. The advantages of the OCT method consist in non-invasiveness and high resolution. In addition, en face OCT investigations permit visualization of the more complex stratified structure at the interface between the polymeric material and the fiber reinforcement.

Nanoparticles with high payloads of pipemidic acid, a poorly soluble crystalline drug: drug-initiated polymerization and self-assembly approach

Directory of Open Access Journals (Sweden)

Elisabetta Pancani

2018-05-01

Full Text Available Nowadays, biodegradable polymers such as poly(lactic acid (PLA, poly(D,L-lactic-co-glycolic acid (PLGA and poly(ε-caprolactone (PCL remain the most common biomaterials to produce drug-loaded nanoparticles (NPs. Pipemidic acid (PIP is a poorly soluble antibiotic with a strong tendency to crystallize. PIP incorporation in PLA/PLGA NPs was challenging because of PIP crystals formation and burst release. As PIP had a poor affinity for the NPs, an alternative approach to encapsulation was used, consisting in coupling PIP to PCL. Thus, a PCL–PIP conjugate was successfully synthesized by an original drug-initiated polymerization in a single step without the need of catalyst. PCL–PIP was characterized by NMR, IR, SEC and mass spectrometry. PCL–PIP was used to prepare self-assembled NPs with PIP contents as high as 27% (w/w. The NPs were characterized by microscopy, DLS, NTA and TRPS. This study paves the way towards the production of NPs with high antibiotic payloads by drug-initiated polymerization. Further studies will deal with the synthesis of novel polymer–PIP conjugates with ester bonds between the drug and PCL. PIP can be considered as a model drug and the strategy developed here could be extended to other challenging antibiotics or anticancer drugs and employed to efficiently incorporate them in NPs. KEY WORDS: Pipemidic acid, Nanoparticle, Antibiotic, Nanoprecipitation, Crystalline drug, Drug-initiated   polymerization

Surface science of single-site heterogeneous olefin polymerization catalysts

OpenAIRE

Kim, Seong H.; Somorjai, Gabor A.

2006-01-01

This article reviews the surface science of the heterogeneous olefin polymerization catalysts. The specific focus is on how to prepare and characterize stereochemically specific heterogeneous model catalysts for the Ziegler–Natta polymerization. Under clean, ultra-high vacuum conditions, low-energy electron irradiation during the chemical vapor deposition of model Ziegler–Natta catalysts can be used to create a “single-site” catalyst film with a surface structure that produces only isotactic ...

Controlling the Plasma-Polymerization Process of N-Vinyl-2-pyrrolidone

DEFF Research Database (Denmark)

Norrman, Kion; Winther-Jensen, Bjørn

2005-01-01

N-vinyl-2-pyrrolidone was plasma-polymerized on glass substrates using a pulsed AC plasma. Pulsed AC plasma produces a chemical surface structure different from that produced by conventional RF plasma; this is ascribed to the different power regimes used. A high degree of control over the structure...... of the chemical surface was obtained using pulsed AC plasma, as shown by ToF-SIMS. It is demonstrated how the experimental conditions to some extent control the chemical structure of the plasma-polymerized film, e.g., film thickness, density of post-plasma-polymerized oligomeric chains, and the density of intact...

Decay Time Measurement for Different Energy Depositions of Plastic Scintillator Fabricated by High Temperature Polymerization Reaction

Energy Technology Data Exchange (ETDEWEB)

Lee, Cheol Ho; Son, Jaebum; Lee, Sangmin; Kim, Tae Hoon; Kim, Yong-Kyun [Hanyang University, Seoul (Korea, Republic of)

2016-10-15

Plastic scintillators are based on organic fluorite. They have many advantages such as fast rise and decay time, high optical transmission, ease of manufacturing, low cost, and large available size. For these reasons they are widely used for particle identification. Also, protection of people against a variety of threats (such as nuclear, radiological, and explosive) represents a true challenge along with the continuing development of science and technology. The plastic scintillator is widely used in various devise, which serves for nuclear, photonics, quantum, and high-energy physics. The plastic scintillator is probably the most widely used organic detector, and polystyrene is one of the most widely used materials in the making of the plastic scintillator detector. Thus, a styrene monomer as a solvent was used to fabricate the plastic scintillator by using high temperature polymerization reaction, and then the emission wavelength and the decay times for different energy depositions were measured by using the fabricated plastic scintillator. A plastic scintillator was fabricated to measure decay time for different energy depositions using the high temperature polymerization. Emission wavelength was measured of 426.05 nm to confirm a scintillator property using the spectrophotometer. Four gamma-ray sources (Cs-137, Co-60, Na-22, and Ba-133) were used to evaluate effect for decay time of different energy depositions. The average decay time of the fabricated plastic scintillator was measured to approximately 4.72 ns slightly higher more than commercial plastic scintillator. In future, light output and linearity will be measured to evaluate other property compared with the commercial scintillator.

Decay Time Measurement for Different Energy Depositions of Plastic Scintillator Fabricated by High Temperature Polymerization Reaction

International Nuclear Information System (INIS)

Lee, Cheol Ho; Son, Jaebum; Lee, Sangmin; Kim, Tae Hoon; Kim, Yong-Kyun

2016-01-01

Plastic scintillators are based on organic fluorite. They have many advantages such as fast rise and decay time, high optical transmission, ease of manufacturing, low cost, and large available size. For these reasons they are widely used for particle identification. Also, protection of people against a variety of threats (such as nuclear, radiological, and explosive) represents a true challenge along with the continuing development of science and technology. The plastic scintillator is widely used in various devise, which serves for nuclear, photonics, quantum, and high-energy physics. The plastic scintillator is probably the most widely used organic detector, and polystyrene is one of the most widely used materials in the making of the plastic scintillator detector. Thus, a styrene monomer as a solvent was used to fabricate the plastic scintillator by using high temperature polymerization reaction, and then the emission wavelength and the decay times for different energy depositions were measured by using the fabricated plastic scintillator. A plastic scintillator was fabricated to measure decay time for different energy depositions using the high temperature polymerization. Emission wavelength was measured of 426.05 nm to confirm a scintillator property using the spectrophotometer. Four gamma-ray sources (Cs-137, Co-60, Na-22, and Ba-133) were used to evaluate effect for decay time of different energy depositions. The average decay time of the fabricated plastic scintillator was measured to approximately 4.72 ns slightly higher more than commercial plastic scintillator. In future, light output and linearity will be measured to evaluate other property compared with the commercial scintillator

The role of hydroperoxides as a precursor in the radiation-induced graft polymerization of methyl methacrylate to ultra-high molecular weight polyethylene

Energy Technology Data Exchange (ETDEWEB)

Enomoto, Ichiro, E-mail: enomoto.ichiro@iri-tokyo.j [Tokyo Metropolitan Industrial Technology Research Institute, KFC bldg., 12F, 1-6-1, Yokoami, Sumida-ku, Tokyo 130-0015 (Japan); School of Engineering, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Katsumura, Yosuke [School of Engineering, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Advanced Science Research Center, Japan Atomic Energy Agency, 2-4 Shirakata Shirane, Tokai-mura, Ibaraki 319-1195 (Japan); Kudo, Hisaaki [School of Engineering, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Sekiguchi, Masayuki [Tokyo Metropolitan Industrial Technology Research Institute, KFC bldg., 12F, 1-6-1, Yokoami, Sumida-ku, Tokyo 130-0015 (Japan)

2010-06-15

A graft polymerization of methyl methacrylate (MMA) to ultra-high molecular weight polyethylene (UHMWPE) with Co-60 gamma-ray irradiation in air at room temperature has been carried out. The grafting yields were measured as a function of the storage time (elapsed time from the end of irradiation to the start of grafting), and it was found that the yields reach at the maximum values at around several days since the end of irradiation. In order to clarify the precursor of the graft polymerization, changes of the radical yields and the carbonyl groups were measured as a function of storage time with ESR and microscopic FT-IR, respectively. From the similarities between the depth profiles of the hydroperoxide formation and the grafting products, it was concluded that the hydroperoxides can be main precursors of the grafting of the radiation-induced polymerization of MMA to UHMWPE under the given conditions.

The role of hydroperoxides as a precursor in the radiation-induced graft polymerization of methyl methacrylate to ultra-high molecular weight polyethylene

International Nuclear Information System (INIS)

Enomoto, Ichiro; Katsumura, Yosuke; Kudo, Hisaaki; Sekiguchi, Masayuki

2010-01-01

A graft polymerization of methyl methacrylate (MMA) to ultra-high molecular weight polyethylene (UHMWPE) with Co-60 γ-ray irradiation in air at room temperature has been carried out. The grafting yields were measured as a function of the storage time (elapsed time from the end of irradiation to the start of grafting), and it was found that the yields reach at the maximum values at around several days since the end of irradiation. In order to clarify the precursor of the graft polymerization, changes of the radical yields and the carbonyl groups were measured as a function of storage time with ESR and microscopic FT-IR, respectively. From the similarities between the depth profiles of the hydroperoxide formation and the grafting products, it was concluded that the hydroperoxides can be main precursors of the grafting of the radiation-induced polymerization of MMA to UHMWPE under the given conditions.

Polymerization of 5-alkyl δ-lactones catalyzed by diphenyl phosphate and their sequential organocatalytic polymerization with monosubstituted epoxides

KAUST Repository

Zhao, Junpeng

2015-02-04

Organocatalytic ring-opening polymerization (ROP) reactions of three renewable 5-alkyl δ-lactones, namely δ-hexalactone (HL), δ-nonalactone (NL) and δ-decalactone (DL), using diphenyl phosphate (DPP) were investigated. Room temperature, together with a relatively high monomer concentration (≥3 M), was demonstrated to be suitable for achieving a living ROP behavior, a high conversion of the lactone, a controlled molecular weight and a low dispersity of the polyester. HL, containing a 5-methyl substituent, showed a much higher reactivity (polymerization rate) and a slightly higher equilibrium conversion than the compounds with longer alkyl substituents (NL and DL). The effectiveness of DPP-catalyzed ROP of 5-alkyl δ-lactones facilitated the one-pot performance following the t-BuP4-promoted ROP of monosubstituted epoxides. It has been shown in an earlier study that substituted polyethers acted as "slow initiators" for non-substituted lactones. However, efficient initiations were observed in the present study as substituted lactones were polymerized from the substituted polyethers. Therefore, this reinforces the previously developed "catalyst switch" strategy, making it a more versatile tool for the synthesis of well-defined polyether-polyester block copolymers from a large variety of epoxide and lactone monomers. © The Royal Society of Chemistry 2015.

A simple method for determining polymeric IgA-containing immune complexes.

Science.gov (United States)

Sancho, J; Egido, J; González, E

1983-06-10

A simplified assay to measure polymeric IgA-immune complexes in biological fluids is described. The assay is based upon the specific binding of a secretory component for polymeric IgA. In the first step, multimeric IgA (monomeric and polymeric) immune complexes are determined by the standard Raji cell assay. Secondly, labeled secretory component added to the assay is bound to polymeric IgA-immune complexes previously fixed to Raji cells, but not to monomeric IgA immune complexes. To avoid false positives due to possible complement-fixing IgM immune complexes, prior IgM immunoadsorption is performed. Using anti-IgM antiserum coupled to CNBr-activated Sepharose 4B this step is not time-consuming. Polymeric IgA has a low affinity constant and binds weakly to Raji cells, as Scatchard analysis of the data shows. Thus, polymeric IgA immune complexes do not bind to Raji cells directly through Fc receptors, but through complement breakdown products, as with IgG-immune complexes. Using this method, we have been successful in detecting specific polymeric-IgA immune complexes in patients with IgA nephropathy (Berger's disease) and alcoholic liver disease, as well as in normal subjects after meals of high protein content. This new, simple, rapid and reproducible assay might help to study the physiopathological role of polymeric IgA immune complexes in humans and animals.

In situ polymerization of monomers for polyphenylquinoxaline/graphite fiber composites

Science.gov (United States)

Serafini, T. T.; Delvigs, P.; Vannucci, R. D.

1974-01-01

Methods currently used to prepare fiber reinforced, high temperature resistant polyphenylquinoxaline (PPQ) composites employ extremely viscous, low solids content solutions of high molecular weight PPQ polymers. An improved approach, described in this report, consists of impregnating the fiber with a solution of the appropriate monomers instead of a solution of previously synthesized high molecular weight polymer. Polymerization of the monomers occurs in situ on the fiber during the solvent removal and curing stages. The in situ polymerization approach greatly simplifies the fabrication of PPQ graphite fiber composites. The use of low viscosity monomeric type solutions facilitates fiber wetting, permits a high solids content, and eliminates the need for prior polymer synthesis.

In situ polymerization of vinyl monomers in polyester yarns

International Nuclear Information System (INIS)

Avny, Y.; Rebenfeld, L.; Weigmann, H.D.

1978-01-01

The effects of a pretreatment of polyester (PET) yarns with a strongly interacting solvent such as dimethylformamide (DMF) on vinyl monomer incorporation were investigated. When the DMF pretreatment is carried out at high temperatures (above 120 0 C), the swollen PET structure is stabilized by solvent-induced secondary crystallization. This substrate is highly suitable for the incorporation of vinyl monomers. In situ polymerization of vinyl monomers in DMF-treated PET was investigated using chemical and γ-irradiation polymerization techniques, both in the presence and in the absence of excess monomer outside the PET fibers. When polymerization was carried out in a system in which a constant supply of free radicals was available from the outside of the PET fibers, lower initiator concentrations and smaller γ-irradiation doses were necessary. These results are attributed to a low efficiency of the initiator inside the PET fiber due to mobility restrictions. Water uptake and moisture regain of PET yarns containing poly(hydroxyethyl methacrylate) and poly(acrylic acid) were also investigated. When most of the vinyl polymer was inside the PET fiber, water absorption was limited. The changes in mechanical properties of the PET yarns resulting from the DMF pretreatment were partially reversed by in situ polymerization of vinyl monomers

GAMMA RADIATION INITIATED POLYMERIZATION OF FLUOROMONOMERS. II. COPOLYMER OF CHLOROTRIFLUOROETHYLENE AND ETHYLENE

Energy Technology Data Exchange (ETDEWEB)

Manno, P. J.

1963-06-15

The radioinduced copolymerization of chlorotrifluoro ethylene and ethylene was studied. The polymerization rate increased with time and radiation intensity, and the Gvalues after 50% polymerization varied from 13,000 at 10/sup 5/ rep/hr to 25,000 at 6 x 10/sup 3/ rep/hr. The polymerization rate is proportional to the 0.7 or 0.8th power of the radiation intensity. The polymerization reaction is highly exothermic, and the optimum conditions for the best polymer properties occurred in a stirred autoclave cooled to 0 deg C containing a monomer-- water mixture and irradiated at 10/sup 4/ rep/hr. Catalytic polymerization was also studied, and the economics of or the preparation of the copolymer by catalytic and radiation processes is discussed briefly. (D.L.C.)

Chelating polymeric membranes

KAUST Repository

Peinemann, Klaus-Viktor

2015-01-22

The present application offers a solution to the current problems associated with recovery and recycling of precious metals from scrap material, discard articles, and other items comprising one or more precious metals. The solution is premised on a microporous chelating polymeric membrane. Embodiments include, but are not limited to, microporous chelating polymeric membranes, device comprising the membranes, and methods of using and making the same.

Thermal polymerization of Moringa oleifera oil; Termopolimerizacao do oleo de Moringa oleifera

Energy Technology Data Exchange (ETDEWEB)

Melo, Tania M.S.; Novack, Katia M.; Leandro, Cristiano, E-mail: tania@iceb.ufop.br [Departamento de Quimica - UFOP, Campus Morro do Cruzeiro, Ouro Preto, MG (Brazil)

2011-07-01

It is increasingly clear both for society and the scientific community, that is necessary to find alternatives to reduce the use of polymeric materials because of their damage to the environment. One way to minimize the environmental problems related to the use of polymers is try to make them quickly degradable. In this study it was obtained a material with polymeric appearance derived from heating of the vegetable oil extracted from seeds of Moringa oleifera. The resulting product is an interesting alternative to obtain polymeric materials that may have biodegradable characteristics, coming from a renewable source and low cost. Moringa oil can be used since it has a high content of unsaturated fatty acids, and its main constituent oleic acid. All samples were characterized by FTIR, NMR and GPC. It was obtained a polymeric material, malleable, high viscosity, with some elasticity, low crystallinity and no unpleasant odor. (author)

Functionalization and Polymerization on the CNT Surfaces

KAUST Repository

Albuerne, Julio

2013-07-01

In this review we focus on the current status of using carbon nanotube (CNT) as a filler for polymer nanocomposites. Starting with the historical background of CNT, its distinct properties and the surface functionalization of the nanotube, the three different surface polymerization techniques, namely grafting "from", "to" and "through/in between" were discussed. Wider focus has been given on "grafting from" surface initiated polymerizations, including atom transfer radical polymerization (ATRP), reversible addition fragmentation chain-transfer (RAFT) Polymerization, nitroxide mediated polymerization (NMP), ring opening polymerization (ROP) and other miscellaneous polymerization methods. The grafting "to" and "through / in between" also discussed and compared with grafting from polymerization. The merits and shortcomings of all three grafting methods were discussed and the bottleneck issue in grafting from method has been highlighted. Furthermore the current and potential future industrial applications were deliberated. Finally the toxicity issue of CNTs in the final product has been reviewed with the limited available literature knowledge. © 2013 Bentham Science Publishers.

Functional bio-based polyesters by enzymatic polymerization

DEFF Research Database (Denmark)

Daugaard, Anders Egede; Hoffmann, Christian; Andersen, Christian

During recent years enzymatic polymerization has become increasingly popular as an alternative to classical polyesterification processes. The high regioselectivity observed for lipases permits preparation of novel polyesters with a high number of functional groups.1 This is particularly interesting...... polymerization was applied to prepare functional water soluble polyesters based on dimethyl itaconate and poly(ethyleneglycol).2 The monomer permits postfunctionalization using thiol-ene chemistry or aza-michael additions, which was used to illustrate the possibilites of preparing functional hydrogels. Hydrogels...... based on the polyesters were shown to be degradable and could be prepared either from the pure polyester or from prefunctionalized polyesters, though the thiol-ene reactions were found to be less effective. Since then a new monomer, trans-2,5-dihydroxy-3-pentenoic acid methyl ester (DPM) has been...

The study of polymeric hydro-gels with unique properties obtained by polymerization with gamma radiation processing

International Nuclear Information System (INIS)

Dragusin, M.

1995-01-01

This thesis presents the work carried out on polymeric hydro-gels obtained by radiation processing using 60 Co gamma rays from the irradiation facility IETI-10.000 (10 k Ci), and on the polymeric hydro-gels obtained by irradiation with the electron beams from a linear accelerator (6 MeV). The aim of the study was to determine the effect of the rate dose and total dose absorbed in the materials. There are presented the preparation methods of homo- and co-polymer hydro-gels (acrylics, namely anionic and neutral monomers (acrylamide, acrylic acid, vinyl acetate) and cationic monomers (di-methyl di-allyl ammonium chloride)) such as floculants, additives, absorbers, etc. Concerning with these we have analysed the preparation methods, the mechanical, thermal, diffusivity, and swelling properties of polymeric hydro-gels in a large variety of gels of type I or II. The technological aspects and end use were studied in connection with the characteristics of the radiation processing of these hydro-gels as a function of chemical composition rate and absorbed dose, swelling degree (low and very high hydro-soluble), mechanical and diffusional properties. (author) 33 figs., 12 tabs., 101 refs

Porous polymeric membranes with thermal and solvent resistance

KAUST Repository

Pulido, Bruno

2017-05-30

Polymeric membranes are highly advantageous over their ceramic counterparts in terms of the simplicity of the manufacturing process, cost and scalability. Their main disadvantages are low stability at temperatures above 200 °C, and in organic solvents. We report for the first time porous polymeric membranes manufactured from poly(oxindolebiphenylylene) (POXI), a polymer with thermal stability as high as 500 °C in oxidative conditions. The membranes were prepared by solution casting and phase inversion by immersion in water. The asymmetric porous morphology was characterized by scanning electronic microscopy. The pristine membranes are stable in alcohols, acetone, acetonitrile and hexane, as well as in aqueous solutions with pH between 0 and 14. The membrane stability was extended for application in other organic solvents by crosslinking, using various dibromides, and the efficiency of the different crosslinkers was evaluated by thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). POXI crosslinked membranes are stable up to 329 °C in oxidative conditions and showed organic solvent resistance in polar aprotic solvents with 99% rejection of Red Direct 80 in DMF at 70 °C. With this development, the application of polymeric membranes could be extended to high temperature and harsh environments, fields currently dominated by ceramic membranes.

Platinum porphyrins as ionophores in polymeric membrane electrodes

DEFF Research Database (Denmark)

Lvova, Larisa; Verrelli, Giorgio; Nardis, Sara

2011-01-01

A comparative study of Pt(II)- and Pt(IV)-porphyrins as novel ionophores for anion-selective polymeric membrane electrodes is performed. Polymeric membranes of different compositions, prepared by varying plasticizers, cationic and anionic additives and Pt porphyrins, have been examined...... within the electrode membranes, while those based on Pt(IV)TPPCl2 operate via a mixed mode carrier mechanism, evidencing also a partial reduction of the starting ionophore to Pt(II)TPP. Spectrophotometric measurements of thin polymeric films indicate that no spontaneous formation of hydroxide ion bridged...... porphyrin dimers occurs in the membrane plasticized both with high or low dielectric constant plasticizer, due to a low oxophilicity of central Pt. The computational study of various anion–Pt(IV)TPPCl2 complex formation by means of semi-empirical and density functional theory (DFT) methods revealed a good...

Ferrocene-quinoxaline Y-shaped chromophores as fascinating second-order NLO building blocks for long lasting highly active SHG polymeric films.

Science.gov (United States)

Senthilkumar, Kabali; Thirumoorthy, Krishnan; Dragonetti, Claudia; Marinotto, Daniele; Righetto, Stefania; Colombo, Alessia; Haukka, Matti; Palanisami, Nallasamy

2016-07-26

The first example of a Y-shaped ferrocene quinoxaline derivative with a surprisingly high and stable second harmonic generation (SHG) response in composite polymeric films is reported. The interesting quadratic hyperpolarizability values of different substituted Y-shaped chromophores are also investigated in solution by the EFISH technique.

The use of radiation-induced graft polymerization for obtaining polymeric biomaterial on the basis of preparation 'Piyavit'

International Nuclear Information System (INIS)

Kudryavtsev, V.N.; Degtyareva, T.V.; Kabanov, V.Ya.

1998-01-01

The purpose of the present study is to obtain hemocompatible polymeric materials. The method of modification of polymer surface have been elaborated using the radiation-induced graft polymerization after which the surface is capable of coupling with the biologically active substances (BAS) produced from the medicinal leeches. At the Biological Department of Lomonosov Moscow State University was created a medicinal preparation 'Piyavit' isolated from the salivary glands secretion of the medicinal leeches (Hirudo medicinalis). It possess a wide spectrum of biological action on the human organism thanks to the presence of an unique complex natural of BAS (enzymes, inhibitors of proteolityc ensymes, prostanoids and et. al) guaranteed the anticoagulating, thrombolytic, antithrombotic, antiphlogistic, antiatherosclerotic, hypotentic effects and et al.. It has several advantages over anticoagulant heparin which is widely used for above mentioned purpose. 'Piyavit' is the multifunctional preparation, has not negative side-effects and is more cheap. The method of obtaining biocompatible polymers (basically polyethylene) with immobilized 'Piyavit' consist of three stages: 1. The modification of polymer surface by the radiation-induced graft polymerization of acrylic acid to obtain grafted chains polyacrylic acid (PAA) with controlled number and length. 2. The treatment of radiation grafted PAA by thionyl chloride that lead to conversion carboxyl groups of PAA in highly reactive acide chloride groups. 3. The covalent immobilization BAS of 'Piyavit' by acylation amino- and hydroxy-groups (functional groups in BAS) by acide chloride of PAA grafted on the polymere. (author)

Hydroperoxide Traces in Common Cyclic Ethers as Initiators for Controlled RAFT Polymerizations.

Science.gov (United States)

Eggers, Steffen; Abetz, Volker

2018-04-01

Herein, a reversible addition-fragmentation chain transfer (RAFT) polymerization is introduced for reactive monomers like N-acryloylpyrrolidine or N,N-dimethylacrylamide working without a conventional radical initiator. As a very straightforward proof of principle, the method takes advantage of the usually inconvenient radical-generating hydroperoxide contaminations in cyclic ethers like tetrahydrofuran or 1,4-dioxane, which are very common solvents in polymer sciences. The polymerizations are surprisingly well controlled and the polymers can be extended with a second block, indicating their high livingness. "Solvent-initiated" RAFT polymerizations hence prove to be a feasible access to tailored materials with minimal experimental effort and standard laboratory equipment, only requiring the following ingredients: hydroperoxide-contaminated solvent, monomer, and RAFT agent. In other respects, however, the potential coinitiating ability of the used solvent is to be considered when investigating the kinetics of RAFT polymerizations or aiming for the synthesis of high-livingness polymers, e.g., multiblock copolymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidative polymerization of lignins by laccase in water-acetone mixture.

Science.gov (United States)

Fiţigău, Ionița Firuța; Peter, Francisc; Boeriu, Carmen Gabriela

2013-01-01

The enzymatic oxidative polymerization of five technical lignins with different molecular properties, i.e. Soda Grass/Wheat straw Lignin, Organosolv Hardwood Lignin, Soda Wheat straw Lignin, Alkali pretreated Wheat straw Lignin, and Kraft Softwood was studied. All lignins were previously fractionated by acetone/water 50:50 (v/v) and the laccase-catalyzed polymerization of the low molecular weight fractions (Mw Reactivity of lignin substrates in laccase-catalyzed reactions was determined by monitoring the oxygen consumption. The oxidation reactions in 50% acetone in water mixture proceed with high rate for all tested lignins. Polymerization products were analyzed by size exclusion chromatography, FT-IR, and (31)P-NMR and evidence of important lignin modifications after incubation with laccase. Lignin polymers with higher molecular weight (Mw up to 17500 g/mol) were obtained. The obtained polymers have potential for applications in bioplastics, adhesives and as polymeric dispersants.

Reactivity of polymeric proanthocyanidins toward salivary proteins and their contribution to young red wine astringency.

Science.gov (United States)

Sun, Baoshan; de Sá, Marta; Leandro, Conceição; Caldeira, Ilda; Duarte, Filomena L; Spranger, Isabel

2013-01-30

Recent studies have indicated the presence of significant amount of highly polymerized and soluble proanthocyanidins in red wine and such compounds interacted readily with proteins, suggesting that they might be particularly astringent. Thus, the objective of this work was to verify the astringency of polymeric proanthocyanidins and their contribution to red wine astringency. The precipitation reactions of the purified oligomeric procyanidins (degree of polymerization ranging from 2 to 12-15) and polymeric procyanidins (degree of polymerization ranging from 12-15 to 32-34) with human salivary proteins were studied; salivary proteins composition changes before and after the reaction was verified by SDS-PAGE and procyanidins composition changes by spectrometric, direct HPLC and thiolysis-HPLC methods. The astringency intensity of these two procyanidin fractions was evaluated by a sensory analysis panel. For verifying the correlation between polymeric proanthocyanidins and young red wine astringency, the levels of total oligomeric and total polymeric proanthocyanidins and other phenolic composition in various young red wines were quantified and the astringency intensities of these wines were evaluated by a sensory panel. The results showed that polymeric proanthocyanidins had much higher reactivity toward human salivary proteins and higher astringency intensity than the oligomeric ones. Furthermore, young red wine astringency intensities were highly correlated to levels of polymeric proanthocyanidins, particularly at low concentration range (correlation coefficient r = 0.9840) but not significant correlated to total polyphenols (r = 0.2343) or other individual phenolic compounds (generally r wine astringency and the levels of polymeric polyphenols in red wines may be used as an indicator for its astringency.

KINETICS OF SUSPENDED EMULSION POLYMERIZATION OF METHYL METHACRYLATE

Institute of Scientific and Technical Information of China (English)

Yong-zhong Bao; Cheng-xi Wang; Zhi-ming Huang; Zhi-xue Weng

2004-01-01

The kinetics of suspended emulsion polymerization of methyl methacrylate (MMA), in which water acted as the dispersed phase and the mixture of MMA and cyclohexane as the continuous phase, was investigated. It showed that the initial polymerization rate (Rp0) and steady-state polymerization rate (Rp) were proportional to the mass ratio between water and oil phase, and increased as the polymerization temperature, the potassium persulphate concentration ([I]) and the Tween20 emulsifier concentration ([S]) increased. The relationships between the polymerization rate and [I] and [S] were obtained as follows: Rp0 ∝ [I]0.73[S]0.32 and Rp ∝ [I]0.71[S]0.23. The above exponents were close to those obtained from normal MMA emulsion polymerization. It also showed that the average molecular weight of the resulting poly(methyl methacrylate) decreased as the polymerization temperature, [I] and [S] increased. Thus, MMA suspended emulsion polymerization could be considered as a combination of many miniature emulsion polymerizations proceeding in water drops and obeyed the classical kinetics of MMA emulsion polymerization.

SYNTHESIS OF BLOCK COPOLYMER BY INTEGRATED LIVING ANIONIC POLYMERIZATION-ATOM TRANSFER RADICAL POLYMERIZATION (ATRP)

Institute of Scientific and Technical Information of China (English)

Bing Liu; Feng Liu; Ning Luo; Sheng-kang Ying; Qing Liu

2000-01-01

Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene)oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator.Then the PS-CH2CH2OCOCCl3 (PS-Cl3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl3) was used as the macroinitiator in the polymerization of (meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared by the integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl3 and the P(S-b-MMA) were identified by FTIR and 1H-NMR spectrum, respectively. A new way to design block copolymers (the combination of LAP and ATRP) was developed.

Schlenk Techniques for Anionic Polymerization

KAUST Repository

Ratkanthwar, Kedar

2015-09-01

Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands for time and skilled technical personnel, HVTs are currently used in only a few research laboratories worldwide. Instead, most researchers in this filed are attracted to more facile Schlenk techniques. The basic principle of this technique followed in all laboratories is substantially the same, i.e. the use of alternate vacuum and inert gas atmosphere in glass apparatus for the purification/charging of monomer, solvents, additives, and for the manipulation of air-sensitive compounds such as alkyl metal initiators, organometallic or organic catalysts. However, it is executed quite differently in each research group in terms of the structure of Schlenk apparatus (manifolds, connections, purification/storage flasks, reactors, etc.), the use of small supplementary devices (soft tubing, cannulas, stopcocks, etc.) and experimental procedures. The operational methods are partly purpose-oriented while also featured by a high flexibility, which makes it impossible to describe in detail each specific one. In this chapter we will briefly exemplify the application of Schlenk techniques for anionic polymerization by describing the performance of a few experiments from our own work.

Inflation of a Polymeric Menbrane

DEFF Research Database (Denmark)

Kristensen, Susanne B.; Larsen, Johannes R.; Hassager, Ole

1998-01-01

We consider an axisymmetric polymeric membrane inflated by a uniform pressure difference acting across the membrane.......We consider an axisymmetric polymeric membrane inflated by a uniform pressure difference acting across the membrane....

Comparative study of pressure-induced polymerization in C60 nanorods and single crystals

International Nuclear Information System (INIS)

Hou Yuanyuan; Liu Bingbing; Wang Lin; Yu Shidan; Yao Mingguang; Chen Ao; Liu Dedi; Zou Yonggang; Li Zepeng; Zou Bo; Cui Tian; Zou Guangtian; Iwasiewicz-Wabnig, Agnieszka; Sundqvist, Bertil

2007-01-01

In this paper, we report a comparative study of pressure-induced polymerization in C 60 nanorods and bulk single crystals, treated simultaneously under various pressures and temperatures in the same experiment. For both materials, orthorhombic, tetragonal and rhombohedral phases have been produced under high pressure and high temperature. The structures have been identified and compared between the two sample types by Raman and photoluminescence spectroscopy. There are differences between the Raman and photoluminescence spectra from the two types of materials for all polymeric phases, but especially for the tetragonal phase. From the comparison between nanorods and bulk samples, we tentatively assign photoluminescence peaks for various polymeric phases

Polystyrene/magnesium hydroxide nanocomposite particles prepared by surface-initiated in-situ polymerization

International Nuclear Information System (INIS)

Liu Hui; Yi Jianhong

2009-01-01

In order to avoid their agglomeration and incompatibility with hydrophobic polystyrene substrate, magnesium hydroxide nanoparticles were encapsulated by surface-initiated in-situ polymerization of styrene. The process contained two steps: electrostatic adsorption of initiator and polymerization of monomer on the surface of magnesium hydroxide. It was found that high adsorption ratio in the electrostatic adsorption of initiator could be attained only in acidic region, and the adsorption belonged to typical physical process. Compared to traditional in-situ polymerization, higher grafting ratio was obtained in surface-initiated in-situ polymerization, which can be attributed to weaker steric hindrance. Both Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM) indicated that polystyrene/magnesium hydroxide nanocomposite particles had been successfully prepared by surface-initiated in-situ polymerization. The resulting samples were also analyzed and characterized by means of contact angle testing, dispersibility evaluation and thermogravimetric analysis

Simulation of styrene polymerization reactors: kinetic and thermodynamic modeling

Directory of Open Access Journals (Sweden)

A. S. Almeida

2008-06-01

Full Text Available A mathematical model for the free radical polymerization of styrene is developed to predict the steady-state and dynamic behavior of a continuous process. Special emphasis is given for the kinetic and thermodynamic models, where the most sensitive parameters were estimated using data from an industrial plant. The thermodynamic model is based on a cubic equation of state and a mixing rule applied to the low-pressure vapor-liquid equilibrium of polymeric solutions, suitable for modeling the auto-refrigerated polymerization reactors, which use the vaporization rate to remove the reaction heat from the exothermic reactions. The simulation results show the high predictive capability of the proposed model when compared with plant data for conversion, average molecular weights, polydispersity, melt flow index, and thermal properties for different polymer grades.

Two-Dimensional Polymer Synthesized via Solid-State Polymerization for High-Performance Supercapacitors.

Science.gov (United States)

Liu, Wei; Ulaganathan, Mani; Abdelwahab, Ibrahim; Luo, Xin; Chen, Zhongxin; Rong Tan, Sherman Jun; Wang, Xiaowei; Liu, Yanpeng; Geng, Dechao; Bao, Yang; Chen, Jianyi; Loh, Kian Ping

2018-01-23

Two-dimensional (2-D) polymer has properties that are attractive for energy storage applications because of its combination of heteroatoms, porosities and layered structure, which provides redox chemistry and ion diffusion routes through the 2-D planes and 1-D channels. Here, conjugated aromatic polymers (CAPs) were synthesized in quantitative yield via solid-state polymerization of phenazine-based precursor crystals. By choosing flat molecules (2-TBTBP and 3-TBQP) with different positions of bromine substituents on a phenazine-derived scaffold, C-C cross coupling was induced following thermal debromination. CAP-2 is polymerized from monomers that have been prepacked into layered structure (3-TBQP). It can be mechanically exfoliated into micrometer-sized ultrathin sheets that show sharp Raman peaks which reflect conformational ordering. CAP-2 has a dominant pore size of ∼0.8 nm; when applied as an asymmetric supercapacitor, it delivers a specific capacitance of 233 F g -1 at a current density of 1.0 A g -1 , and shows outstanding cycle performance.

Mechanical and Electrical Properties of Sulfur-Containing Polymeric Materials Prepared via Inverse Vulcanization

Directory of Open Access Journals (Sweden)

Sergej Diez

2017-02-01

Full Text Available Recently, new methods have been developed for the utilization of elemental sulfur as a feedstock for novel polymeric materials. One promising method is the inverse vulcanization, which is used to prepare polymeric structures derived from sulfur and divinyl comonomers. However, the mechanical and electrical properties of the products are virtually unexplored. Hence, in the present study, we synthesized a 200 g scale of amorphous, hydrophobic as well as translucent, hyperbranched polymeric sulfur networks that provide a high thermal resistance (>220 °C. The polymeric material properties of these sulfur copolymers can be controlled significantly by varying the monomers as well as the feed content. The investigated comonomers are divinylbenzene (DVB and 1,3-diisopropenylbenzene (DIB. Plastomers with low elastic content and high shape retention containing 12.5%–30% DVB as well as low viscose waxy plastomers with a high flow behavior containing a high DVB content of 30%–35% were obtained. Copolymers with 15%–30% DIB act, on the one hand, as thermoplastics and, on the other hand, as vitreous thermosets with a DIB of 30%–35%. Results of the thermogravimetric analysis (TGA, the dynamic scanning calorimetry (DSC and mechanical characterization, such as stress–strain experiments and dynamic mechanical thermal analysis, are discussed with the outcome that they support the assumption of a polymeric cross-linked network structure in the form of hyper-branched polymers.

High-performance polymeric photovoltaic cells with a gold chloride-treated polyacrylonitrile hole extraction interlayer

Science.gov (United States)

Jeong, Ji-Ho; Noh, Yong-Jin; Kim, Seok-Soon; Kwon, Sung-Nam; Na, Seok-In

2018-03-01

We introduce a high efficiency polymeric photovoltaic cell (PPV) to be obtained by polyacrylonitrile (PAN) hole extraction layer (HEL) modification with gold chloride (AuCl3). The role of PAN HELs with AuCl3 and their effects on solar cell performances were studied with ultraviolet photoemission spectroscopy, atomic force microscopy, internal resistances in PPVs, and current-voltage power curves. The resultant PPVs with AuCl3-treated PAN HELs showed improved cell efficiency compared to PSCs with no interlayer and PAN without AuCl3. Furthermore, with AuCl3-treated PAN, we finally achieved a high efficiency of 6.91%, and a desirable PPV-stability in poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b‧]dithiophe-ne-2,6-diyl][3-fluoro-2-[(2-thylhexyl)carbonyl]-thieno[3,4-b]thiophenediyl

Polymeric membrane materials for artificial organs.

Science.gov (United States)

Kawakami, Hiroyoshi

2008-01-01

Many polymeric materials have already been used in the field of artificial organs. However, the materials used in artificial organs are not necessarily created with the best material selectivity and materials design; therefore, the development of synthesized polymeric membrane materials for artificial organs based on well-defined designs is required. The approaches to the development of biocompatible polymeric materials fall into three categories: (1) control of physicochemical characteristics on material surfaces, (2) modification of material surfaces using biomolecules, and (3) construction of biomimetic membrane surfaces. This review will describe current issues regarding polymeric membrane materials for use in artificial organs.

THE EFFECTS OF N-2-HYDROXYETHYL-N-METHYL-P-TOLUIDINE ON METHYL METHACRYLATE RADICAL POLYMERIZATION AND ACRYLONITRILE PHOTOINDUCED POLYMERIZATION

Institute of Scientific and Technical Information of China (English)

QIU Kunyuan; ZHANG Zhanghua; FENG Xinde

1992-01-01

The effects of N-2-hydroxyethyl-N-methyl-p-toluidine (HMT) on MMA polymerization using organic peroxide as an initiator and on AN photoinduced polymerization have been investigated respectively. The kinetics of polymerization and the overall activation energy of polymerization were determined. Based on kinetics study and the end group analysis of the polymer obtained by UV spectrum method, the initiation mechanism is proposed.

Light-harvesting organic photoinitiators of polymerization.

Science.gov (United States)

Lalevée, Jacques; Tehfe, Mohamad-Ali; Dumur, Frédéric; Gigmes, Didier; Graff, Bernadette; Morlet-Savary, Fabrice; Fouassier, Jean-Pierre

2013-02-12

Two new photoinitiators with unprecedented light absorption properties are proposed on the basis of a suitable truxene skeleton where several UV photoinitiators PI units such as benzophenone and thioxanthone are introduced at the periphery and whose molecular orbitals MO can be coupled with those of the PI units: a red-shifted absorption and a strong increase of the molecular extinction coefficients (by a ≈ 20-1000 fold factor) are found. These compounds are highly efficient light-harvesting photoinitiators. The scope and practicality of these photoinitiators of polymerization can be dramatically expanded, that is, both radical and cationic polymerization processes are accessible upon very soft irradiation conditions (halogen lamp, LED…︁) thanks to the unique light absorption properties of the new proposed structures. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Production methodologies of polymeric and hydrogel particles for drug delivery applications.

Science.gov (United States)

Lima, Ana Catarina; Sher, Praveen; Mano, João F

2012-02-01

Polymeric particles are ideal vehicles for controlled delivery applications due to their ability to encapsulate a variety of substances, namely low- and high-molecular mass therapeutics, antigens or DNA. Micro and nano scale spherical materials have been developed as carriers for therapies, using appropriated methodologies, in order to achieve a prolonged and controlled drug administration. This paper reviews the methodologies used for the production of polymeric micro/nanoparticles. Emulsions, phase separation, spray drying, ionic gelation, polyelectrolyte complexation and supercritical fluids precipitation are all widely used processes for polymeric micro/nanoencapsulation. This paper also discusses the recent developments and patents reported in this field. Other less conventional methodologies are also described, such as the use of superhydrophobic substrates to produce hydrogel and polymeric particulate biomaterials. Polymeric drug delivery systems have gained increased importance due to the need for improving the efficiency and versatility of existing therapies. This allows the development of innovative concepts that could create more efficient systems, which in turn may address many healthcare needs worldwide. The existing methods to produce polymeric release systems have some critical drawbacks, which compromise the efficiency of these techniques. Improvements and development of new methodologies could be achieved by using multidisciplinary approaches and tools taken from other subjects, including nanotechnologies, biomimetics, tissue engineering, polymer science or microfluidics.

21 CFR 175.300 - Resinous and polymeric coatings.

Science.gov (United States)

2010-04-01

... descriptions: (1) Coatings cured by oxidation. (2) Coatings cured by polymerization, condensation, and/or cross... condensation product formed by the reaction of hydrogenated castor oil with polyamide derived from...-oil emulsion, high- or low-fat. B. Oil-in-water emulsion, high- or low-fat. V. Low moisture fats and...

Characterization of Z-RAFT star polymerization of butyl acrylate by size-exclusion chromatography

NARCIS (Netherlands)

Boschmann, D.; Edam, R.; Schoenmakers, P.J.; Vana, P.

2009-01-01

Z-RAFT star polymerization of butyl acrylate using multifunctional trithiocarbonate-type RAFT agents carrying methyl propionate as the leaving group were used to form star polymers having 3, 4, and 6 arms. The polymerizations showed well controlled behavior up to high monomer conversions. By using a

Nanoparticles from a controlled polymerization process

International Nuclear Information System (INIS)

Tirumala, V.R.; Caneba, G.T.; Dar, Y.; Wang, H.-H.; Mancini, D.C.

2003-01-01

Free-radical retrograde precipitation polymerization process in the past has shown excellent control characteristics over reaction rate, molecular weight, and in the entrapment of live radicals for the generation of block copolymers. The same principle has now been extended to study the reaction confinement to a nanoscale region. Nanosized polymer particles have been reported to form from block copolymers, conventional precipitation polymerization methods, or through emulsion polymerization approaches. In this work, we present a new method of generating nanosized polymer particles by polymerizing the monomer in an environment that precipitates the polymer above the lower critical solution temperature. The nanoparticles have been characterized by both tapping-mode atomic force microscopy observations and in situ synchrotron time-resolved small-angle X-ray scattering analysis. The results from both the techniques showed the formation of nanoparticles in the size range of 15-30 nm, directly from the polymerization process.

Optimal control of batch emulsion polymerization of vinyl chloride

Energy Technology Data Exchange (ETDEWEB)

Damslora, Andre Johan

1998-12-31

The highly exothermic polymerization of vinyl chloride (VC) is carried out in large vessels where the heat removal represents a major limitation of the production rate. Many emulsion polymerization reactors are operated in such a way that a substantial part of the heat transfer capacity is left unused for a significant part of the total batch time. To increase the reaction rate so that it matches the heat removal capacity during the course of the reaction, this thesis proposes the use of a sufficiently flexible initiator system to obtain a reaction rate which is high throughout the reaction and real-time optimization to compute the addition policy for the initiator. This optimization based approach provides a basis for an interplay between design and control and between production and research. A simple model is developed for predicting the polymerization rate. The model is highly nonlinear and open-loop unstable and may serve as an interesting case for comparison of nonlinear control strategies. The model is fitted to data obtained in a laboratory scale reactor. Finally, the thesis discusses optimal control of the emulsion polymerization reactor. Reduction of the batch cycle time is of major economic importance, as long as the quality parameters are within their specifications. The control parameterization had a major influence on the performance. A differentiable spline parameterization was applied and the optimization is illustrated in a number of cases. The best performance is obtained when the reactor temperature is obtained when the optimization is combined with some form of closed-loop control of the reactor temperature. 112 refs., 48 figs., 4 tabs.

Conductive cotton prepared by polyaniline in situ polymerization using laccase.

Science.gov (United States)

Zhang, Ya; Dong, Aixue; Wang, Qiang; Fan, Xuerong; Cavaco-Paulo, Artur; Zhang, Ying

2014-09-01

The high-redox-potential catalyst laccase, isolated from Aspergillus, was first used as a biocatalyst in the oxidative polymerization of water-soluble conductive polyaniline, and then conductive cotton was prepared by in situ polymerization under the same conditions. The polymerization of aniline was performed in a water dispersion of sodium dodecylbenzenesulfonate (SDBS) micellar solution with atmospheric oxygen serving as the oxidizing agent. This method is ecologically clean and permits a greater degree of control over the kinetics of the reaction. The conditions for polyaniline synthesis were optimized. Characterizations of the conducting polyaniline and cotton were carried out using Fourier transform infrared spectroscopy, UV-vis spectroscopy, cyclic voltammetry, the fabric induction electrostatic tester, and the far-field EMC shielding effectiveness test fixture.

Polymerization Behavior and Mechanical Properties of High-Viscosity Bulk Fill and Low Shrinkage Resin Composites.

Science.gov (United States)

Shibasaki, S; Takamizawa, T; Nojiri, K; Imai, A; Tsujimoto, A; Endo, H; Suzuki, S; Suda, S; Barkmeier, W W; Latta, M A; Miyazaki, M

The present study determined the mechanical properties and volumetric polymerization shrinkage of different categories of resin composite. Three high viscosity bulk fill resin composites were tested: Tetric EvoCeram Bulk Fill (TB, Ivoclar Vivadent), Filtek Bulk Fill posterior restorative (FB, 3M ESPE), and Sonic Fill (SF, Kerr Corp). Two low-shrinkage resin composites, Kalore (KL, GC Corp) and Filtek LS Posterior (LS, 3M ESPE), were used. Three conventional resin composites, Herculite Ultra (HU, Kerr Corp), Estelite ∑ Quick (EQ, Tokuyama Dental), and Filtek Supreme Ultra (SU, 3M ESPE), were used as comparison materials. Following ISO Specification 4049, six specimens for each resin composite were used to determine flexural strength, elastic modulus, and resilience. Volumetric polymerization shrinkage was determined using a water-filled dilatometer. Data were evaluated using analysis of variance followed by Tukey's honestly significant difference test (α=0.05). The flexural strength of the resin composites ranged from 115.4 to 148.1 MPa, the elastic modulus ranged from 5.6 to 13.4 GPa, and the resilience ranged from 0.70 to 1.0 MJ/m 3 . There were significant differences in flexural properties between the materials but no clear outliers. Volumetric changes as a function of time over a duration of 180 seconds depended on the type of resin composite. However, for all the resin composites, apart from LS, volumetric shrinkage began soon after the start of light irradiation, and a rapid decrease in volume during light irradiation followed by a slower decrease was observed. The low shrinkage resin composites KL and LS showed significantly lower volumetric shrinkage than the other tested materials at the measuring point of 180 seconds. In contrast, the three bulk fill resin composites showed higher volumetric change than the other resin composites. The findings from this study provide clinicians with valuable information regarding the mechanical properties and

Peptide block copolymers by N-carboxyanhydride ring-opening polymerization and atom transfer radical polymerization: The effect of amide macroinitiators

NARCIS (Netherlands)

Habraken, G.J.M.; Koning, C.E.; Heise, A.

2009-01-01

The synthesis of polypeptide-containing block copolymers combining N-carboxyanhydride (NCA) ring-opening polymerization and atom transfer radical polymerization (ATRP) was investigated. An amide initiator comprising an amine function for the NCA polymerization and an activated bromide for ATRP was

Structural analysis of fructans

International Nuclear Information System (INIS)

Spies, T.

1991-01-01

The fructan sinistrin from Urginea maritima (red squill), fructans from Triticum aestivum (wheat), Agropyron repens (quack grass) and Pucinella peisonis were analyzed by NMR spectroscopy and the reductive cleavage method. Sinistrin was found to be a branched mixed type fructan between inulin type and levan type with (2→1) and (2→6) linked β-D-fructofuranosyl residues in the same molecule. The average degree of polymerization (d. p.) is 31. The α-D-glucopyranosyl residue in the molecule is not only linked like in sucrose and also like in neokestose. The quackgrass fructan is highly branched, has an average d. p. of 45, but has a levan backbone with a few amount of β-(2→1) linked β-D-fructofuranosyl residues. The fructan from Pucinella peisonis is very low branched, has an average d. p. of 10 and has only (2→6) linked β-D-fructofuranosyl residues in the molecule. The low molecular oligomers from sinistrin and wheat were separated by gel filtration and semi preparative reversed phase hplc. The purified oligomers were then analyzed by the reductive cleavage method and NMR spectroscopy. The trisaccharides 1-kestose and neokestose and 5 tetrasaccharides, among them the branched molecule bifurcose and the unbranched molecule nystose, were identified in sinistrin. With this information a new model of sinistrin is given. In wheat 1-kestose, 6-kestose, a pentasaccharide and bifurcose were found. The 13 C NMR spectrum of 6-kestose is presented and discussed. A new evaporative light scattering detector was used to analyze inulooligosaccharides and inulin using reversed phase hplc with gradient elution. The advantages of this detector for the detection of saccharides are discussed. (author)

Porous polymeric membranes with thermal and solvent resistance

KAUST Repository

Pulido, Bruno; Waldron, Christopher; Zolotukhin, M.G.; Nunes, Suzana Pereira

2017-01-01

Polymeric membranes are highly advantageous over their ceramic counterparts in terms of the simplicity of the manufacturing process, cost and scalability. Their main disadvantages are low stability at temperatures above 200 °C, and in organic

Self-folding polymeric containers for encapsulation and delivery of drugs.

Science.gov (United States)

Fernandes, Rohan; Gracias, David H

2012-11-01

Self-folding broadly refers to self-assembly processes wherein thin films or interconnected planar templates curve, roll-up or fold into three dimensional (3D) structures such as cylindrical tubes, spirals, corrugated sheets or polyhedra. The process has been demonstrated with metallic, semiconducting and polymeric films and has been used to curve tubes with diameters as small as 2nm and fold polyhedra as small as 100nm, with a surface patterning resolution of 15nm. Self-folding methods are important for drug delivery applications since they provide a means to realize 3D, biocompatible, all-polymeric containers with well-tailored composition, size, shape, wall thickness, porosity, surface patterns and chemistry. Self-folding is also a highly parallel process, and it is possible to encapsulate or self-load therapeutic cargo during assembly. A variety of therapeutic cargos such as small molecules, peptides, proteins, bacteria, fungi and mammalian cells have been encapsulated in self-folded polymeric containers. In this review, we focus on self-folding of all-polymeric containers. We discuss the mechanistic aspects of self-folding of polymeric containers driven by differential stresses or surface tension forces, the applications of self-folding polymers in drug delivery and we outline future challenges. Copyright © 2012 Elsevier B.V. All rights reserved.

Tunable, Quantitative Fenton-RAFT Polymerization via Metered Reagent Addition.

Science.gov (United States)

Nothling, Mitchell D; McKenzie, Thomas G; Reyhani, Amin; Qiao, Greg G

2018-05-10

A continuous supply of radical species is a key requirement for activating chain growth and accessing quantitative monomer conversions in reversible addition-fragmentation chain transfer (RAFT) polymerization. In Fenton-RAFT, activation is provided by hydroxyl radicals, whose indiscriminate reactivity and short-lived nature poses a challenge to accessing extended polymerization times and quantitative monomer conversions. Here, an alternative Fenton-RAFT procedure is presented, whereby radical generation can be finely controlled via metered dosing of a component of the Fenton redox reaction (H 2 O 2 ) using an external pumping system. By limiting the instantaneous flux of radicals and ensuring sustained radical generation over tunable time periods, metered reagent addition reduces unwanted radical "wasting" reactions and provides access to consistent quantitative monomer conversions with high chain-end fidelity. Fine tuning of radical concentration during polymerization is achieved simply via adjustment of reagent dose rate, offering significant potential for automation. This modular strategy holds promise for extending traditional RAFT initiation toward more tightly regulated radical concentration profiles and affords excellent prospects for the automation of Fenton-RAFT polymerization. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of Zeolitic Imidazolate Framework-8 (ZIF-8) Membrane on Porous Polymeric Support via Contra-Diffusion Method

KAUST Repository

Tan, Xiaoyu

2016-01-01

way to
fabricate defect-free and thin ZIF-8 membranes on porous polymeric supports showing high selectivity and high gas permeance. The ZIF-8 layers were produced via a contra-diffusion method. Several polymeric membranes were employed as support

Synthesis and polymerization of vinyl triazolium ionic liquids

Science.gov (United States)

Luebke, David; Nulwala, Hunaid; Matyjaszewski, Krzysztof; Adzima, Brian

2018-05-15

Herein, we describe polymerized ionic liquids, demonstrate the synthesis of polymerized ionic liquids, and demonstrate the polymerization of triazolium monomers. One embodiment shows the polymeriazation of the triazolium monomers with bis(trifluoromethanesulfonyl)imide anions. In another embodiment we show the feasibility of copolymerizing with commodity monomers such as styrene using free radical polymerization techniques.

Developing thin-film-composite forward osmosis membranes on the PES/SPSf substrate through interfacial polymerization

KAUST Repository

Wang, Kaiyu; Chung, Tai Shung Neal; Amy, Gary L.

2011-01-01

A new scheme has been developed to fabricate high-performance forward osmosis (FO) membranes through the interfacial polymerization reaction on porous polymeric supports. p-Phenylenediamine and 1,3,5-trimesoylchloride were adopted as the monomers

Preparations of spherical polymeric particles from Tanzanian ...

African Journals Online (AJOL)

Spherical Polymeric Particles (SPP) have been prepared from Tanzanian Cashew Nut Shell Liquid (CNSL) by suspension polymerization technique involving either step-growth or chain- growth polymerization mechanisms. The sizes of the SPP, which ranged from 0.1 to 2.0 mm were strongly influenced by the amounts of ...

High Thermoelectric Power Factor Organic Thin Films through Combination of Nanotube Multilayer Assembly and Electrochemical Polymerization.

Science.gov (United States)

Culebras, Mario; Cho, Chungyeon; Krecker, Michelle; Smith, Ryan; Song, Yixuan; Gómez, Clara M; Cantarero, Andrés; Grunlan, Jaime C

2017-02-22

In an effort to produce effective thermoelectric nanocomposites with multiwalled carbon nanotubes (MWCNT), layer-by-layer assembly was combined with electrochemical polymerization to create synergy that would produce a high power factor. Nanolayers of MWCNT stabilized with poly(diallyldimethylammonium chloride) or sodium deoxycholate were alternately deposited from water. Poly(3,4-ethylene dioxythiophene) [PEDOT] was then synthesized electrochemically by using this MWCNT-based multilayer thin film as the working electrode. Microscopic images show a homogeneous distribution of PEDOT around the MWCNT. The electrical resistance, conductivity (σ) and Seebeck coefficient (S) were measured before and after the PEDOT polymerization. A 30 bilayer MWCNT film (<1 μm thick) infused with PEDOT is shown to achieve a power factor (PF = S 2 σ) of 155 μW/m K 2 , which is the highest value ever reported for a completely organic MWCNT-based material and competitive with lead telluride at room temperature. The ability of this MWCNT-PEDOT film to generate power was demonstrated with a cylindrical thermoelectric generator that produced 5.5 μW with a 30 K temperature differential. This unique nanocomposite, prepared from water with relatively inexpensive ingredients, should open up new opportunities to recycle waste heat in portable/wearable electronics and other applications where low weight and mechanical flexibility are needed.

Volumetric polymerization shrinkage of contemporary composite resins

Directory of Open Access Journals (Sweden)

Halim Nagem Filho

2007-10-01

Full Text Available The polymerization shrinkage of composite resins may affect negatively the clinical outcome of the restoration. Extensive research has been carried out to develop new formulations of composite resins in order to provide good handling characteristics and some dimensional stability during polymerization. The purpose of this study was to analyze, in vitro, the magnitude of the volumetric polymerization shrinkage of 7 contemporary composite resins (Definite, Suprafill, SureFil, Filtek Z250, Fill Magic, Alert, and Solitaire to determine whether there are differences among these materials. The tests were conducted with precision of 0.1 mg. The volumetric shrinkage was measured by hydrostatic weighing before and after polymerization and calculated by known mathematical equations. One-way ANOVA (a or = 0.05 was used to determine statistically significant differences in volumetric shrinkage among the tested composite resins. Suprafill (1.87±0.01 and Definite (1.89±0.01 shrank significantly less than the other composite resins. SureFil (2.01±0.06, Filtek Z250 (1.99±0.03, and Fill Magic (2.02±0.02 presented intermediate levels of polymerization shrinkage. Alert and Solitaire presented the highest degree of polymerization shrinkage. Knowing the polymerization shrinkage rates of the commercially available composite resins, the dentist would be able to choose between using composite resins with lower polymerization shrinkage rates or adopting technical or operational procedures to minimize the adverse effects deriving from resin contraction during light-activation.

Antimicrobial activity of silver nanoparticles encapsulated in poly-N-isopropylacrylamide-based polymeric nanoparticles.

Science.gov (United States)

Qasim, Muhammad; Udomluck, Nopphadol; Chang, Jihyun; Park, Hansoo; Kim, Kyobum

2018-01-01

In this study, we analyzed the antimicrobial activities of poly- N -isopropylacrylamide (pNIPAM)-based polymeric nanoparticles encapsulating silver nanoparticles (AgNPs). Three sizes of AgNP-encapsulating pNIPAM- and pNIPAM-NH 2 -based polymeric nanoparticles were fabricated. Highly stable and uniformly distributed AgNPs were encapsulated within polymeric nanoparticles via in situ reduction of AgNO 3 using NaBH 4 as the reducing agent. The formation and distribution of AgNPs was confirmed by UV-visible spectroscopy, transmission electron microscopy, and inductively coupled plasma optical emission spectrometry, respectively. Both polymeric nanoparticles showed significant bacteriostatic activities against Gram-negative ( Escherichia coli ) and Gram-positive ( Staphylococcus aureus ) bacteria depending on the nanoparticle size and amount of AgNO 3 used during fabrication.

Gamma radiation-polymerized methacrylates used as heavy metals adsorbents

International Nuclear Information System (INIS)

Barrera D, C.; Roa M, G.; Balderas H, P.; Bilyeu, B.; Urena N, F.

2009-01-01

Heavy metal removal from aqueous solution is a priority research area since the actual methods are costly and a major drawback is the large amounts of sludge generated when applying traditional techniques. Adsorption is a physiochemical wastewater treatment process, which is gaining prominence as a means of producing high quality effluents, which are low in metal ion concentrations. The development of inexpensive adsorbents for the treatment of wastewater is an important area in environmental sciences. In this work we describe some of the physical and chemical phenomena that take place in the polymerization of methacrylates when gamma radiation is used. We explain how polymeric material characterization equipment are used for obtaining information regarding the material properties. Then we explain how the new polymeric material obtained can be use for the wastewater treatment. Finally, a comparison in the heavy metal removal from aqueous solution with other sorbent materials is presented. (Author)

Polymerization of epoxidized triglycerides with fluorosulfonic acid

Science.gov (United States)

The use of triglycerides as agri-based renewable raw materials for the development of new products is highly desirable in view of uncertain future petroleum prices. A new method of polymerizing epoxidized soybean oil has been devised with the use of fluorosulfonic acid. Depending on the reaction con...

Molecular and biochemical characteristics of the inulosucrase HugO from Streptomyces viridochromogenes DSM40736 (Tü494)

NARCIS (Netherlands)

Frasch, Hans-Jörg; Leeuwen, Sander S van; Dijkhuizen, Lubbert

2017-01-01

Polyfructans are synthesized from sucrose by plants (mostly inulin) and by both Gram-negative and Gram-positive bacteria (mostly levan). In the phylum Actinobacteria only levan synthesis by Actinomyces species has been reported. We have identified a putative fructansucrase gene (hugO) in

Radiation-induced polymerization and radiation effect on polymers

International Nuclear Information System (INIS)

Seguchi, Tadao

1977-12-01

The processes of radiation-induced polymerization of monomers and also radiation effects on polymers have been studied by instrumental analyses of electron spin resonance (ESR), nuclear magnetic resonance (NMR) and electron microscopy. In radiation-induced polymerization, graft-copolymerization and absorbed state polymerization were taken up. For graft-copolymerization, monomers such as methylmethacrylate and butadiene were made to react with irradiated polyethylene, and behaviors of the initiating radicals and propagating radicals were followed under the reaction by ESR. For absorbed state polymerization, acrylonitrile/zeolite and methylmethacrylate/zeolite were chosen. Absorbed monomers were irradiated at 77 0 K and polymerized at room temperature. Active species and the concentrations were measured by ESR and the yields of polymer were observed by NMR. In radiation effect on polymers, polyvinylfluoride, polyvinylidenfluoride and polytetrafluoroethylene were taken up. Active species trapped in the polymer matrixes were identified and decay and reactivity of the species were also studied. On the basis of information from the electron microscopy and x-ray analysis, radiation effects on these polymers are described. In polytetrafluoroethylene produced by radiation polymerization, the relation between morphology and polymerization conditions and also the process of crystallization during polymerization were studied. (auth.)

Flexible high-loading particle-reinforced polyurethane magnetic nanocomposite fabrication through particle-surface-initiated polymerization

International Nuclear Information System (INIS)

Guo Zhanhu; Park, Sung; Wei Suying; Pereira, Tony; Moldovan, Monica; Karki, Amar B; Young, David P; Hahn, H Thomas

2007-01-01

Flexible high-loading nanoparticle-reinforced polyurethane magnetic nanocomposites fabricated by the surface-initiated polymerization (SIP) method are reported. Extensive field emission scanning electron microscopic (SEM) and atomic force microscopic (AFM) observations revealed a uniform particle distribution within the polymer matrix. X-ray photoelectron spectrometry (XPS) and differential thermal analysis (DTA) revealed a strong chemical bonding between the nanoparticles and the polymer matrix. The elongation of the SIP nanocomposite under tensile test was about four times greater than that of the composite fabricated by a conventional direct mixing fabrication method. The nanocomposite shows particle-loading-dependent magnetic properties, with an increase of coercive force after the magnetic nanoparticles were embedded into the polymer matrix, arising from the increased interparticle distance and the introduced polymer-particle interactions

Interface polymerization synthesis of conductive polymer/graphite oxide@sulfur composites for high-rate lithium-sulfur batteries

International Nuclear Information System (INIS)

Wang, Xiwen; Zhang, Zhian; Yan, Xiaolin; Qu, Yaohui; Lai, Yanqing; Li, Jie

2015-01-01

Highlights: • A hybrid nanostructure that incorporate the merits of conductive polymer nanorods and graphite oxide sheets. • A novel approach based on interface polymerization for synthesizing CP/GO@S ternary composite. • CP/GO@S ternary composite cathode shows enhanced electrochemical properties compared with CP@S binary composite cathode. • PEDOT/GO@S composite is the material system that have best electrochemical performance in all CP/GO@S ternary composites. - Abstract: The novel ternary composites, conductive polymers (CPs)/graphene oxide (GO)@sulfur composites were successfully synthesized via a facile one-pot route and used as cathode materials for Li-S batteries The poly(3,4-ethylenedioxythiophene) (PEDOT)/GO and polyaniline (PANI)/GO composites were prepared by interface polymerization of monomers on the surface of GO sheets. Then sulfur was in-situ deposited on the CPs/GO composites in same solution. The component and structure of the composites were characterized by XPS, TGA, FTIR, SEM, TEM and electrochemical measurements. In this structure, the CPs nanostructures are believed to serve as a conductive matrix and an adsorbing agent, while the highly conductive GO will physically and chemically confine the sulfur and polysulfide within cathode. The PEDOT/GO@S composites with the sulfur content of 66.2 wt% exhibit a reversible discharge capacity of 800.2 mAh g −1 after 200 cycles at 0.5 C, which is much higher than that of PANI/GO@S composites (599.1 mAh g −1 ) and PANI@S (407.2 mAh g −1 ). Even at a high rate of 4 C, the PEDOT/GO@S composites still retain a high specific capacity of 632.4 mAh g −1

Polymerization of N-(fluoro phenyl) maleimides

International Nuclear Information System (INIS)

Barrales-Rienda, J.M.; Ramos, J.G.; Chaves, M.S.

1979-01-01

Poly(N-aryl maleimide)s of characteristic structures have been synthesized and some of their physical properties studied. The polymerization of N-(fluoro phenyl) maleimides by free-radical initiation in bulk or in solution and by anionic catalyst have been studied to compare the characteristics of polymerization by γ-ray irradiation with that by free-radical initiation. The polymers were characterized by elemental analysis, intrinsic viscosity, spectroscopy (IR and NMR), programmed thermogravimetric analysis, and x-ray diffraction. Spectra of polymers prepared by radiation and anionic polymerization were nearly identical with those of polymers prepared by free-radical polymerization initiated by azobisisobutyronitrile in bulk or in solution and by the self-initiated thermal polymerization. A variety of reaction conditions were tried, but all attempts to change the molecular structure of the polymers were unsuccessful. Rates of thermal degradation for poly[N-(fluoro phenyl) maleimide]s have been analyzed by using a multiple-heating-rate procedure. Overall activation energy, order of reaction, and frequency factor have been evaluated. 6 figures, 8 tables

Facile and Reliable in Situ Polymerization of Poly(Ethyl Cyanoacrylate)-Based Polymer Electrolytes toward Flexible Lithium Batteries.

Science.gov (United States)

Cui, Yanyan; Chai, Jingchao; Du, Huiping; Duan, Yulong; Xie, Guangwen; Liu, Zhihong; Cui, Guanglei

2017-03-15

Polycyanoacrylate is a very promising matrix for polymer electrolyte, which possesses advantages of strong binding and high electrochemical stability owing to the functional nitrile groups. Herein, a facile and reliable in situ polymerization strategy of poly(ethyl cyanoacrylate) (PECA) based gel polymer electrolytes (GPE) via a high efficient anionic polymerization was introduced consisting of PECA and 4 M LiClO 4 in carbonate solvents. The in situ polymerized PECA gel polymer electrolyte achieved an excellent ionic conductivity (2.7 × 10 -3 S cm -1 ) at room temperature, and exhibited a considerable electrochemical stability window up to 4.8 V vs Li/Li + . The LiFePO 4 /PECA-GPE/Li and LiNi 1.5 Mn 0.5 O 4 /PECA-GPE/Li batteries using this in-situ-polymerized GPE delivered stable charge/discharge profiles, considerable rate capability, and excellent cycling performance. These results demonstrated this reliable in situ polymerization process is a very promising strategy to prepare high performance polymer electrolytes for flexible thin-film batteries, micropower lithium batteries, and deformable lithium batteries for special purpose.

Measurement and Analysis of in vitro Actin Polymerization

Science.gov (United States)

Doolittle, Lynda K.; Rosen, Michael K.; Padrick, Shae B.

2014-01-01

Summary The polymerization of actin underlies force generation in numerous cellular processes. While actin polymerization can occur spontaneously, cells maintain control over this important process by preventing actin filament nucleation and then allowing stimulated polymerization and elongation by several regulated factors. Actin polymerization, regulated nucleation and controlled elongation activities can be reconstituted in vitro, and used to probe the signaling cascades cells use to control when and where actin polymerization occurs. Introducing a pyrene fluorophore allows detection of filament formation by an increase in pyrene fluorescence. This method has been used for many years and continues to be broadly used, owing to its simplicity and flexibility. Here we describe how to perform and analyze these in vitro actin polymerization assays, with an emphasis on extracting useful descriptive parameters from kinetic data. PMID:23868594

Effect of composite resin polymerization modes on temperature rise in human dentin of different thicknesses: an in vitro study

International Nuclear Information System (INIS)

Baggio Aguiar, Flavio Henrique; Kanda Peres Barros, Gisele; Alves Nunes Leite Lima, Debora; Bovi Ambrosano, Glaucia Maria; Lovadino, Jose Roberto

2006-01-01

The aim of this in vitro study was to evaluate the effect of different polymerization modes on temperature rise in human dentin of different thicknesses, and to evaluate the relation between dentin thickness and temperature rise (TR). For this purpose, 60 specimens were assigned into 20 groups (n = 3): five polymerization modes (1-conventional; 2-soft-start; 3-high intensity; 4-ramp cure: progressive and high intensity; 5-high intensity with the tip of the light-curing unit at a distance of 1.3 cm for 10 s and the tip leaning on the sample) at four dentin thicknesses (0, 1, 2, 3 mm). During composite sample polymerization (2 mm), the temperature was measured by a digital laser thermometer (CMSS2000-SL/SKF). The statistical analyses were conducted by ANOVA (p = 0.05) and post-hoc Tukey's test. There were statistical differences of TR among polymerization modes and dentin thicknesses. The temperature rise was dependent on the polymerization mode and the dentin thickness: the thicker the dentin and the lower the polymerization mode energy, the lower the temperature rise

In situ self-polymerization of unsaturated metal methacrylate and its dispersion mechanism in rubber-based composites

Energy Technology Data Exchange (ETDEWEB)

Wen, Shipeng; Zhou, Yao; Yao, Lu [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); Zhang, Liqun [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 (China); Chan, Tung W. [Department of Materials Science and Engineering, Virginia Polytechnic Institute and State University, VA 24061 (United States); Liang, Yongri [Beijing National Laboratory for Molecular Sciences, Joint Laboratory of Polymer Science and Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); Liu, Li, E-mail: LiuL@mail.buct.edu.cn [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China)

2013-11-10

Highlights: • In situ self-polymerization of unsaturated metal methacrylate was investigated mainly by the thermal effect. • UMM with low melting point can self-polymerize to a large extent. • The fine dispersion phase is composed of poly(UMM) nanoparticles formed by in situ self-polymerization in the rubber matrix. • The UMM crystals in the presence of peroxide and rubber undergo the processes of melting, diffusion, polymerization, and phase separation in this order. - Abstract: Unsaturated metal methacrylate (UMM) as one kind of functional filler has played an important role in reinforcing rubber materials. The in situ self-polymerization of UMM in UMM/rubber composite leads to the uniform dispersion of poly(UMM) in the rubber matrix, while the crosslinking of rubber and grafting between UMM and rubber chains occur simultaneously, making it difficult to clarify the effect of the in situ polymerization on the dispersion of poly(UMM) in the rubber matrix. In this work, we investigated the dispersion mechanism of UMM without rubber matrix for the first time using differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. Three types of UMMs including zinc methacrylate (Zn(MA){sub 2}), sodium methacrylate (Na(MA)) and samarium methacrylate (Sm(MA){sub 3}) were chosen to investigate the in situ self-polymerization of UMM. Based on DSC results, we conclude that the crystals with low melting point tend to self-polymerize first and generate a large amount of heat in the presence of peroxide. The high heat of reaction can melt the crystals with high melting point, and more UMM molecules are dissolved in the rubber matrix, thus increasing the extent of the in situ polymerization. Hence, the UMM with low melting point can self-polymerize to a large extent. Our findings provide in-depth understanding of the dispersion mechanism of UMM in rubber.

In situ self-polymerization of unsaturated metal methacrylate and its dispersion mechanism in rubber-based composites

International Nuclear Information System (INIS)

Wen, Shipeng; Zhou, Yao; Yao, Lu; Zhang, Liqun; Chan, Tung W.; Liang, Yongri; Liu, Li

2013-01-01

Highlights: • In situ self-polymerization of unsaturated metal methacrylate was investigated mainly by the thermal effect. • UMM with low melting point can self-polymerize to a large extent. • The fine dispersion phase is composed of poly(UMM) nanoparticles formed by in situ self-polymerization in the rubber matrix. • The UMM crystals in the presence of peroxide and rubber undergo the processes of melting, diffusion, polymerization, and phase separation in this order. - Abstract: Unsaturated metal methacrylate (UMM) as one kind of functional filler has played an important role in reinforcing rubber materials. The in situ self-polymerization of UMM in UMM/rubber composite leads to the uniform dispersion of poly(UMM) in the rubber matrix, while the crosslinking of rubber and grafting between UMM and rubber chains occur simultaneously, making it difficult to clarify the effect of the in situ polymerization on the dispersion of poly(UMM) in the rubber matrix. In this work, we investigated the dispersion mechanism of UMM without rubber matrix for the first time using differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. Three types of UMMs including zinc methacrylate (Zn(MA) 2 ), sodium methacrylate (Na(MA)) and samarium methacrylate (Sm(MA) 3 ) were chosen to investigate the in situ self-polymerization of UMM. Based on DSC results, we conclude that the crystals with low melting point tend to self-polymerize first and generate a large amount of heat in the presence of peroxide. The high heat of reaction can melt the crystals with high melting point, and more UMM molecules are dissolved in the rubber matrix, thus increasing the extent of the in situ polymerization. Hence, the UMM with low melting point can self-polymerize to a large extent. Our findings provide in-depth understanding of the dispersion mechanism of UMM in rubber

Micro patterning of cell and protein non-adhesive plasma polymerized coatings for biochip applications

DEFF Research Database (Denmark)

Bouaidat, Salim; Berendsen, C.; Thomsen, P.

2004-01-01

Micro scale patterning of bioactive surfaces is desirable for numerous biochip applications. Polyethyleneoxide-like (PEO-like) coating with non-fouling functionality has been deposited using low frequency AC plasma polymerization. The non-fouling properties of the coating were tested with human c...... and versatility of the plasma-polymerized coatings, make this technology highly suitable for bio-MEMS and biochip applications, where patterned high contrast non-fouling surfaces are needed....

Vapor phase polymerization deposition of conducting polymer/graphene nanocomposites as high performance electrode materials.

Science.gov (United States)

Yang, Yajie; Li, Shibin; Zhang, Luning; Xu, Jianhua; Yang, Wenyao; Jiang, Yadong

2013-05-22

In this paper, we report chemical vapor phase polymerization (VPP) deposition of novel poly(3,4-ethylenedioxythiophene) (PEDOT)/graphene nanocomposites as solid tantalum electrolyte capacitor cathode films. The PEDOT/graphene films were successfully prepared on porous tantalum pentoxide surface as cathode films through the VPP procedure. The results indicated that the high conductivity nature of PEDOT/graphene leads to the decrease of cathode films resistance and contact resistance between PEDOT/graphene and carbon paste. This nanocomposite cathode film based capacitor showed ultralow equivalent series resistance (ESR) ca. 12 mΩ and exhibited better capacitance-frequency performance than the PEDOT based capacitor. The leakage current investigation revealed that the device encapsulation process does not influence capacitor leakage current, indicating the excellent mechanical strength of PEDOT-graphene films. The graphene showed a distinct protection effect on the dielectric layer from possible mechanical damage. This high conductivity and mechanical strength graphene based conducting polymer nanocomposites indicated a promising application future for organic electrode materials.

Nucleotide Selectivity in Abiotic RNA Polymerization Reactions

Science.gov (United States)

Coari, Kristin M.; Martin, Rebecca C.; Jain, Kopal; McGown, Linda B.

2017-09-01

In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

Nucleotide Selectivity in Abiotic RNA Polymerization Reactions.

Science.gov (United States)

Coari, Kristin M; Martin, Rebecca C; Jain, Kopal; McGown, Linda B

2017-09-01

In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

Practice insights on patient care-management overview for chemoradiation toxic mucositis-guidelines, guideline-supported therapies and high potency polymerized cross-linked sucralfate (ProThelial).

Science.gov (United States)

McCullough, Ricky W

2018-01-01

Aim To offer a practice insight for the management of chemoradiation toxic mucositis. Method Review chemoradiation toxic mucositis, its pathobiology and breadth of symptom presentation. Review mucositis guidelines and guideline-supported anti-mucositis therapies. Offer guidance on guidelines and an abbreviated review of high potency cross-linked sucralfate for management of chemoradiation toxic mucositis. Result There are six major mucositis guidelines but only one that is current and regularly updated. Guidelines from the Multinational Association Supportive Cancer Care suggest 14 interventions gleaned from controlled trials, 12 of which are off-label uses of therapies that offer statistically significant but incrementally beneficial outcomes. Several evidence-based limitations of guidelines are discussed. Data on high potency polymerized cross-linked sucralfate confirming complete prevention and rapid (2-3 days) elimination, sustained throughout cancer treatment is verified as high quality evidence in accordance to standards adopted by Agency for Healthcare Research and Quality. A 96-97% reduction in mucositis duration qualifies as a positive Glasziou treatment effect, which is discussed as an additional measure of evidence-based medicine. Conclusion Statistically significant but fractional treatment effects of guideline-supported interventions are not likely to substantially alter the course of mucositis when it occurs nor completely prevent its onset. Complete prevention and rapid sustained elimination should be the goal, therefore high potency polymerized cross-linked sucralfate may be useful. Where guidelines fail, institution-based protocols led by oncology pharmacists could succeed. In an effort to eliminate toxic mucositis, enhance compliance to chemoradiation regimens, and improve survival, such protocols for practice may verify pharmacoeconomic benefits, if any, in using high potency polymerized cross-linked sucralfate to manage toxic mucositis.

Bulk-fill resin composites: polymerization contraction, depth of cure, and gap formation.

Science.gov (United States)

Benetti, A R; Havndrup-Pedersen, C; Honoré, D; Pedersen, M K; Pallesen, U

2015-01-01

The bulk-filling of deep, wide dental cavities is faster and easier than traditional incremental restoration. However, the extent of cure at the bottom of the restoration should be carefully examined in combination with the polymerization contraction and gap formation that occur during the restorative procedure. The aim of this study, therefore, was to compare the depth of cure, polymerization contraction, and gap formation in bulk-fill resin composites with those of a conventional resin composite. To achieve this, the depth of cure was assessed in accordance with the International Organization for Standardization 4049 standard, and the polymerization contraction was determined using the bonded-disc method. The gap formation was measured at the dentin margin of Class II cavities. Five bulk-fill resin composites were investigated: two high-viscosity (Tetric EvoCeram Bulk Fill, SonicFill) and three low-viscosity (x-tra base, Venus Bulk Fill, SDR) materials. Compared with the conventional resin composite, the high-viscosity bulk-fill materials exhibited only a small increase (but significant for Tetric EvoCeram Bulk Fill) in depth of cure and polymerization contraction, whereas the low-viscosity bulk-fill materials produced a significantly larger depth of cure and polymerization contraction. Although most of the bulk-fill materials exhibited a gap formation similar to that of the conventional resin composite, two of the low-viscosity bulk-fill resin composites, x-tra base and Venus Bulk Fill, produced larger gaps.

NMR relaxation dispersion of Miglyol molecules confined inside polymeric micro-capsules.

Science.gov (United States)

Nechifor, Ruben; Ardelean, Ioan; Mattea, Carlos; Stapf, Siegfried; Bogdan, Mircea

2011-11-01

Frequency dependent NMR relaxation studies have been carried out on Miglyol molecules confined inside core shell polymeric capsules to obtain a correlation between capsule dimension and the measurable parameters. The polymeric capsules were prepared using an interfacial polymerization technique for three different concentrations of Miglyol. It was shown that the variation of Miglyol concentration influences the capsule dimension. Their average size was estimated using the pulsed field gradient diffusometry technique. The relaxation dispersion curves were obtained at room temperature by a combined use of a fast field cycling instrument and a high-field instrument. The frequency dependence of relaxation rate shows a transition from a diffusion-limited to a surface-limited relaxation regime. Copyright © 2011 John Wiley & Sons, Ltd.

Studies on Rate Enhancement of Polymerization in NMRP

Institute of Scientific and Technical Information of China (English)

HUANG Jian-ying; XU Miao-qing; YAN Ming-fa; CHEN Yi-hong; CHU Jia-yan; ZHUANG Jia-ming; DAI Li-zong; ZOU You-si

2005-01-01

In NMRP, the polymerization of MMA, the polymerization of St and the copolymerization of MMA with St were distinctly accelerated by the addition of a small amount of MN. The polymerization proceeds in a living fashion as indicated by the increase in molecular weight with the increase of time and conversion and a relatively low polydispersity. It has been found that the addition of MN results in a nearly one hundred times higher rate of the polymerization of MMA, a nearly twenty times higher rate of the polymerization of St and a nearly fifteen times higher rate of the copolymerization of St and MMA.

Crosslinked polymeric ionic liquids as solid-phase microextraction sorbent coatings for high performance liquid chromatography.

Science.gov (United States)

Yu, Honglian; Merib, Josias; Anderson, Jared L

2016-03-18

Neat crosslinked polymeric ionic liquid (PIL) sorbent coatings for solid-phase microextraction (SPME) compatible with high-performance liquid chromatography (HPLC) are reported for the first time. Six structurally different PILs were crosslinked to nitinol supports and applied for the determination of select pharmaceutical drugs, phenolics, and insecticides. Sampling conditions including sample solution pH, extraction time, desorption solvent, desorption time, and desorption solvent volume were optimized using design of experiment (DOE). The developed PIL sorbent coatings were stable when performing extractions under acidic pH and remained intact in various organic desorption solvents (i.e., methanol, acetonitrile, acetone). The PIL-based sorbent coating polymerized from the IL monomer 1-vinyl-3-(10-hydroxydecyl) imidazolium chloride [VC10OHIM][Cl] and IL crosslinker 1,12-di(3-vinylbenzylimidazolium) dodecane dichloride [(VBIM)2C12] 2[Cl] exhibited superior extraction performance compared to the other studied PILs. The extraction efficiency of pharmaceutical drugs and phenolics increased when the film thickness of the PIL-based sorbent coating was increased while many insecticides were largely unaffected. Satisfactory analytical performance was obtained with limits of detection (LODs) ranging from 0.2 to 2 μg L(-1) for the target analytes. The accuracy of the analytical method was examined by studying the relative recovery of analytes in real water samples, including tap water and lake water, with recoveries varying from 50.2% to 115.9% and from 48.8% to 116.6%, respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

High-resolution 3D imaging of polymerized photonic crystals by lab-based x-ray nanotomography with 50-nm resolution

Science.gov (United States)

Yin, Leilei; Chen, Ying-Chieh; Gelb, Jeff; Stevenson, Darren M.; Braun, Paul A.

2010-09-01

High resolution x-ray computed tomography is a powerful non-destructive 3-D imaging method. It can offer superior resolution on objects that are opaque or low contrast for optical microscopy. Synchrotron based x-ray computed tomography systems have been available for scientific research, but remain difficult to access for broader users. This work introduces a lab-based high-resolution x-ray nanotomography system with 50nm resolution in absorption and Zernike phase contrast modes. Using this system, we have demonstrated high quality 3-D images of polymerized photonic crystals which have been analyzed for band gap structures. The isotropic volumetric data shows excellent consistency with other characterization results.

Nonperturbative Renormalization Group Approach to Polymerized Membranes

Science.gov (United States)

Essafi, Karim; Kownacki, Jean-Philippe; Mouhanna, Dominique

2014-03-01

Membranes or membrane-like materials play an important role in many fields ranging from biology to physics. These systems form a very rich domain in statistical physics. The interplay between geometry and thermal fluctuations lead to exciting phases such flat, tubular and disordered flat phases. Roughly speaking, membranes can be divided into two group: fluid membranes in which the molecules are free to diffuse and thus no shear modulus. On the other hand, in polymerized membranes the connectivity is fixed which leads to elastic forces. This difference between fluid and polymerized membranes leads to a difference in their critical behaviour. For instance, fluid membranes are always crumpled, whereas polymerized membranes exhibit a phase transition between a crumpled phase and a flat phase. In this talk, I will focus only on polymerized phantom, i.e. non-self-avoiding, membranes. The critical behaviour of both isotropic and anisotropic polymerized membranes are studied using a nonperturbative renormalization group approach (NPRG). This allows for the investigation of the phase transitions and the low temperature flat phase in any internal dimension D and embedding d. Interestingly, graphene behaves just as a polymerized membrane in its flat phase.

Highly Active and Isospecific Styrene Polymerization Catalyzed by Zirconium Complexes Bearing Aryl-substituted [OSSO]-Type Bis(phenolate Ligands

Directory of Open Access Journals (Sweden)

Norio Nakata

2016-01-01

Full Text Available [OSSO]-type dibenzyl zirconium(IV complexes 9 and 10 possessing aryl substituents ortho to the phenoxide moieties (ortho substituents, phenyl and 2,6-dimethylphenyl (Dmp were synthesized and characterized. Upon activation with dMAO (dried methylaluminoxane, complex 9 was found to promote highly isospecific styrene polymerizations ([mm] = 97.5%–99% with high molecular weights Mw up to 181,000 g·mmol−1. When the Dmp-substituted pre-catalyst 10/dMAO system was used, the highest activity, over 7700 g·mmol(10−1·h−1, was recorded involving the formation of precisely isospecific polystyrenes of [mm] more than 99%.

AZIDE-ALKYNE CLICK POLYMERIZATION: AN UPDATE

Institute of Scientific and Technical Information of China (English)

Hong-kun Li; Jing-zhi Sun; An-jun Qin; Ben Zhong Tang

2012-01-01

The great achievements of click chemistry have encouraged polymer scientists to use this reaction in their field.This review assembles an update of the advances of using azide-alkyne click polymerization to prepare functional polytriazoles (PTAs) with linear and hyperbranched structures.The Cu(Ⅰ)-mediated click polymerization furnishes 1,4-regioregular PTAs,whereas,the metal-free click polymerization of propiolates and azides produces PTAs with 1,4-regioisomer contents up to 90％.The PTAs display advanced functions,such as aggregation-induced emission,thermal stability,biocompatibility and optical nonlinearity.

Preparation and characterization of pyrromethene-567 dye-doped polymer samples using Gamma Irradiation Polymerization Method (GIPM)

Energy Technology Data Exchange (ETDEWEB)

Al-Ghamdi, Attieh A., E-mail: aaaalghamdi4@kau.edu.sa [Center of Nanotechnology, King Abdulaziz University, Jeddah (Saudi Arabia); Mahrous, Eiman M. [Taibah University, Department of Physics, Madinah (Saudi Arabia); Al-Enizi, Abdullah M. [King Saud University, Department of Chemistry, Riyadh (Saudi Arabia); Azam, Ameer [Center of Nanotechnology, King Abdulaziz University, Jeddah (Saudi Arabia)

2015-01-15

Dye-doped polymer gain media laser samples of pyrromethene-567 in a mixture with methyl methacrylate and 2-hydroxyethyl methacrylate copolymer have been prepared and synthesized by the Conventional Thermal Polymerization Method (CTPM) using an oven, and by the Gamma Irradiation Polymerization Method (GIPM) using Cobalt-60 ({sup 60}Co). Physical properties comprising absorption molar coefficients, absorption cross sections, fluorescence quantum yields, fluorescence life times, and emission cross sections were determined and calculated from the measured absorption and emission spectra. The efficiency and photo-stability of samples fabricated by both methods were measured and compared. The time required for synthesis was reduced by 90% using the GIPM. Complete polymerization of the GIPM sample was found to be at 7 kGy. Further, the GIPM produces high laser damage resistance material, which might be attributed to the highly dense polymeric network structure formed as a result of the effect of gamma radiation on MMA and HEMA monomers. - Highlights: • Samples of PM-567 in a mixture with MMA/HEMA were synthesized by the GIPM. • The time required for synthesis was reduced by 90% using the GIPM. • Complete polymerization of the GIPM sample was at 7 kGy. • The laser media produced is fast and free of contamination that gives high purity material. • The GIPM produced a high laser damage resistance material.

Effects of Prepolymerized Particle Size and Polymerization Kinetics on Volumetric Shrinkage of Dental Modeling Resins

Directory of Open Access Journals (Sweden)

Tae-Yub Kwon

2014-01-01

Full Text Available Dental modeling resins have been developed for use in areas where highly precise resin structures are needed. The manufacturers claim that these polymethyl methacrylate/methyl methacrylate (PMMA/MMA resins show little or no shrinkage after polymerization. This study examined the polymerization shrinkage of five dental modeling resins as well as one temporary PMMA/MMA resin (control. The morphology and the particle size of the prepolymerized PMMA powders were investigated by scanning electron microscopy and laser diffraction particle size analysis, respectively. Linear polymerization shrinkage strains of the resins were monitored for 20 minutes using a custom-made linometer, and the final values (at 20 minutes were converted into volumetric shrinkages. The final volumetric shrinkage values for the modeling resins were statistically similar (P>0.05 or significantly larger (P<0.05 than that of the control resin and were related to the polymerization kinetics (P<0.05 rather than the PMMA bead size (P=0.335. Therefore, the optimal control of the polymerization kinetics seems to be more important for producing high-precision resin structures rather than the use of dental modeling resins.

Highly efficient one-pot/one-step synthesis of multiblock copolymers from three-component polymerization of carbon dioxide, epoxide and lactone.

Science.gov (United States)

Li, Yang; Hong, Jiali; Wei, Renjian; Zhang, Yingying; Tong, Zaizai; Zhang, Xinghong; Du, Binyang; Xu, Junting; Fan, Zhiqiang

2015-02-01

It is a long-standing challenge to combine mixed monomers into multiblock copolymer (MBC) in a one-pot/one-step polymerization manner. We report the first example of MBC with biodegradable polycarbonate and polyester blocks that were synthesized from highly efficient one-pot/one-step polymerization of cyclohexene oxide (CHO), CO 2 and ε-caprolactone (ε-CL) in the presence of zinc-cobalt double metal cyanide complex and stannous octoate. In this protocol, two cross-chain exchange reactions (CCER) occurred at dual catalysts respectively and connected two independent chain propagation procedures ( i.e. , polycarbonate formation and polyester formation) simultaneously in a block-by-block manner, affording MBC without tapering structure. The multiblock structure of MBC was determined by the rate ratio of CCER to the two chain propagations and could be simply tuned by various kinetic factors. This protocol is also of significance due to partial utilization of renewable CO 2 and improved mechanical properties of the resultant MBC.

A new lithography of functional plasma polymerized thin films

International Nuclear Information System (INIS)

Kim, Sung-O

2001-01-01

The preparation of the resist for the vacuum lithography was carried out by plasma polymerization. The resist manufactured by plasma polymerization is a monomer produced by MMA (Methyl methacrylate). The functional groups of MMA appeared in the PPMMA (Plasma Polymerized Methyl methacrylate) as well, and this was confirmed through an analysis using FT-IR. The polymerization rate increased as a function of the plasma power and decreased as a function of the system pressure. The sensitivity and contrast of the plasma polymerized thin films were 15 μC/cm2 and 4.3 respectively. The size of the pattern manufactured by Vacuum Lithography using the plasma polymerized thin films was 100 nm

Gamma irradiation effect on acrylated-epoxidized soybean oil: polymerization and characterization

International Nuclear Information System (INIS)

Hernandez-lopez, S.; Sanchez-Mendieta, V.; Vigueras-Santiago, E.; Martin Del Campo-Lopez, E.; Urena-Nunez, F.

2006-01-01

In this work we present the gamma-irradiation dose effect on acrylated-epoxidized soybean oil (AESO). AESO started to polymerize at 12 kGy and at higher doses (24, 110 and 340 kGy) there is an increase in cross-linking reaction without degradation, thermal or structural changes. Polymeric products were glassy, thermosetting, insoluble, which no longer melt upon heating, and no Tg was observed between -30 to 300 deg C. These polymers were obtained with a specific shape and different properties in comparison with the thermal PolyAESO (rubber) due to higher cross-linking achieved by gamma irradiation. NMR, FT-IR and DSC techniques evidenced these facts. Friction and scratching properties were dependent of irradiation dose. Due to an increase in cross-linking density, lower friction values, reached at high doses (110 and 340 kGy), were accompanied by a lower scratching penetration depth in these polymers. Gamma-ray polymerization could be an alternative and efficient method for in situ synthesis of thermosetting polymers, copolymers and composites with given shapes, controlled polymerization degrees and optimized properties

Cross-linking of polymeric materials

International Nuclear Information System (INIS)

Bloom, L.I.; Du Plessis, T.A.; Meij, G.O.

1991-01-01

The invention provides a method of producing a cured polymeric artifact from a polymeric thermoplastic starting material, the material of the artifact having reduced thermoplasticity relative to the starting material and exhibiting an enhanced degree of cross-linking relative to the starting material. The method includes subjecting a polymeric thermoplastic starting material, which is capable of being cross-linked by irradiation, to sufficient irradiation partially to cross-linked the starting material to produce a thermoplastic partially cross-linked intermediate material. The thermoplasticity of the intermediate material is then reduced by heating it to raise its melting point. The invention also provides a method of making a partially cross-linked feedstocks and a master batch for use in making such artifacts

Ring-opening polymerization of ω-pentadecalactone catalyzed by phosphazene superbases

KAUST Repository

Ladelta, Viko

2016-12-12

A fast and living ring-opening polymerization (ROP) of ω-pentadecalactone (PDL), a representative monomer of macrolactones, was achieved using a primary alcohol as the initiator and t-BuP or t-octP as the catalyst. The use of t-BuP instead of the t-BuP superbase slows down the polymerization rate. The ROP of PDL proceeds to high conversion not only at 80 °C in bulk but also at room temperature and in dilute solution. The synthesized PDL homopolymers and block copolymers with poly(ethylene glycol) were characterized by high-temperature GPC (HT-GPC), H NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Melting temperatures, determined by differential scanning calorimetry, are also reported.

Ring-opening polymerization of ω-pentadecalactone catalyzed by phosphazene superbases

KAUST Repository

Ladelta, Viko; Bilalis, Panayiotis; Gnanou, Yves; Hadjichristidis, Nikolaos

2016-01-01

A fast and living ring-opening polymerization (ROP) of ω-pentadecalactone (PDL), a representative monomer of macrolactones, was achieved using a primary alcohol as the initiator and t-BuP or t-octP as the catalyst. The use of t-BuP instead of the t-BuP superbase slows down the polymerization rate. The ROP of PDL proceeds to high conversion not only at 80 °C in bulk but also at room temperature and in dilute solution. The synthesized PDL homopolymers and block copolymers with poly(ethylene glycol) were characterized by high-temperature GPC (HT-GPC), H NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Melting temperatures, determined by differential scanning calorimetry, are also reported.

Fluid Effects in Polymers and Polymeric Composites

CERN Document Server

Weitsman, Y Jack

2012-01-01

Fluid Effects in Polymers and Polymeric Composites, written by the late Dr. Y. Jack Weitsman, addresses the wide range of parameters that affect the interaction of fluids with polymers and polymeric composites. The book aims at broadening the scope of available data, mostly limited up to this time to weight-gain recordings of fluid ingress into polymers and composites, to the practical circumstances of fluctuating exposure. Various forms of experimental data are given, in conjunction with theoretical models derived from basic scientific principles, and correlated with severity of exposure conditions and interpreted by means of rationally based theoretical models. The practical implications of the effects of fluids are discussed. The issue of fluid effects on polymers and polymeric composites is of concern to engineers and scientists active in aerospace and naval structures, as an increasing portion of these structures are made of polymeric composites and employ polymeric adhesives as a joining device. While...

Tubulin polymerization-stimulating activity of Ganoderma triterpenoids.

Science.gov (United States)

Kohno, Toshitaka; Hai-Bang, Tran; Zhu, Qinchang; Amen, Yhiya; Sakamoto, Seiichi; Tanaka, Hiroyuki; Morimoto, Satoshi; Shimizu, Kuniyoshi

2017-04-01

Tubulin polymerization is an important target for anticancer therapies. Even though the potential of Ganoderma triterpenoids against various cancer targets had been well documented, studies on their tubulin polymerization-stimulating activity are scarce. This study was conducted to evaluate the effect of Ganoderma triterpenoids on tubulin polymerization. A total of twenty-four compounds were investigated using an in vitro tubulin polymerization assay. Results showed that most of the studied triterpenoids exhibited microtuble-stabilizing activity to different degrees. Among the investigated compounds, ganoderic acid T-Q, ganoderiol F, ganoderic acid S, ganodermanontriol and ganoderic acid TR were found to have the highest activities. A structure-activity relationship (SAR) analysis was performed. Extensive investigation of the SAR suggests the favorable structural features for the tubulin polymerization-stimulating activity of lanostane triterpenes. These findings would be helpful for further studies on the potential mechanisms of the anticancer activity of Ganoderma triterpenoids and give some indications on the design of tubulin-targeting anticancer agents.

A qualitative chemometric study of resin composite polymerization

Directory of Open Access Journals (Sweden)

Regina Ferraz Mendes

2008-01-01

Full Text Available Objective: An experiment was carried out to assess the effect produced by different polymerization techniques on resin composite color after it has been immersed in coffee. Methods: Samples were manufactured using TPH Spectrum composite. It was polymerized for 10 or 40 seconds, with the light tip at one or zero millimeters from the resin surface, and afterwards the samples were immersed in coffee for 24 hours or 7 days. Ten different evaluators classified the samples according to their degree of staining. Results: The samples that were polymerized for 10 seconds were more susceptible to staining than the ones polymerized by 40 seconds. Samples immersed in coffee for 7 days were more susceptible to staining than the ones immersed for 24 hours. Conclusion: The variables polymerization time and immersion time were determinant in the staining susceptibility of the studied composite by coffee. However, there was no significant difference, irrespective of whether the resin was polymerized 10 or zero millimeters away from the resin surface.

Radiation-induced emulsion polymerization of tetrafluoroethylene

International Nuclear Information System (INIS)

Suwa, Takeshi

1979-10-01

The radiation-induced emulsifier-free emulsion polymerization of tetrafluoroethylene (TFE) has been studied at initial pressure 2 - 25 kg/cm 2 and temperature 30 0 - 110 0 C for dose rate 0.57 x 10 4 - 3.0 x 10 4 rad/hr. Polytetrafluoroethylene (PTFE), a hydrophobic polymer, forms as a stable latex in the absence of an emulsifier. Stability of the latex is governed by the dose rate/TFE pressure ratio; it increases with sufficient TFE monomer. PTFE particles produced in this polymerization system are stable due to the carboxyl end groups and adsorption of OH - and HF on the particles. PTFE latex of molecular weight higher than 2 x 10 7 is obtained by addition of a radical scavenger such as hydroquinone. The molecular weight of PTFE can be measured from the heat of crystallization conveniently with high reliability, which was found in the course of study on the melting and crystallization behavior. (author)

Volumetric polymerization shrinkage of contemporary composite resins

OpenAIRE

Nagem Filho, Halim; Nagem, Haline Drumond; Francisconi, Paulo Afonso Silveira; Franco, Eduardo Batista; Mondelli, Rafael Francisco Lia; Coutinho, Kennedy Queiroz

2007-01-01

The polymerization shrinkage of composite resins may affect negatively the clinical outcome of the restoration. Extensive research has been carried out to develop new formulations of composite resins in order to provide good handling characteristics and some dimensional stability during polymerization. The purpose of this study was to analyze, in vitro, the magnitude of the volumetric polymerization shrinkage of 7 contemporary composite resins (Definite, Suprafill, SureFil, Filtek Z250, Fill ...

Theoretical Investigation of Oxazine 170 Perchlorate Doped Polymeric Optical Fiber Amplifier

Directory of Open Access Journals (Sweden)

Piotr Miluski

2017-01-01

Full Text Available Optical signal amplification in the waveguiding structure of optical fibers can be used for optical telecommunication systems and new light sources constructions. Organic dyes doped materials are interesting for new applications in polymeric optical fibers technology due to their benefits (efficient fluorescence, high absorption cross section, and easy processing. This article presents a numerical simulation of gain in poly(methyl methacrylate optical fiber doped by Oxazine 170 Perchlorate. The calculated gain characteristic for the used dye molar concentration (0.2·10-6–1.4·10-6 and pump power (1–10 kW is presented. The fabricated fluorescent polymeric optical fiber is also shown. The presented analysis can be used for optical amplifier construction based on dye-doped polymeric optical fiber (POF.

High-definition polymeric membranes: construction of 3D lithographed channel arrays through control of natural building blocks dynamics.

Science.gov (United States)

Speranza, Valentina; Trotta, Francesco; Drioli, Enrico; Gugliuzza, Annarosa

2010-02-01

The fabrication of well-defined interfaces is in high demand in many fields of biotechnologies. Here, high-definition membrane-like arrays are developed through the self-assembly of water droplets, which work as natural building blocks for the construction of ordered channels. Solution viscosity together with the dynamics of the water droplets can decide the final formation of three-dimensional well-ordered patterns resembling anodic structures, especially because solvents denser than water are used. Particularly, the polymer solution viscosity is demonstrated to be a powerful tool for control of the mobility of submerged droplets during the microfabrication process. The polymeric patterns are structured at very high levels of organization and exhibit well-established transport-surface property relationships, considered basics for any types of advanced biotechnologies.

Deformation and flow of polymeric materials

CERN Document Server

Münstedt, Helmut

2014-01-01

This book describes the properties of single polymer molecules and polymeric materials and the methods how to characterize them. Molar masses, molar mass distributions and branching structure are discussed in detail. These properties are decisive for a deeper understanding of structure/properties relationships of polymeric materials. This book therefore describes and discusses them in detail. The mechanical behavior as a function of time and temperature is a key subject of the book. The authors present it on the basis of many original results they have obtained in their long research careers. They present the temperature dependence of mechanical properties of various polymeric materials in a wide temperature range: from cryogenic temperatures to the melt. Besides an extensive data collection on the transitions of various different polymeric materials, they also carefully present the physical explanations of the observed phenomena. Glass transition and melting temperatures are discussed, particularly, with the...

Synthesis of High cis-Polybutadiene in Styrene Solution with Neodymium-Based Catalysts: Towards the Preparation of HIPS and ABS via In Situ Bulk Polymerization

Directory of Open Access Journals (Sweden)

Ramón Díaz de León

2016-01-01

Full Text Available In a first step, 1,3-butadiene was selectively polymerized at 60°C in styrene as solvent using NdV3/DIBAH/EASC as the catalyst system. The catalyst system activation process, the addition order of monomers and catalyst components, and the molar ratios [Al]/[Nd] and [Cl]/[Nd] were studied. The catalyst system allowed the selective 1,3-butadiene polymerization, reaching conversions between 57.5 and 88.1% with low polystyrene contents in the order of 6.3 to 15.4%. Molecular weights ranging from 39,000 to 150,000 g/mol were obtained, while cis-1,4 content was found in the interval of 94.4 to 96.4%. On the other hand, the glass transition temperatures of synthesized materials were established in the range of −101.9 to −107.4°C, explained by the presence of polystyrene segments in the polybutadiene chains; in the same sense, the polybutadienes did not show the typical melting endotherm of high cis-polybutadienes. In a second step, the resulting styrene/high cis-1,4 polybutadiene solutions were used to synthesize ABS (adding a fraction of acrylonitrile monomer and HIPS via in situ bulk polymerizations and the results were discussed in terms of morphological development, molecular parameters, dynamical mechanical behavior, and mechanical properties.

Use of computed tomography in nondestructive testing of polymeric materials

International Nuclear Information System (INIS)

Persson, S.; Oestman, E.

1985-01-01

Computed tomography has been used to detect imperfections and to measure cross-link density gradients in polymeric products, such as airplane tires, rubber shock absorbers, and filament-wound high-pressure tanks

Evaluation of linear polymerization shrinkage, flexural strength and modulus of elasticity of dental composites

Directory of Open Access Journals (Sweden)

Gabriela Queiroz de Melo Monteiro

2010-03-01

Full Text Available Linear polymerization shrinkage (LPS, flexural strength (FS and modulus of elasticity (ME of 7 dental composites (Filtek Z350™, Filtek Z250™/3M ESPE; Grandio™, Polofil Supra™/VOCO; TPH Spectrum™, TPH3™, Esthet-X™/Denstply were measured. For the measurement of LPS, composites were applied to a cylindrical metallic mold and polymerized (n = 8. The gap formed at the resin/mold interface was observed using scanning electron microscopy (1500×. For FS and ME, specimens were prepared according to the ISO 4049 specifications (n = 10. Statistical analysis of the data was performed with one-way ANOVA and the Tukey test. TPH Spectrum presented significantly higher LPS values (29.45 µm. Grandio had significantly higher mean values for FS (141.07 MPa and ME (13.91 GPa. The relationship between modulus of elasticity and polymerization shrinkage is the main challenge for maintenance of the adhesive interface, thus composites presenting high shrinkage values, associated with a high modulus of elasticity tend to disrupt the adhesive interface under polymerization.

21 CFR 870.3650 - Pacemaker polymeric mesh bag.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Pacemaker polymeric mesh bag. 870.3650 Section 870...) MEDICAL DEVICES CARDIOVASCULAR DEVICES Cardiovascular Prosthetic Devices § 870.3650 Pacemaker polymeric mesh bag. (a) Identification. A pacemaker polymeric mesh bag is an implanted device used to hold a...

Elaboration of highly hydrophobic polymeric surface — a potential strategy to reduce the adhesion of pathogenic bacteria?

Energy Technology Data Exchange (ETDEWEB)

Poncin-Epaillard, F., E-mail: fabienne.poncin-epaillard@univ-lemans.fr [Institut des Molécules et Matériaux du Mans (IMMM), département Polymères, Colloïdes et Interfaces, UMR CNRS 6283 Université LUNAM, av. O. Messiaen, 72085 Le Mans (France); Herry, J.M. [INRA-AgroParisTech, UMR 1319 MICALIS, équipe B2HM, 25 avenue de la République, 91300 Massy (France); Marmey, P.; Legeay, G. [CTTM, 20 rue Thalès de Milet 72000 Le Mans (France); Debarnot, D. [Institut des Molécules et Matériaux du Mans (IMMM), département Polymères, Colloïdes et Interfaces, UMR CNRS 6283 Université LUNAM, av. O. Messiaen, 72085 Le Mans (France); Bellon-Fontaine, M.N. [INRA-AgroParisTech, UMR 1319 MICALIS, équipe B2HM, 25 avenue de la République, 91300 Massy (France)

2013-04-01

Different polymeric surfaces have been modified in order to reach a high hydrophobic character, indeed the superhydrophobicity property. For this purpose, polypropylene and polystyrene have been treated by RF or μwaves CF{sub 4} plasma with different volumes, the results were compared according to the density of injected power. The effect of pretreatment such as mechanical abrasion or plasma activation was also studied. The modified surfaces were shown as hydrophobic, or even superhydrophobic depending of defects density. They were characterized by measurement of wettability and roughness at different scales, i.e. macroscopic, mesoscopic and atomic. It has been shown that a homogeneous surface at the macroscopic scale could be heterogeneous at lower mesoscopic scale. This was associated with the crystallinity of the material. The bioadhesion tests were performed with Gram positive and negative pathogenic strains: Listeria monocytogenes, Pseudomonas aeruginosa and Hafnia alvei. They have demonstrated an antibacterial efficiency of very hydrophobic and amorphous PS treated for all strains tested and a strain-dependent efficiency with modified PP surface being very heterogeneous at the mesoscopic scale. Thus, these biological results pointed out not only the respective role of the surface chemistry and topography in bacterial adhesion, but also the dependence on the peaks and valley distribution at bacteria dimension scale. Highlights: ► Simple, eco-friendly modification of polymers leading to highly hydrophobic property ► Plasma treatment inducing surface fluorination and roughness ► Study of non-adhesion of different types of bacteria onto such polymeric surfaces ► Dependence of their non-adhesion on surface topography whatever their characteristics.

Highly Branched Polyisobutylene by Radical Polymerization under Li[CB11(CH3)(12)] Catalysis

Czech Academy of Sciences Publication Activity Database

Volkis, V.; Shoemaker, R. K.; Michl, Josef

2012-01-01

Roč. 45, č. 23 (2012), s. 9250-9257 ISSN 0024-9297 Institutional research plan: CEZ:AV0Z40550506 Keywords : Dodecamethylcarba-closo-dodecaborate(-)Anion * polymerization * LiCB11(CH3)(12) Subject RIV: CC - Organic Chemistry Impact factor: 5.521, year: 2012

RAFT polymerization and some of its applications.

Science.gov (United States)

Moad, Graeme; Rizzardo, Ezio; Thang, San H

2013-08-01

Reversible addition-fragmentation chain transfer (RAFT) is one of the most robust and versatile methods for controlling radical polymerization. With appropriate selection of the RAFT agent for the monomers and reaction conditions, it is applicable to the majority of monomers subject to radical polymerization. The process can be used in the synthesis of well-defined homo-, gradient, diblock, triblock, and star polymers and more complex architectures, which include microgels and polymer brushes. In this Focus Review we describe how the development of RAFT and RAFT application has been facilitated by the adoption of continuous flow techniques using tubular reactors and through the use of high-throughput methodology. Applications described include the use of RAFT in the preparation of polymers for optoelectronics, block copolymer therapeutics, and star polymer rheology control agents. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study on radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. II. Radiation-induced polymerization of methyl methacrylate adsorbed on several inorganic substances

International Nuclear Information System (INIS)

Fukano, K.; Kageyama, E.

1975-01-01

The radiation-induced polymerization of methyl methacrylate (MMA) adsorbed on such inorganic substances as silica gel, white carbon, silicic acid anhydride, zeolite, and activated alumina was carried out to compare with the case of styrene. The rate of radiation-induced polymerization adsorbed on inorganic substances was high compared with that of radiation-induced bulk state polymerization, as was the case with styrene. Inorganic substrates which contain aluminum as a component element are more likely to be grafted than those which consist of SiO 2 alone, as with styrene. The molecular weight distribution of unextractable polymer and extractable polymer differs, depending on the type of inorganic substance. Experiments by a preirradiation method were carried out in case of silica gel, white carbon, and silicic acid anhydride. GPC spectra of the polymer obtained were different from those of polymer formed by the simultaneous irradiation method. It appears that all the unextractable polymer is grafted to the inorganic surface with chemical bond

Cascade synthesis of chiral block copolymers combining lipase catalyzed ring opening polymerization and atom transfer radical polymerization

NARCIS (Netherlands)

Peeters, J.W.; Palmans, A.R.A.; Veld, M.A.J.; Scheijen, F.J.E.; Heise, A.; Meijer, E.W.

2004-01-01

The enantioselective polymerization of methyl-substituted -caprolactones using Novozym 435 as the catalyst was investigated. All substituted monomers could be polymerized except 6-methyl--caprolactone (6-MeCL), which failed to propagate after ring opening. Interestingly, an odd-even effect in the

FtsZ Polymerization Assays : Simple Protocols and Considerations

NARCIS (Netherlands)

Król, Ewa; Scheffers, Dirk-Jan

2013-01-01

During bacterial cell division, the essential protein FtsZ assembles in the middle of the cell to form the so-called Z-ring. FtsZ polymerizes into long filaments in the presence of GTP in vitro, and polymerization is regulated by several accessory proteins. FtsZ polymerization has been extensively

Glycine Polymerization on Oxide Minerals

Science.gov (United States)

Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

2017-06-01

It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH3 + group of adsorbed Gly to the nucleophilic NH2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

Glycine Polymerization on Oxide Minerals.

Science.gov (United States)

Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

2017-06-01

It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH 3 + group of adsorbed Gly to the nucleophilic NH 2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

Template Synthesis of Nanostructured Polymeric Membranes by Inkjet Printing.

Science.gov (United States)

Gao, Peng; Hunter, Aaron; Benavides, Sherwood; Summe, Mark J; Gao, Feng; Phillip, William A

2016-02-10

The fabrication of functional nanomaterials with complex structures has been serving great scientific and practical interests, but current fabrication and patterning methods are generally costly and laborious. Here, we introduce a versatile, reliable, and rapid method for fabricating nanostructured polymeric materials. The novel method is based on a combination of inkjet printing and template synthesis, and its utility and advantages in the fabrication of polymeric nanomaterials is demonstrated through three examples: the generation of polymeric nanotubes, nanowires, and thin films. Layer-by-layer-assembled nanotubes can be synthesized in a polycarbonate track-etched (PCTE) membrane by printing poly(allylamine hydrochloride) and poly(styrenesulfonate) sequentially. This sequential deposition of polyelectrolyte ink enables control over the surface charge within the nanotubes. By a simple change of the printing conditions, polymeric nanotubes or nanowires were prepared by printing poly(vinyl alcohol) in a PCTE template. In this case, the high-throughput nature of the method enables functional nanomaterials to be generated in under 3 min. Furthermore, we demonstrate that inkjet printing paired with template synthesis can be used to generate patterns comprised of chemically distinct nanomaterials. Thin polymeric films of layer-by-layer-assembled poly(allylamine hydrochloride) and poly(styrenesulfonate) are printed on a PCTE membrane. Track-etched membranes covered with the deposited thin films reject ions and can potentially be utilized as nanofiltration membranes. When the fabrication of these different classes of nanostructured materials is demonstrated, the advantages of pairing template synthesis with inkjet printing, which include fast and reliable deposition, judicious use of the deposited materials, and the ability to design chemically patterned surfaces, are highlighted.

Identification of a premature termination of DNA polymerization in ...

Indian Academy of Sciences (India)

2013-04-25

Apr 25, 2013 ... strands to the 5′ end of the template strands, forming double- stranded DNA with ... duplex stem is important for high processive polymerization. HIV-1 reverse ... KF has been used as a model to study DNA polymerase.

Dual-cyclical nucleic acid strand-displacement polymerization based signal amplification system for highly sensitive determination of p53 gene.

Science.gov (United States)

Xu, Jianguo; Wu, Zai-Sheng; Li, Hongling; Wang, Zhenmeng; Le, Jingqing; Zheng, Tingting; Jia, Lee

2016-12-15

In the present study, we proposed a novel dual-cyclical nucleic acid strand-displacement polymerization (dual-CNDP) based signal amplification system for highly sensitive determination of tumor suppressor genes. The system primarily consisted of a signaling hairpin probe (SHP), a label-free hairpin probe (LHP) and an initiating primer (IP). The presence of target DNA was able to induce one CNDP through continuous process of ligation, polymerization and nicking, leading to extensively accumulation of two nicked triggers (NT1 and NT2). Intriguingly, the NT1 could directly hybridize SHP, while the NT2 could act as the target analog to induce another CNDP. The resulting dual-CNDP contributed the striking signal amplification, and only a very weak blank noise existed since the ligation template of target was not involved. In this case, the target could be detected in a wide linear range (5 orders of magnitude), and a low detection limit (78 fM) was obtained, which is superior to most of the existing fluorescent methods. Moreover, the dual-CNDP sensing system provided a high selectivity towards target DNA against mismatched target and was successfully applied to analysis of target gene extracted from cancer cells or in human serum-contained samples, indicating its great potential for practical applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Comparative study of transgenic Brachypodium distachyon expressing sucrose:fructan 6-fructosyltransferases from wheat and timothy grass with different enzymatic properties.

Science.gov (United States)

Tamura, Ken-Ichi; Sanada, Yasuharu; Tase, Kazuhiro; Kawakami, Akira; Yoshida, Midori; Yamada, Toshihiko

2014-04-01

Fructans can act as cryoprotectants and contribute to freezing tolerance in plant species, such as in members of the grass subfamily Pooideae that includes Triticeae species and forage grasses. To elucidate the relationship of freezing tolerance, carbohydrate composition and degree of polymerization (DP) of fructans, we generated transgenic plants in the model grass species Brachypodium distachyon that expressed cDNAs for sucrose:fructan 6-fructosyltransferases (6-SFTs) with different enzymatic properties: one cDNA encoded PpFT1 from timothy grass (Phleum pratense), an enzyme that produces high-DP levans; a second cDNA encoded wft1 from wheat (Triticum aestivum), an enzyme that produces low-DP levans. Transgenic lines expressing PpFT1 and wft1 showed retarded growth; this effect was particularly notable in the PpFT1 transgenic lines. When grown at 22 °C, both types of transgenic line showed little or no accumulation of fructans. However, after a cold treatment, wft1 transgenic plants accumulated fructans with DP = 3-40, whereas PpFT1 transgenic plants accumulated fructans with higher DPs (20 to the separation limit). The different compositions of the accumulated fructans in the two types of transgenic line were correlated with the differences in the enzymatic properties of the overexpressed 6-SFTs. Transgenic lines expressing PpFT1 accumulated greater amounts of mono- and disaccharides than wild type and wft1 expressing lines. Examination of leaf blades showed that after cold acclimation, PpFT1 overexpression increased tolerance to freezing; by contrast, the freezing tolerance of the wft1 expressing lines was the same as that of wild type plants. These results provide new insights into the relationship of the composition of water-soluble carbohydrates and the DP of fructans to freezing tolerance in plants.

Polypropylene/graphite nanocomposites by in situ polymerization

International Nuclear Information System (INIS)

Milani, Marceo A.; Galland, Giselda B.; Quijada, Raul

2011-01-01

This work presents the synthesis of nanocomposites of polypropylene/graphite by in situ polymerization using metallocene catalyst and graphene nanosheets. Initially was analyzed which of the metallocene catalysts rac-Et(Ind) 2 ZrCl 2 or rac-Me 2 Si(Ind) 2 ZrCl 2 produces polypropylene with mechanical properties more relevant. Then it were performed the in situ polymerization reactions to obtain the nanocomposites. The polymeric materials were characterized by XRD, DSC, GPC and DMTA. (author)

Nanoimages show disruption of tubulin polymerization by chlorpyrifos oxon: Implications for neurotoxicity

International Nuclear Information System (INIS)

Grigoryan, Hasmik; Lockridge, Oksana

2009-01-01

Organophosphorus agents cause cognitive deficits and depression in some people. We hypothesize that the mechanism by which organophosphorus agents cause these disorders is by modification of proteins in the brain. One such protein could be tubulin. Tubulin polymerizes to make the microtubules that transport cell components to nerve axons. The goal of the present work was to measure the effect of the organophosphorus agent chlorpyrifos oxon on tubulin polymerization. An additional goal was to identify the amino acids covalently modified by chlorpyrifos oxon in microtubule polymers and to compare them to the amino acids modified in unpolymerized tubulin dimers. Purified bovine tubulin (0.1 mM) was treated with 0.005-0.1 mM chlorpyrifos oxon for 30 min at room temperature and then polymerized by addition of 1 mM GTP to generate microtubules. Microtubules were visualized by atomic force microscopy. Chlorpyrifos oxon-modified residues were identified by tandem ion trap electrospray ionization and matrix-assisted laser desorption/ionization mass spectrometry of tryptic peptides. Nanoimaging showed that low concentrations (0.005 and 0.01 mM) of chlorpyrifos oxon yielded short, thin microtubules. A concentration of 0.025 mM stimulated polymerization, while high concentrations (0.05 and 0.1 mM) caused aggregation. Of the 17 tyrosines covalently modified by chlorpyrifos oxon in unpolymerized tubulin dimers, only 2 tyrosines were labeled in polymerized microtubules. The two labeled tyrosines in polymerized tubulin were Tyr 103 in EDAANNY*R of alpha tubulin, and Tyr 281 in GSQQY*R of beta tubulin. In conclusion, chlorpyrifos oxon binding to tubulin disrupts tubulin polymerization. These results may lead to an understanding of the neurotoxicity of organophosphorus agents.

Efficiency of polymerization of bulk-fill composite resins: a systematic review.

Science.gov (United States)

Reis, André Figueiredo; Vestphal, Mariana; Amaral, Roberto Cesar do; Rodrigues, José Augusto; Roulet, Jean-François; Roscoe, Marina Guimarães

2017-08-28

This systematic review assessed the literature to evaluate the efficiency of polymerization of bulk-fill composite resins at 4 mm restoration depth. PubMed, Cochrane, Scopus and Web of Science databases were searched with no restrictions on year, publication status, or article's language. Selection criteria included studies that evaluated bulk-fill composite resin when inserted in a minimum thickness of 4 mm, followed by curing according to the manufacturers' instructions; presented sound statistical data; and comparison with a control group and/or a reference measurement of quality of polymerization. The evidence level was evaluated by qualitative scoring system and classified as high-, moderate- and low- evidence level. A total of 534 articles were retrieved in the initial search. After the review process, only 10 full-text articles met the inclusion criteria. Most articles included (80%) were classified as high evidence level. Among several techniques, microhardness was the most frequently method performed by the studies included in this systematic review. Irrespective to the "in vitro" method performed, bulk fill RBCs were partially likely to fulfill the important requirement regarding properly curing in 4 mm of cavity depth measured by depth of cure and / or degree of conversion. In general, low viscosities BFCs performed better regarding polymerization efficiency compared to the high viscosities BFCs.

Study on the immobilization of alpha-amylase by radiation-induced polymerization at low-temperature, (3)

International Nuclear Information System (INIS)

Yoshida, Masaru; Kumakura, Minoru; Kaetsu, Isao

1975-07-01

The immobilization of α-amylase in high concentration (50-200 mg) by radiation induced polymerization at low temperature, with HEMA has been studied. A feature of the high concentration α-amylase system is phase separation of the mixed solution prior to polymerization, markedly at HEMA concentrations above 50%. Useful immobilization is possible, however, by irradiation of the suspended composition at -196 0 C, which is obtained by shaking the phase-separated system. At temperatures below 0 0 C, the immobilization is possible, but not above this because of the phase separation. The polymerizability of HEMA changes abruptly at 0 0 C. The largest polymerization rate is obtained at -24 0 C, possibly due to phase change by crystallization of water of the buffer solution at 0 0 C. Activity of the immobilized high-concentration α-amylase is as high as 80-85% being somewhat higher than that in the low-concentration case. (auth.)

A guide to the synthesis of block copolymers using reversible-addition fragmentation chain transfer (RAFT) polymerization.

Science.gov (United States)

Keddie, Daniel J

2014-01-21

The discovery of reversible-deactivation radical polymerization (RDRP) has provided an avenue for the synthesis of a vast array of polymers with a rich variety of functionality and architecture. The preparation of block copolymers has received significant focus in this burgeoning research field, due to their diverse properties and potential in a wide range of research environments. This tutorial review will address the important concepts behind the design and synthesis of block copolymers using reversible addition-fragmentation chain transfer (RAFT) polymerization. RAFT polymerization is arguably the most versatile of the RDRP methods due to its compatibility with a wide range of functional monomers and reaction media along with its relative ease of use. With an ever increasing array of researchers that possess a variety of backgrounds now turning to RDRP, and RAFT in particular, to prepare their required polymeric materials, it is pertinent to discuss the important points which enable the preparation of high purity functional block copolymers with targeted molar mass and narrow molar mass distribution using RAFT polymerization. The key principles of appropriate RAFT agent selection, the order of monomer addition in block synthesis and potential issues with maintaining high end-group fidelity are addressed. Additionally, techniques which allow block copolymers to be accessed using a combination of RAFT polymerization and complementary techniques are touched upon.

Magnetic Levitation To Characterize the Kinetics of Free-Radical Polymerization.

Science.gov (United States)

Ge, Shencheng; Semenov, Sergey N; Nagarkar, Amit A; Milette, Jonathan; Christodouleas, Dionysios C; Yuan, Li; Whitesides, George M

2017-12-27

This work describes the development of magnetic levitation (MagLev) to characterize the kinetics of free-radical polymerization of water-insoluble, low-molecular-weight monomers that show a large change in density upon polymerization. Maglev measures density, and certain classes of monomers show a large change in density when monomers covalently join in polymer chains. MagLev characterized both the thermal polymerization of methacrylate-based monomers and the photopolymerization of methyl methacrylate and made it possible to determine the orders of reaction and the Arrhenius activation energy of polymerization. MagLev also made it possible to monitor polymerization in the presence of solids (aramid fibers, and carbon fibers, and glass fibers). MagLev offers a new analytical technique to materials and polymer scientists that complements other methods (even those based on density, such as dilatometry), and will be useful in investigating polymerizations, evaluating inhibition of polymerizations, and studying polymerization in the presence of included solid materials (e.g., for composite materials).

Method for forming polymerized microfluidic devices

Science.gov (United States)

Sommer, Gregory J.; Hatch, Anson V.; Wang, Ying-Chih; Singh, Anup K.; Renzi, Ronald F.; Claudnic, Mark R.

2013-03-12

Methods for making a microfluidic device according to embodiments of the present invention include defining.about.cavity. Polymer precursor solution is positioned in the cavity, and exposed to light to begin the polymerization process and define a microchannel. In some embodiments, after the polymerization process is partially complete, a solvent rinse is performed, or fresh polymer precursor introduced into the microchannel. This may promote removal of unpolymerized material from the microchannel and enable smaller feature sizes. The polymer precursor solution may contain an iniferter. Polymerized features therefore may be capped with the iniferter, which is photoactive. The iniferter may aid later binding of a polyacrylamide gel to the microchannel surface.

Preparation and characterization of a novel polymeric based solid-solid phase change heat storage material

International Nuclear Information System (INIS)

Xi Peng; Gu Xiaohua; Cheng Bowen; Wang Yufei

2009-01-01

Here we reported a two-step procedure for preparing a novel polymeric based solid-solid phase change heat storage material. Firstly, a copolymer monomer containing a polyethylene glycol monomethyl ether (MPEG) phase change unit and a vinyl unit was synthesized via the modification of hydrogen group of MPEG. Secondly, by copolymerization of the copolymer monomer and phenyl ethylene, a novel polymeric based solid-solid phase change heat storage material was prepared. The composition, structure and properties of the novel polymeric based solid-solid phase change material were characterized by IR, 1 H NMR, DSC, WAXD, and POM, respectively. The results show that the novel polymeric based solid-solid phase change material possesses of excellent crystal properties and high phase change enthalpy.

Ternary hybrid polymeric nanocomposites through grafting of polystyrene on graphene oxide-TiO_2 by surface initiated atom transfer radical polymerization (SI-ATRP)

International Nuclear Information System (INIS)

Kumar, Arvind; Bansal, Ankushi; Behera, Babita; Jain, Suman L.; Ray, Siddharth S.

2016-01-01

A ternary hybrid of graphene oxide-titania-polystyrene (GO-TiO_2-PS) nanocomposite is developed where polystyrene composition is regulated by controlling growth of polymer chains and nanoarchitectonics is discussed. Graphene Oxide-TiO_2 (GO-TiO_2) nanocomposite is prepared by in-situ hydrothermal method and the surface is anchored with α-bromoisobutyryl bromide to activate GO-TiO_2 as initiator for polymerization. In-situ grafting of polystyrene through surface initiated atom transfer radical polymerization (SI- ATRP) on this Br-functionalized nano-composite initiator yields GO-TiO_2-PS ternary hybrid. Varying the monomer amount and keeping the concentration of initiator constant, polystyrene chain growth is regulated with narrow poly-dispersivity to achieve desired composition. This composite is well characterized by various analytical techniques like FTIR, XRD, DSC, SEM, TEM, and TGA. - Highlights: • Nanocomposite of ternary hybrid of GO-TiO_2 with polystyrene. • PS is surface grafted on GO-TiO_2. • Polymer chain lengths are well regulated by SI-ATRP living polymerization. • Thermal stability of this hybrid is relatively high.

Polymeric micelles as a drug carrier for tumor targeting

Directory of Open Access Journals (Sweden)

Neha M Dand

2013-01-01

Full Text Available Polymeric micelle can be targeted to tumor site by passive and active mechanism. Some inherent properties of polymeric micelle such as size in nanorange, stability in plasma, longevity in vivo, and pathological characteristics of tumor make polymeric micelles to be targeted at the tumor site by passive mechanism called enhanced permeability and retention effect. Polymeric micelle formed from the amphiphilic block copolymer is suitable for encapsulation of poorly water soluble, hydrophobic anticancer drugs. Other characteristics of polymeric micelles such as separated functionality at the outer shell are useful for targeting the anticancer drug to tumor by active mechanisms. Polymeric micelles can be conjugated with many ligands such as antibodies fragments, epidermal growth factors, α2 -glycoprotein, transferrine, and folate to target micelles to cancer cells. Application of heat and ultrasound are the alternative methods to enhance drug accumulation in tumoral cells. Targeting using micelles can also be done to tumor angiogenesis which is the potentially promising target for anticancer drugs. This review summarizes about recently available information regarding targeting the anticancer drug to the tumor site using polymeric micelles.

STUDIES ON VINYL POLYMERIZATION WITH INITIATION SYSTEM CONTAINING AMINE DERIVATIVES

Institute of Scientific and Technical Information of China (English)

QIU Kunyuan; ZHANG Jingyi; FENG Xinde(S. T. Voong)

1983-01-01

Two main types of amine-containing initiation systems were studied in this work. In the case of MMA polymerization initiated by BPO-amine (DMT, DHET, DMA) redox systems, it was found that the polymerization rate and colour stability of the polymer for different amine systems were in the following order: DMT≈DHET＞DMA. Accordingly, BPO-DMT and BPO-DHET are effective initiators. In the case of MEMA polymerization by amine (DMT, DHET, DMA) alone, it was found that the polymerization rate and the percentage of conversion for these different amine systems were in the following order: DMT≥DHET＞DMA. The polymerization rate and the percentage of conversion also increased with the increase of DMT concentration. From the kinetic investigation the rate equation of Rp=K [DMT]1/2 [MEMA]3/2 was obtained, and the overall activation energy of polymerization was calculated to be 34.3 KJ/mol (8.2 Kcal/mol). Moreover, the polymerization of MEMA in the presence of DMT was strongly inhibited by hydroquinone, indicating the polymerization being free radical in nature. From these results, the mechanism of MEMA polymerization initiated by amine was proposed.

Functionalization of nanochannels by radio-induced grafting polymerization on PET track-etched membranes

International Nuclear Information System (INIS)

Soto Espinoza, S.L.; Arbeitman, C.R.; Clochard, M.C.; Grasselli, M.

2014-01-01

The application of swift-heavy ion bombardment to polymers is a well-established technique to manufacture micro- and nanopores onto polymeric films to obtain porous membranes. A few years ago, it was realized that, during ion bombardment, the high energy deposition along the ion path through the polymer reached cylindrical damage regions corresponding to the core trace and the penumbra. After the etching procedure, there are still enough active sites left in the penumbra that can be used to initiate a polymerization process selectively inside the membrane pores. In this study, we report the grafting polymerization of glycidyl methacrylate onto etched PET foils to obtain functionalized nanochannels. Grafted polymers were labeled with a fluorescent tag and analyzed by different fluorescence techniques such as direct fluorescence, fluorescence microscopy and confocal microscopy. These techniques allowed identifying and quantifying the grafted regions on the polymeric foils. - Highlights: • Irradiated PET foils with swift-heavy ions were etched and grafted in a step-by-step process. • Grafting polymerization was performed on the remaining active sites after etching. • Track-etched PET membranes were fluorescently labeled by chemical functionalization. • Functionalized track-etched PET membranes were analyzed by fluorescence and confocal microscopy

Chitin nanofiber elucidates the elicitor activity of polymeric chitin in plants

Directory of Open Access Journals (Sweden)

Mayumi eEgusa

2015-12-01

Full Text Available Chitin, an N-acetyl-D-glucosamine polymer, is a component of fungal cell walls and a microbe/pathogen-associated molecular pattern that elicits plant defense responses. As polymeric chitin is difficult to handle due to its insolubility in water, many studies on chitin-induced immune responses have used water-soluble low-molecular weight chitin instead. Thus, it is unclear if polymeric chitin can induce resistance. Here, we examined the elicitor activity of chitin nanofiber (CNF of submicron thickness prepared from polymeric chitin. CNF showed a high dispersing ability in water and induced both reactive oxygen species (ROS production and chitin-induced defense-related gene expression in Arabidopsis thaliana seedlings. The Arabidopsis chitin elicitor receptor kinase 1 (Atcerk1 mutant, which is impaired in chitin perception, also failed to respond to CNF. CNF exposure triggered ROS generation in suspension-cultured cells from Oryza sativa. Furthermore, pre-treatment of Arabidopsis leaves with CNF effectively reduced pathogen infection by both the fungus Alternaria brassicicola and the bacterium Pseudomonas syringae pv. tomato DC3000. These results demonstrate that CNF has elicitor activity and will help define the role of polymeric chitin in plant immune responses.

Synthesis and Characterization of Polyethylene/Starch Nanocomposites: A Spherical Starch-Supported Catalyst and In Situ Ethylene Polymerization.

Science.gov (United States)

Zhanga, Hao; Xi, Shixia; Wang, Shuwei; Liu, Jingsheng; Yoon, Keun-Byoung; Lee, Dong-Ho; Zhang, Hexin; Zhang, Xuequan

2017-01-01

In the present article, a novel spherical starch-supported vanadium (V)-based Ziegler-Natta catalyst was synthesized. The active centers of the obtained catalyst well dispersed in the starch through the SEM-EDX analysis. The effects of reaction conditions on ethylene polymerization were studied. The synthesized catalyst exhibited high activity toward ethylene polymerization in the presence of ethylaluminium sesquichloride (EASC) cocatalyst. Interestingly, the fiber shape PE was obtained directly during the polymerization process.

A balance between membrane elasticity and polymerization energy sets the shape of spherical clathrin coats

Science.gov (United States)

Saleem, Mohammed; Morlot, Sandrine; Hohendahl, Annika; Manzi, John; Lenz, Martin; Roux, Aurélien

2015-02-01

In endocytosis, scaffolding is one of the mechanisms to create membrane curvature by moulding the membrane into the spherical shape of the clathrin cage. However, the impact of membrane elastic parameters on the assembly and shape of clathrin lattices has never been experimentally evaluated. Here, we show that membrane tension opposes clathrin polymerization. We reconstitute clathrin budding in vitro with giant unilamellar vesicles (GUVs), purified adaptors and clathrin. By changing the osmotic conditions, we find that clathrin coats cause extensive budding of GUVs under low membrane tension while polymerizing into shallow pits under moderate tension. High tension fully inhibits polymerization. Theoretically, we predict the tension values for which transitions between different clathrin coat shapes occur. We measure the changes in membrane tension during clathrin polymerization, and use our theoretical framework to estimate the polymerization energy from these data. Our results show that membrane tension controls clathrin-mediated budding by varying the membrane budding energy.

Polyolefin nanocomposites in situ polymerization

Energy Technology Data Exchange (ETDEWEB)

Galland, Griselda Barrera; Fim, Fabiana de C.; Milani, Marceo A.; Silva, Silene P. da; Forest, Tadeu; Radaelli, Gislaine, E-mail: griselda.barrera@ufrgs.br [Universidade Federal do Rio Grande de Sul - UFRGS, Porto Alegre, RS (Brazil); Basso, Nara R.S. [Pontificia Universidade Catolica do Rio Grande do Sul, Porto Alegre, RS (Brazil); Quijada, Raul [Universidad de Chile, Santiago (Chile)

2011-07-01

Polyethylene and polypropylene nanocomposites using grapheme nanosheets and treated chrysotile have been synthesized by in situ polymerization using metallocene catalysts. The fillers have been submitted to acid, thermal and/ou ultrasound treatments before to introduce them into the polymerization reactor. A complete characterization of the fillers has been done. The nanocomposites have been characterized by SEM, TEM, DRX and AFM. The thermal, mechanic -dynamic, mechanical and electrical properties of the nanocomposites are discussed. (author)

Polyolefin nanocomposites in situ polymerization

International Nuclear Information System (INIS)

Galland, Griselda Barrera; Fim, Fabiana de C.; Milani, Marceo A.; Silva, Silene P. da; Forest, Tadeu; Radaelli, Gislaine; Basso, Nara R.S.; Quijada, Raul

2011-01-01

Polyethylene and polypropylene nanocomposites using grapheme nanosheets and treated chrysotile have been synthesized by in situ polymerization using metallocene catalysts. The fillers have been submitted to acid, thermal and/ou ultrasound treatments before to introduce them into the polymerization reactor. A complete characterization of the fillers has been done. The nanocomposites have been characterized by SEM, TEM, DRX and AFM. The thermal, mechanic -dynamic, mechanical and electrical properties of the nanocomposites are discussed. (author)

Sixtieth Anniversary of Ziegler-Natta Catalysts and Stereospecific Polymerization

Directory of Open Access Journals (Sweden)

Janović Z.

2015-07-01

Full Text Available This review article highlights the history of the discoveries of organometallic catalysts and stereospecific polymerization of α-olefins, dienes and a number of vinyl monomers by Karl Ziegler and Giulio Natta sixty years ago, their developments and recent progress. As one of the most important achievements in the field of catalysis, macromolecular science and polymer materials, their inventors were awarded the Nobel Prize in Chemistry in 1963 “for their discoveries in the field of chemistry and technology of high polymers”. These discoveries have stimulated an intensive, both basic and applied research all over the world, up to the present times, leading to great development of the polymer industry. The important biographical data and scientific advancements of K. Ziegler and G. Natta are presented as well. Karl Ziegler, a German scientist, Director of Max Planck Institute for Coal Research in Mülheim, besides many scientific achievements, in 1953 discovered a new process for the polymerization of ethylene into linear polyethylene under mild conditions by using titanium chloride and alkyl aluminium catalytic system that was superior to all existing polymerization. Giulio Natta, an Italian scientist, Director of the Department of Industrial Chemistry at Polytechnic, University of Milan, besides many achievements in petrochemical processes, in 1954 obtained for the first time isotactic polypropylene and Montecatini Co. started its production already in 1958. He conducted pioneering studies on the chain microstructure of synthetic organic polymers and postulated the mechanisms of stereospecific polymerizations. Since the discovery of the Zeigler-Natta catalyst, stereospecific polymerization and processes, significant developments have occurred. The breakthrough in polymerization processes such as fluid bed, liquid phase loop reactor and reactor granule technology led to significant development and growth of polyolefin production. In the 1980s

Biodegradable polymeric foam with food waste; Shokumotsu zansa wo mochiita seibunkai kobunshi hahhotai

Energy Technology Data Exchange (ETDEWEB)

Mishima, Kenji; Matsuyama, Kiyoshi; Yamauchi, Satoru; Takarabe, Shin' ichi

1999-09-01

A huge amount of food waste such as tea and beer dregs becomes a serious problem because of the lack of industrial waste space in Japan. On the other hand, the new polymeric foam is expected to be developed since the dangerous pollution of endorphin disrupters from industrial polymer foam is pointed out. In this work, we try to develop the biodegradable polymeric foam using the tea and beer dregs as secondary resources. And we examined the degradability of biodegradable polymer in the hydrothermal water for fundamental knowledge of polymeric foam production. We used an extruder equipped with a high pressure device to make the polymeric foam. And we examined the effect of the component ratio on the foam properties, foaming rate, strength, shrinkage rate, water-resistant. As a result, it was found that the amount of polymer is effective of quality of form and the biodegradability can be controlled by the amount of water and temperature. (author)

On-demand photoinitiated polymerization

Science.gov (United States)

Boydston, Andrew J; Grubbs, Robert H; Daeffler, Chris; Momcilovic, Nebojsa

2013-12-10

Compositions and methods for adjustable lenses are provided. In some embodiments, the lenses contain a lens matrix material, a masking compound, and a prepolymer. The lens matrix material provides structure to the lens. The masking compound is capable of blocking polymerization or crosslinking of the prepolymer, until photoisomerization of the compound is triggered, and the compound is converted from a first isomer to a second isomer having a different absorption profile. The prepolymer is a composition that can undergo a polymerization or crosslinking reaction upon photoinitiation to alter one or more of the properties of the lenses.

Stimuli-responsive biodegradable polymeric micelles for targeted cancer therapy

NARCIS (Netherlands)

Talelli, M.A.

2011-01-01

Thermosensitive and biodegradable polymeric micelles based on mPEG-b-pHPMAmLacn have shown very promising results during the past years. The results presented in this thesis illustrate the high potential of these micelles for anticancer therapy and imaging and fully justify further pharmaceutical

Novel Carbazole Skeleton-Based Photoinitiators for LED Polymerization and LED Projector 3D Printing

Directory of Open Access Journals (Sweden)

Assi Al Mousawi

2017-12-01

Full Text Available Radical chemistry is a very convenient way to produce polymer materials. Here, an application of a particular photoinduced radical chemistry is illustrated. Seven new carbazole derivatives Cd1–Cd7 are incorporated and proposed as high performance near-UV photoinitiators for both the free radical polymerization (FRP of (methacrylates and the cationic polymerization (CP of epoxides utilizing Light Emitting Diodes LEDs @405 nm. Excellent polymerization-initiating abilities are found and high final reactive function conversions are obtained. Interestingly, these new derivatives display much better near-UV polymerization-initiating abilities compared to a reference UV absorbing carbazole (CARET 9H-carbazole-9-ethanol demonstrating that the new substituents have good ability to red shift the absorption of the proposed photoinitiators. All the more strikingly, in combination with iodonium salt, Cd1–Cd7 are likewise preferred as cationic photoinitiators over the notable photoinitiator bis(2,4,6-trimethylbenzoylphenylphosphine oxide (BAPO for mild irradiation conditions featuring their remarkable reactivity. In particular their utilization in the preparation of new cationic resins for LED projector 3D printing is envisioned. A full picture of the included photochemical mechanisms is given.

Studies on the polymerization of acrolein oxime, 6

International Nuclear Information System (INIS)

Masuda, Seizo; Tamai, Harumi; Ota, Tadatoshi; Torii, Munetomo; Tanaka, Masami.

1979-01-01

Radiation-induced polymerization and copolymerization of acrolein oxime are investigated in different solvents and at a wide range of temperature for obtaining information on the reaction mechanism. Acrolein oxime is polymerized ionically, irrespective of dryness of the sample. Arrhenius plots for the polymerization rate, which do not yield a linear relation, can be adequately approximated by two straight lines. An anionic mechanism is operative above the room temperature, while a cationic mechanism predominates below -23 0 C. The reaction in the intermediate temperature range proceeds by a competitive mechanism, and the rate of the anionic and cationic polymerizations becomes equal at the temperature near -5 0 C. The reaction rate is proportional to the square root of dose rate at room temperature and -23 0 C. On the basis of these data, it is proposed that the polymerization of acrolein oxime by γ-irradiation proceeds by free-ionic mechanisms. (author)

Conformational and Structural Properties of High Functionality Dendrimer-like Star Polymers Synthesized from Living Polymerization Techniques; TOPICAL

International Nuclear Information System (INIS)

Pople, John A.

2001-01-01

The design, synthesis and solution properties of dendritic-linear hybrid macromolecules is described. The synthetic strategy employs living ring-opening polymerization in combination with selective and quantitative organic transformations for the preparation of new molecular architectures similar to classical star polymers and dendrimers. The polymers were constructed from high molecular weight poly(e-caprolactone) initiated from the surface hydroxyl groups of dendrimers derived from bis(hydroxymethyl) propionic acid (bis-MPA) in the presence of stannous 2-ethyl hexanoate (Sn(Oct)2). In this way, star and hyperstar poly(e-caprolactones) were elaborated depending on the generation of dendrimer employed. The ROP from these hydroxy groups was found to be a facile process leading to controlled molecular weight, low dispersity products (Mw/Mn) and lt; 1.15. In addition to the use of dendrimers as building blocks to star polymers, functional dendrons derived from bis-MPA were attached to chain ends of the star polymers, yielding structures that closely resemble that of the most advanced dendrimers. Measurements of the solution properties (hydrodynamic volume vs. molecular weight) on the dendritic-linear hybrids show a deviation from linearity, with a lower than expected hydrodynamic volume, analogous to the solution properties of dendrimers of high generation number. The onset of the deviation begins with the polymers initiated from the second generation dendrimer of bis-MPA and becomes more exaggerated with the higher generations. It was found that polymerization amplifies the nonlinear solution behavior of dendrimers. Small angle neutron scattering (SANS) measurements revealed that the radius of gyration scaled with arm functionality (f) as f 2/3, in accordance with the Daoud-Cotton model for many arm star polymer

Kinetics of waterborne fluoropolymers prepared by one-step semi-continuous emulsion polymerization of chlorotrifluoroethylene, vinyl acetate, butyl acrylate and Veova 10

Science.gov (United States)

Liu, H. Z.; Wang, M. H.; Wang, Z. F.; Bian, J. M.

2018-01-01

Due to using gaseous fluorine monomer with toxicity, waterborne fluoropolymers are synthesized by semi-continuous high-pressure emulsion polymerization method which differs from free-pressure emulsion polymerization. To dates, the research on preparing process and kinetics for high-pressure emulsion polymerization is reported relatively less, which hinders researchers from understanding of mechanisms for monomer-fluorinated emulsion polymerization. The paper also provides a new method by element auxiliary analysis to calculate kinetics parameters of high-pressure emulsion polymerization. Based on aforementioned consideration, waterborne fluoropolymers were prepared by copolymerization of chlorotrifluoroethylene (CTFE), vinyl acetate (VAc), butyl acrylate (BA) and vinyl ester of versatic acid (Veova 10) using potassium persulfate as initiator and mixed surfactants. The kinetics of emulsion polymerization of waterborne fluoropolymers was then investigated. Effects of emulsifier concentration, initiator concentration, and polymerization temperature on polymerization rate (Rp) were evaluated, and relationship was described as Rp∝[I]0.10 and Rp∝[E]0.12. The apparent activation energy was determined to be 33.61 kJ·mol-1. Moreover, the relative conversion rate of CTFE with the other monomers was observed, and results indicated that CTFE monomer more uniformly copolymerized with the other monomers. The resulting emulsion properties and pressure change in an autoclave were evaluated at different stirring rates. The initial reaction time, defined as the beginning time of dropwise addition, was determined by the change in solid content and particle size of emulsion.

Fluoropolymer materials and architectures prepared by controlled radical polymerizations

DEFF Research Database (Denmark)

Hansen, Natanya Majbritt Louie; Jankova Atanasova, Katja; Hvilsted, Søren

2007-01-01

This review initially summarizes the mechanisms, merits and limitations of the three controlled radical polymerizations: nitroxide mediated polymerization (NMP), atom transfer radical polymerization (ATRP) or metal catalyzed living radical polymerization, and reversible addition–fragmentation chain...... transfer (RAFT) polymerization. This is followed by two parts, one dealing with homo- and copolymerizations of fluorinated methacrylates and acrylates, and a second where fluorinated styrenes, alone or in combination with other monomers, are the main issues. In these parts, initiators (including...... properties and functionalities that can be obtained from these novel fluorinated materials and architectures are especially emphasized. Thus, various amphiphilic, biocompatible or low energy materials, fluorinated nanoparticles and nanoporous films/membranes as well as materials for submicron and nanolevel...

Online observation of emulsion polymerization by fluorescence technique

CERN Document Server

Rudschuck, S; Fuhrmann, J

1999-01-01

An online observation of local polarity via fluorescence spectroscopy was used to study the formation and growth of polymer particles during an emulsifier-free heterogeneous polymerization. The reaction mixture consisted of styrene dispersed in water and the polymerization was initiated by a macro-initiator (hydrolyzed propene-maleic acid copolymer with t-butyl perester groups). Pyrenyl probes were attached to the backbone of the initiator to analyze the heterogeneous reaction. The experimental results allow a clear distinction of different time regions during the heterogeneous polymerization. Information about the heating period, the latex formation, the particle growth and the final stage of the polymerization process (gel point) were obtained. (11 refs).

Vinyl acetate polymerization by ionizing radiation

International Nuclear Information System (INIS)

Mesquita, Andrea Cercan

2002-01-01

The aim of this work is the synthesis and characterization of the poly(vinyl acetate) using the ionizing radiation. Six polymerizations of vinyl acetate were carried out using three techniques of polymerization: in bulk, emulsion and solution. In the technique of solution polymerization were used two solvents, the alcohol ethyl and the methylethylketone, in two proportions 1:0.5 and 1:1 related to the monomer. The solutions were irradiated with gamma rays from a 60 Co source, with dose rate between 5.25 kGy/h and 6.26 kGy/h. The polymers obtained were characterized by Fourier Transform Infrared Spectroscopy (FTIR). The glass transition temperature (Tg) was investigated by Differential Scanning Calorimeter (DSC). The molecular weight was analyzed by the technique of Gel Permeation Chromatography (GPC). Tests of density, hardness and Vicat softening temperature were carried out. The infrared spectroscopy and others results confirmed that the polymers obtained by polymerization of vinyl acetate in bulk, emulsion and solution, using ionizing radiation, really correspond at poly(vinyl acetate). (author)

Synthesis of New Silicon-linked Lanthanocene Complexes and Their High Catalytic Activity for Methyl Methacrylate Polymerization with Nanometric Sodium Hydride as Co-catalyst

Institute of Scientific and Technical Information of China (English)

谢小敏; 黄吉玲

2005-01-01

The synthesis and characterization of four new silicon-linked lanthanocene complexes with pendant phenyl groups on cyclopentadiene were reported. Based on the data of elemental analyses, MS and IR, the complexes were presumed to be unsolvated and dimeric complexes [Me2Si(C5H3CMe2C6H5)2LnC1]2 [Ln=Er (1), Gd (2), Sm (3), Dy (4)]. In conjunction with AlEt3 or sodium hydride as the co-catalyst, these complexes could efficiently catalyze the polymerization of methyl methacrylate (MMA). When the nanometric sodium hydride was used as a co-catalyst, the complexes were highly effective for the polymerization of MMA. At low temperature and in short time, in [MeESi(C5H3CMe2C6H5)2LnC1]2/NaH (nanometric) system, the polymer was obtained in more than 80% yield and the molecular weight was greater than 105. The activity reached that of organolanthanide hydride as a single-component catalyst. In ]MeESi(C5H3CMe2C6H5)2ErC1]2/Nail (nanometric) system, the effects of the molar ratio of MMA/catalyst and catalyst/co-catalyst, and the temperature on polymerization were studied.

Preparation of polymeric aluminium ferric chloride from bauxite tailings

Directory of Open Access Journals (Sweden)

Ma D.

2013-01-01

Full Text Available Bauxite tailings are the main solid wastes in the ore dressing process. The Al2O3 and Fe2O3 contents in bauxite tailings can reach 50% and 13% respectively. The present study proposed a feasible method to use bauxite tailings to prepare polymeric aluminium ferric chloride (PAFC, a new composite inorganic polymer for water purification. Bauxite tailings roasted reacting with hydrochloric acid under air, pickle liquor which mainly contains Fe3+, Al3+ was generated, then calcium aluminate was used to adjust pH value and the basicity of the pickle liquor, the PAFC was subsequently prepared after the polymerization process. The optimal synthesizing parameters for the preparation of PAFC obtained were as follows: the concentration of hydrochloric acid of 24 wt%, ratio of hydrochloric acid to bauxite tailings of 6:1, temperature of 90ºC, leaching time of 2.5 hours, ration of pickle liquor to calcium aluminate of 12:1, polymerization temperature of 90ºC and polymerization time of about 3 hours. The basicity of PAFC was higher than 68%, the sum concentration of Al2O3 and Fe2O3 was beyond 12.5%. The results of flocculation tests indicate that the PAFC has a better performance of removing the turbidity of wastewater compared to PAC, and PAFC prepared by bauxite tailings is a kind of high quality flocculants.

In situ polymerization of L-Lactide in the presence of fumed silica

International Nuclear Information System (INIS)

Prebe, A.; Alcouffe, P.; Cassagnau, Ph.; Gerard, J.F.

2010-01-01

Chemiorheology, i.e. rheological changes during the polymerization, of a biosourced monomer, i.e. L-Lactide, containing fumed silica have been studied. For that purpose, the reaction was proceeded in situ between the plates of a dynamic rheometer. The polymerization kinetics was followed from the variation of the complex shear modulus versus reaction time. Moreover, at temperatures lower than the crystallization temperature, it was possible to follow the crystallization process while the polymerization takes place. Adding fumed silica particles into the monomer leads to the formation of a physical (percolated) network from particle-particle interactions, i.e. silica, in the L-Lactide probably hydrophilic interactions. The gel-like structure was kept while the polymerization as long as the strain remains low indicating that the silica particle network remains weak. Furthermore, the mechanism of the break down of the gel structure under large deformation as well as the recovery was discussed. It seems that the non-linearity effect of the nanocomposites stems in the silica inter-particle interactions. It was found that silica particles do not have any effect on the temperature of crystallization - molar mass relation but could act as nucleating agent. In situ polymerization of L-Lactide in the presence of 5 wt.% of modified fumed silica was carried out in a reactor. It was found that fumed hydrophilic silica leaded to a microcomposite with highly dense agglomerates in the polymer matrix whereas with a less hydrophilic silica it was possible to decrease the size of the agglomerates increasing the dispersion. The finest dispersion state was achieved with the 'initiating' functionalized silica leading to a 'grafting from' polymerization of the L-Lactide. Such functionalized silica leads to a nanoscale dispersion in a one-step bulk polymerization with only a few small agglomerates.

In situ polymerization of L-Lactide in the presence of fumed silica

Energy Technology Data Exchange (ETDEWEB)

Prebe, A. [Universite de Lyon, F-69361, Lyon (France); CNRS, UMR 5223, Ingenierie des Materiaux Polymeres, F-69622, Villeurbanne (France); Universite Claude Bernard Lyon 1, F-69622, Villeurbanne (France); INSA Lyon, F-69621, Villeurbanne (France); Alcouffe, P. [Universite de Lyon, F-69361, Lyon (France); CNRS, UMR 5223, Ingenierie des Materiaux Polymeres, F-69622, Villeurbanne (France); Universite Claude Bernard Lyon 1, F-69622, Villeurbanne (France); Cassagnau, Ph., E-mail: philippe.cassagnau@univ-lyon1.fr [Universite de Lyon, F-69361, Lyon (France); CNRS, UMR 5223, Ingenierie des Materiaux Polymeres, F-69622, Villeurbanne (France); Universite Claude Bernard Lyon 1, F-69622, Villeurbanne (France); Gerard, J.F. [Universite de Lyon, F-69361, Lyon (France); CNRS, UMR 5223, Ingenierie des Materiaux Polymeres, F-69622, Villeurbanne (France); INSA Lyon, F-69621, Villeurbanne (France)

2010-11-01

Chemiorheology, i.e. rheological changes during the polymerization, of a biosourced monomer, i.e. L-Lactide, containing fumed silica have been studied. For that purpose, the reaction was proceeded in situ between the plates of a dynamic rheometer. The polymerization kinetics was followed from the variation of the complex shear modulus versus reaction time. Moreover, at temperatures lower than the crystallization temperature, it was possible to follow the crystallization process while the polymerization takes place. Adding fumed silica particles into the monomer leads to the formation of a physical (percolated) network from particle-particle interactions, i.e. silica, in the L-Lactide probably hydrophilic interactions. The gel-like structure was kept while the polymerization as long as the strain remains low indicating that the silica particle network remains weak. Furthermore, the mechanism of the break down of the gel structure under large deformation as well as the recovery was discussed. It seems that the non-linearity effect of the nanocomposites stems in the silica inter-particle interactions. It was found that silica particles do not have any effect on the temperature of crystallization - molar mass relation but could act as nucleating agent. In situ polymerization of L-Lactide in the presence of 5 wt.% of modified fumed silica was carried out in a reactor. It was found that fumed hydrophilic silica leaded to a microcomposite with highly dense agglomerates in the polymer matrix whereas with a less hydrophilic silica it was possible to decrease the size of the agglomerates increasing the dispersion. The finest dispersion state was achieved with the 'initiating' functionalized silica leading to a 'grafting from' polymerization of the L-Lactide. Such functionalized silica leads to a nanoscale dispersion in a one-step bulk polymerization with only a few small agglomerates.

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst.

Science.gov (United States)

Yeow, Jonathan; Xu, Jiangtao; Boyer, Cyrille

2016-06-08

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (λ = 460 nm, 0.7 mW/cm(2)), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

A multifunctional polymeric nanofilm with robust chemical performances for special wettability

Science.gov (United States)

Wang, Yabin; Lin, Feng; Dong, Yaping; Liu, Zhong; Li, Wu; Huang, Yudong

2016-02-01

A multifunctional polymeric nanofilm of a triazinedithiolsilane compound, which can protect metallic substrates and activate the corresponding surface simultaneously, is introduced onto a copper mesh surface via facile solution-immersion approaches. The resultant interface exhibits hydrophilic features due to the existence of silanol groups (SiOH) outward and has the potential to act as a superhydrophilic and underwater superoleophobic material. As the polymeric nanofilm atop the copper mesh is modified with long-chain octadecyltrichlorosilane (OTS), the functionalized surface becomes superhydrophobic and superoleophilic. The OTS-modified polymeric nanofilm shows outstanding chemical durability and stability that are seldom concurrently satisfied for a material with special wettability, owing to its inherent architecture. These textures generate high separation efficiency, durable separation capability and excellent thermal stability. The protective ability, originating from the textures of the underlying cross-linked disulfide units (-SS-) and siloxane networks (SiOSi) on the top of the nanofilm, prolongs the chemical durability. The activating capability stemming from the residual SiOH groups improves the chemical stability as a result of the chemical bonds developed by these sites. The significant point of this investigation lies in enlightening us on the fabrication of multifunctional polymeric nanofilms on different metal surfaces using various triazinedithiolsilane compounds, and on the construction of interfaces with controllable wettable performances in demanding research or industrial applications.A multifunctional polymeric nanofilm of a triazinedithiolsilane compound, which can protect metallic substrates and activate the corresponding surface simultaneously, is introduced onto a copper mesh surface via facile solution-immersion approaches. The resultant interface exhibits hydrophilic features due to the existence of silanol groups (SiOH) outward and has

RADIOCHEMICAL YIELDS OF GRAFT POLYMERIZATION REACTIONS OF CELLULOSE

Energy Technology Data Exchange (ETDEWEB)

Arthur, Jr, J C; Blouin, F A

1963-12-15

The preparation of radioinduced graft polymers of cotton cellulose, while retaining the fibrous nature and high molecular weight of the cellulose, depended primarily on the radiochemical yields of cellulose reactions and of graft polymerization reactions. Yields of the initial major molecular changes in cellulosic polymer indicated that, in the case of scission of the molecule and carboxyl group formation, chain reactions were not initiated by radiation; however, in the case of carbonyl group formation chain reactions were initiated but quickly terminated. Generally, experimental procedures, used in graft polymerization reactions, were: simultaneous irradiation reactions, that is, application of monomers or solutions of monomers to cellulose or chemically modified celluloses, then irradiation; and post-irradiation reactions, that is, irradiation of cellulose or chemically modified celluloses, then after removal from the field of radiation, contacting the irradiated cellulose with monomer. Some of the most important factors influencing the radiochemical yields of graft polymerization reactions, of styrene and acrylonitrile onto cellulose were: concentration of monomer in treating solution; solvent; ratio of monomer solution to cellulose; prior chemical modification of cellulose; and absence of oxygen, particularly in post-irradiation reactions. Experimental data are presented, and the direct and indirect effects of Co/sup 60/ gamma radiation on these reactions are discussed. (auth)

Self-catalyzed photo-initiated RAFT polymerization for fabrication of fluorescent polymeric nanoparticles with aggregation-induced emission feature.

Science.gov (United States)

Zeng, Guangjian; Liu, Meiying; Jiang, Ruming; Huang, Qiang; Huang, Long; Wan, Qing; Dai, Yanfeng; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

2018-02-01

In recent years, the fluorescent polymeric nanoparticles (FPNs) with aggregation-induced emission (AIE) feature have been extensively exploited in various biomedical fields owing to their advantages, such as low toxicity, biodegradation, excellent biocompatibility, good designability and optical properties. Therefore, development of a facile, efficient and well designable strategy should be of great importance for the biomedical applications of these AIE-active FPNs. In this work, a novel method for the fabrication of AIE-active FPNs has been developed through the self-catalyzed photo-initiated reversible addition fragmentation chain transfer (RAFT) polymerization using an AIE dye containing chain transfer agent (CTA), which could initiate the RAFT polymerization under light irradiation. The results suggested that the final AIE-active FPNs (named as TPE-poly(St-PEGMA)) showed great potential for biomedical applications owing to their optical and biological properties. More importantly, the method described in the work is rather simple and effective and can be further extended to prepare many other different AIE-active FPNs owing to the good monomer adoptability of RAFT polymerization. Copyright © 2017 Elsevier B.V. All rights reserved.

Gruzinski gambit / Nikolai Hrustaljov

Index Scriptorium Estoniae

Hrustaljov, Nikolai

2005-01-01

Anapas lõppes SRÜ ja Baltimaade XIV avatud filmifestival "Kinoshokk 2005". Žürii andis parima näitlejanna preemia Maarja Jakobsonile tema rolli eest P. Urbla filmis "Stiilipidu". Parima filmi auhinna sai grusiin Levan Tutberidze "Jalutuskäik Mägi-Karabahhis" ja parima režii auhinna samuti grusiin Levan Zakareishvili filmi eest "Thbilisi-Thbilisi"

Triumf gruzinskogo kino / Irina Ivanova

Index Scriptorium Estoniae

Ivanova, Irina

2005-01-01

Anapas lõppes SRÜ ja Baltimaade XIV avatud filmifestival "Kinoshokk 2005". Žürii andis parima näitlejanna preemia Maarja Jakobsonile tema rolli eest P. Urbla filmis "Stiilipidu". Parima filmi auhinna sai grusiin Levan Tutberidze "Jalutuskäik Mägi-Karabahhis" ja parima režii auhinna samuti grusiin Levan Zakareishvili filmi eest "Thbilisi-Thbilisi"

The interval high rate discharge behavior of Li3V2(PO4)3/C cathode based on in situ polymerization method

International Nuclear Information System (INIS)

Mao, Wen-feng; Yan, Ji; Xie, Hui; Tang, Zhi-yuan; Xu, Qiang

2013-01-01

An in situ polymerization assisted fast sol–gel method was introduced to synthesize high performance Li 3 V 2 PO 4 /C (LVP/C) cathode material. The crystal structure, surface morphology and electrochemical performances of the LVP/C samples sintered at different temperatures were investigated. The composite sintered at 750 °C exhibits the highest specific discharge capacity of 119.02 mAh g −1 (440.35 Wh g −1 ) at 10 C rate. The Li + diffusion coefficient ranges from 10 −6 to 10 −8 cm 2 s −1 based on different scanning rates and the electronic conductivity is about 10 −5 S cm −1 . For comparison, an ex situ polymerization method was also employed to obtain the LVP/C composite. A novel charge/discharge testing mode was designed to investigate the electrochemical behavior of the as-prepared LVP/C composite for practical application in electric vehicle cells. The obtained high power density and the special testing mode prove the LVP/C composite would be a promising candidate for the electric vehicle application and deserves further investigation

Aqueous dispersion polymerization: a new paradigm for in situ block copolymer self-assembly in concentrated solution.

Science.gov (United States)

Sugihara, Shinji; Blanazs, Adam; Armes, Steven P; Ryan, Anthony J; Lewis, Andrew L

2011-10-05

Reversible addition-fragmentation chain transfer polymerization has been utilized to polymerize 2-hydroxypropyl methacrylate (HPMA) using a water-soluble macromolecular chain transfer agent based on poly(2-(methacryloyloxy)ethylphosphorylcholine) (PMPC). A detailed phase diagram has been elucidated for this aqueous dispersion polymerization formulation that reliably predicts the precise block compositions associated with well-defined particle morphologies (i.e., pure phases). Unlike the ad hoc approaches described in the literature, this strategy enables the facile, efficient, and reproducible preparation of diblock copolymer spheres, worms, or vesicles directly in concentrated aqueous solution. Chain extension of the highly hydrated zwitterionic PMPC block with HPMA in water at 70 °C produces a hydrophobic poly(2-hydroxypropyl methacrylate) (PHPMA) block, which drives in situ self-assembly to form well-defined diblock copolymer spheres, worms, or vesicles. The final particle morphology obtained at full monomer conversion is dictated by (i) the target degree of polymerization of the PHPMA block and (ii) the total solids concentration at which the HPMA polymerization is conducted. Moreover, if the targeted diblock copolymer composition corresponds to vesicle phase space at full monomer conversion, the in situ particle morphology evolves from spheres to worms to vesicles during the in situ polymerization of HPMA. In the case of PMPC(25)-PHPMA(400) particles, this systematic approach allows the direct, reproducible, and highly efficient preparation of either block copolymer vesicles at up to 25% solids or well-defined worms at 16-25% solids in aqueous solution.

A comparison of three dimensional change in maxillary complete dentures between conventional heat polymerizing and microwave polymerizing techniques

Directory of Open Access Journals (Sweden)

Shinsuke Sadamori

2007-03-01

Full Text Available The purpose of this study was to measure and compare two different polymerizing processes, heat polymerizing (HP and microwave polymerizing (MP, on the three dimensional changes in the fitting surface and artificial teeth of maxillary complete dentures. A threedimensional coordinate measurement system was used to record distortion of the specimens. The distortion of the fitting surface was measured from the reference plane on the fitting side from which a coordinate system was set, and the movement of the artificial teeth and the distortion of the polished surface was measured from the reference plane of the artificial tooth side, from which a coordinate system was set. It was clearly showed that various distortions of denture specimens after polymerization process can be measured with this three-coordinate measuring machine. The study showed that the overall distortion of the fitting surface in HP specimens was shown to be larger than in MP ones.

Study on irradiated polymerization of acrylonitrile by NMR

International Nuclear Information System (INIS)

Zhao Xin; Lin Hao

1999-01-01

Sup 13 C CP/MAS spectra and nuclear Overhauser effects (NOE) at room temperature have been measured for acrylonitrile (AN) in homophase irradiated polymerization. With the increase of radiation dose the chemical shift of cracking peaks and NOE are variation. This implies that the polymerized mechanism of AN were changed with the variation of irradiated doses and dose rate. There is the stronger affinity electron group (-CN) in acrylonitrile monomer. It may be polymerized by various ways and mechanism and be gained the polymer of difference structures and molecular weight of polyacrylonitrile (PAN). Starmicarbon and Starker obtained higher molecular weight of polyacrylonitrile by peroxysulfate-pyrosulfite in oxidation-reduction system. The superhigh molecular weight of PAN was synthesized chemically according to the method of Wu et. al. by suspension polymerization. In this paper we discussed that the relative concentrations of steric dyads and triads in the chain structure in PAN and the irradiation polymerized mechanism of acrylonitrile monomer in room temperature by different dose and dose rate

Factors affecting toxicity and efficacy of polymeric nanomedicines

International Nuclear Information System (INIS)

Igarashi, Eiki

2008-01-01

Nanomedicine is the application of nanotechnology to medicine. The purpose of this article is to review common characteristics of polymeric nanomedicines with respect to passive targeting. We consider several biodegradable polymeric nanomedicines that are between 1 and 100 nm in size, and discuss the impact of this technology on efficacy, pharmacokinetics, toxicity and targeting. The degree of toxicity of polymeric nanomedicines is strongly influenced by the biological conditions of the local environment, which influence the rate of degradation or release of polymeric nanomedicines. The dissemination of polymeric nanomedicines in vivo depends on the capillary network, which can provide differential access to normal and tumor cells. The accumulation of nanomedicines in the microlymphatics depends upon retention time in the blood and extracellular compartments, as well as the type of capillary endothelium surrounding specific tissues. Finally, the toxicity or efficacy of intact nanomedicines is also dependent upon tissue type, i.e., non-endocrine or endocrine tissue, spleen, or lymphatics, as well as tumor type

Development of high-speed reactive processing system for carbon fiber-reinforced polyamide-6 composite: In-situ anionic ring-opening polymerization

International Nuclear Information System (INIS)

Kim, Sang-Woo; Seong, Dong Gi; Yi, Jin-Woo; Um, Moon-Kwang

2016-01-01

In order to manufacture carbon fiber-reinforced polyamide-6 (PA-6) composite, we optimized the reactive processing system. The in-situ anionic ring-opening polymerization of ε-caprolactam was utilized with proper catalyst and initiator for PA-6 matrix. The mechanical properties such as tensile strength, inter-laminar shear strength and compressive strength of the produced carbon fiber-reinforced PA-6 composite were measured, which were compared with the corresponding scanning electron microscope (SEM) images to investigate the polymer properties as well as the interfacial interaction between fiber and polymer matrix. Furthermore, kinetics of in-situ anionic ring-opening polymerization of ε-caprolactam will be discussed in the viewpoint of increasing manufacturing speed and interfacial bonding between PA-6 matrix and carbon fiber during polymerization.

Development of high-speed reactive processing system for carbon fiber-reinforced polyamide-6 composite: In-situ anionic ring-opening polymerization

Energy Technology Data Exchange (ETDEWEB)

Kim, Sang-Woo; Seong, Dong Gi; Yi, Jin-Woo; Um, Moon-Kwang [Composites Research Division, Korea Institute of Materials Science (KIMS), Changwon, Gyeongnam, 642–831 (Korea, Republic of)

2016-05-18

In order to manufacture carbon fiber-reinforced polyamide-6 (PA-6) composite, we optimized the reactive processing system. The in-situ anionic ring-opening polymerization of ε-caprolactam was utilized with proper catalyst and initiator for PA-6 matrix. The mechanical properties such as tensile strength, inter-laminar shear strength and compressive strength of the produced carbon fiber-reinforced PA-6 composite were measured, which were compared with the corresponding scanning electron microscope (SEM) images to investigate the polymer properties as well as the interfacial interaction between fiber and polymer matrix. Furthermore, kinetics of in-situ anionic ring-opening polymerization of ε-caprolactam will be discussed in the viewpoint of increasing manufacturing speed and interfacial bonding between PA-6 matrix and carbon fiber during polymerization.

Resveratrol immobilization and release in polymeric hydrogels

International Nuclear Information System (INIS)

Momesso, Roberta Grazzielli Ramos Alves Passarelli

2010-01-01

Resveratrol (3, 4', 5-trihydroxystilbene) is a polyphenolic produced by a wide variety of plants in response to injury and found predominantly in grape skins. This active ingredient has been shown to possess benefits for the health, such as the antioxidant capacity which is related to the prevention of several types of cancer and skin aging. However, the oral bioavailability of resveratrol is poor and makes its topical application interesting. The purpose of this study was to immobilize resveratrol in polymeric hydrogels to obtain a release device for topical use. The polymeric matrices composed of poli(N-vinyl-2-pyrrolidone) (PVP), poly(ethyleneglycol) (PEG) and agar or PVP and glycerol irradiated at 20 kGy dose were physical-chemically characterized by gel fraction and swelling tests and its preliminary biocompatibility by in vitro test of cytotoxicity using the technique of neutral red uptake. Due to low solubility of resveratrol in water, the addition of 2% ethanol to the matrices was verified. All matrices showed a high crosslinking degree, capacity of swelling and the preliminary cytotoxicity test showed nontoxicity effect. The devices were obtained by resveratrol immobilization in polymeric matrices, carried out in a one-or-two-steps process, that is, before or after irradiation, respectively. The one step resveratrol devices were characterized by gel fraction, swelling tests and preliminary biocompatibility, and their properties were maintained even after the resveratrol incorporation. The devices containing 0,05% of resveratrol obtained by one-step process and 0,1% of resveratrol obtained by two-steps process were submitted to the release test during 24 h. Resveratrol quantification was done by high performance liquid chromatography (HPLC). The results obtained in the kinetics of release showed that only the devices obtained by two-step process release the resveratrol, which demonstrate antioxidant capacity after the release. (author)

Polymeric molecular sieve membranes via in situ cross-linking of non-porous polymer membrane templates.

Science.gov (United States)

Qiao, Zhen-An; Chai, Song-Hai; Nelson, Kimberly; Bi, Zhonghe; Chen, Jihua; Mahurin, Shannon M; Zhu, Xiang; Dai, Sheng

2014-04-16

High-performance polymeric membranes for gas separation are attractive for molecular-level separations in industrial-scale chemical, energy and environmental processes. Molecular sieving materials are widely regarded as the next-generation membranes to simultaneously achieve high permeability and selectivity. However, most polymeric molecular sieve membranes are based on a few solution-processable polymers such as polymers of intrinsic microporosity. Here we report an in situ cross-linking strategy for the preparation of polymeric molecular sieve membranes with hierarchical and tailorable porosity. These membranes demonstrate exceptional performance as molecular sieves with high gas permeabilities and selectivities for smaller gas molecules, such as carbon dioxide and oxygen, over larger molecules such as nitrogen. Hence, these membranes have potential for large-scale gas separations of commercial and environmental relevance. Moreover, this strategy could provide a possible alternative to 'classical' methods for the preparation of porous membranes and, in some cases, the only viable synthetic route towards certain membranes.

Photoinitiated Polymerization-Induced Self-Assembly of Glycidyl Methacrylate for the Synthesis of Epoxy-Functionalized Block Copolymer Nano-Objects.

Science.gov (United States)

Tan, Jianbo; Liu, Dongdong; Huang, Chundong; Li, Xueliang; He, Jun; Xu, Qin; Zhang, Li

2017-08-01

Herein, a novel photoinitiated polymerization-induced self-assembly formulation via photoinitiated reversible addition-fragmentation chain transfer dispersion polymerization of glycidyl methacrylate (PGMA) in ethanol-water at room temperature is reported. It is demonstrated that conducting polymerization-induced self-assembly (PISA) at low temperatures is crucial for obtaining colloidal stable PGMA-based diblock copolymer nano-objects. Good control is maintained during the photo-PISA process with a high rate of polymerization. The polymerization can be switched between "ON" and "OFF" in response to visible light. A phase diagram is constructed by varying monomer concentration and degree of polymerization. The PGMA-based diblock copolymer nano-objects can be further cross-linked by using a bifunctional primary amine reagent. Finally, silver nanoparticles are loaded within cross-linked vesicles via in situ reduction, exhibiting good catalytic properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A combined interfacial and in-situ polymerization strategy to construct well-defined core-shell epoxy-containing SiO2-based microcapsules with high encapsulation loading, super thermal stability and nonpolar solvent tolerance

Directory of Open Access Journals (Sweden)

Yin Jia

2016-10-01

Full Text Available SiO2-based microcapsules containing hydrophobic molecules exhibited potential applications such as extrinsic self-healing, drug delivery, due to outstanding thermal and chemical stability of SiO2. However, to construct SiO2-based microcapsules with both high encapsulation loading and long-term structural stability is still a troublesome issue, limiting their further utilization. We herein design a single-batch route, a combined interfacial and in-situ polymerization strategy, to fabricate epoxy-containing SiO2-based microcapsules with both high encapsulation loading and long-term structural stability. The final SiO2-based microcapsules preserve high encapsulation loading of 85.7 wt% by controlling exclusively hydrolysis and condensed polymerization at oil/water interface in the initial interfacial polymerization step. In the subsequent in-situ polymerization step, the initial SiO2-based microcapsules as seeds could efficiently harvest SiO2 precursors and primary SiO2 particles to finely tune the SiO2 wall thickness, thereby enhancing long-term structural stability of the final SiO2-based microcapsules including high thermal stability with almost no any weight loss until 250°C, and strong tolerance against nonpolar solvents such as CCl4 with almost unchanged core-shell structure and unchanged core weight after immersing into strong solvents for up to 5 days. These SiO2-based microcapsules are extremely suited for processing them into anticorrosive coating in the presence of nonpolar solvents for self-healing application.

Investigations into Alternative Desorption Agents for Amidoxime-Based Polymeric Uranium Adsorbents

Energy Technology Data Exchange (ETDEWEB)

Gill, Gary A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Kuo, Li-Jung [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Strivens, Jonathan E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Wood, Jordana R. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Wai, Chien [LCW Supercritical Technologies, Inc., Seattle, WA (United States); Pan, Horng-Bin [Univ. of Idaho, Moscow, ID (United States)

2015-06-01

Amidoxime-based polymeric braid adsorbents that can extract uranium (U) from seawater are being developed to provide a sustainable supply of fuel for nuclear reactors. A critical step in the development of the technology is to develop elution procedures to selectively remove U from the adsorbents and to do so in a manner that allows the adsorbent material to be reused. This study investigates use of high concentrations of bicarbonate along with targeted chelating agents as an alternative means to the mild acid elution procedures currently in use for selectively eluting uranium from amidoxime-based polymeric adsorbents.

Polymeric Coatings for Combating Biocorrosion

Science.gov (United States)

Guo, Jing; Yuan, Shaojun; Jiang, Wei; Lv, Li; Liang, Bin; Pehkonen, Simo O.

2018-03-01

Biocorrosion has been considered as big trouble in many industries and marine environments due to causing great economic loss. The main disadvantages of present approaches to prevent corrosion include being limited by environmental factors, being expensive, inapplicable to field, and sometimes inefficient. Studies show that polymer coatings with anti-corrosion and anti-microbial properties have been widely accepted as a novel and effective approach to preventbiocorrosion. The main purpose of this review is to summarize up the progressive status of polymer coatings used for combating microbially-induced corrosion. Polymers used to synthesize protective coatings are generally divided into three categories: i) traditional polymers incorporated with biocides, ii) antibacterial polymers containing quaternary ammonium compounds, and iii) conductive polymers. The strategies to synthesize polymer coatings resort mainly to grafting anti-bacterial polymers from the metal substrate surface using novel surface-functionalization approaches, such as free radical polymerization, chemically oxidative polymerization and surface-initiated atom transfer radical polymerization, as opposed to the traditional approaches of dip coating or spin coating.

Olefin metathesis and metathesis polymerization

CERN Document Server

Ivin, K J

1997-01-01

This book is a follow-up to Ivins Olefin Metathesis, (Academic Press, 1983). Bringing the standard text in the field up to date, this Second Edition is a result of rapid growth in the field, sparked by the discovery of numerous well-defined metal carbene complexes that can act as very efficient initiators of all types of olefin metathesis reaction, including ring-closing metathesis of acyclic dienes, enynes, and dienynes; ring-opening metathesis polymerizationof cycloalkenes, acyclic diene metathesis polymerization; and polymerization of alkynes, as well as simple olefin metathesis. Olefin Metathesis and Metathesis Polymerization provides a broad, up-to-date account of the subject from its beginnings in 1957 to the latest applications in organic synthesis. The book follows the same format as the original, making it useful toteachers and to researchers, and will be of particular interest to those working in the fields of organic chemistry, polymer chemistry, organometallic chemistry, catalysis, materials scien...

Polymeric implant of methylprednisolone for spinal injury ...

African Journals Online (AJOL)

Polymeric implant of methylprednisolone for spinal injury: preparation and characterization. Bo Yin, Jian-Jun Ji, Ming Yang. Abstract. Purpose: To improve the effectiveness and reduce the systemic side effects of methylprednisolone in traumatic spinal injuries, its polymeric implants were prepared using chitosan and sodium ...

Initiation of MMA polymerization by iniferters based on dithiocarbamates

Directory of Open Access Journals (Sweden)

Jovanović Slobodan M.

2005-01-01

Full Text Available Twelve modified dithiocarbamates and a thiuramdisulfide used for the initiation of methyl methacrylate (MMA polymerization were synthesized in this study. The polymerization of MMA was followed by determine the yield and molar mass of the obtained PMMA as a function of polymerization time. Four of the synthesized dithiocarbamates S-benzyl-N,N-dibenzyldithiocarbamate, S-allyl-N,N-dibenzyldithiocarbamate S-benzyl-N,N-diisobutyldithiocarbamate and S-benzoyl-N,N-diisobutyldithiocarbamate, as well as N,N,N',N'-tetrabenzylthiuramdisulfide acted as iniferters. They were active as the initiators of the photo and/or thermally initiated radical polymerization of MMA in bulk and inert solvents (benzene and toluene. S Benzyl - N,N - dibenzyldithiocarbamate can be successfully used for the initiation of MMA polymerization in a polar solvent such as dimethylacetamide.

Adsorption of trichloroethylene and benzene vapors onto hypercrosslinked polymeric resin

Energy Technology Data Exchange (ETDEWEB)

Liu Peng [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); Long Chao, E-mail: clong@nju.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); State Environmental Protection Engineering Center for Organic Chemical Industrial Waste Water Disposal and Resources Reuse, Nanjing 210046 (China); Jiangsu Engineering Research Center for Organic Pollution Control and Resources Reuse, Nanjing 210046 (China); Li Qifen [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); Qian Hongming [State Environmental Protection Engineering Center for Organic Chemical Industrial Waste Water Disposal and Resources Reuse, Nanjing 210046 (China); Jiangsu Engineering Research Center for Organic Pollution Control and Resources Reuse, Nanjing 210046 (China); Li Aimin; Zhang Quanxing [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); State Environmental Protection Engineering Center for Organic Chemical Industrial Waste Water Disposal and Resources Reuse, Nanjing 210046 (China); Jiangsu Engineering Research Center for Organic Pollution Control and Resources Reuse, Nanjing 210046 (China)

2009-07-15

In this research, the adsorption equilibria of trichloroethylene (TCE) and benzene vapors onto hypercrosslinked polymeric resin (NDA201) were investigated by the column adsorption method in the temperature range from 303 to 333 K and pressures up to 8 kPa for TCE, 12 kPa for benzene. The Toth and Dubinin-Astakov (D-A) equations were tested to correlate experimental isotherms, and the experimental data were found to fit well by them. The good fits and characteristic curves of D-A equation provided evidence that a pore-filling phenomenon was involved during the adsorption of TCE and benzene onto NDA-201. Moreover, thermodynamic properties such as the Henry's constant and the isosteric enthalpy of adsorption were calculated. The isosteric enthalpy curves varied with the surface loading for each adsorbate, indicating that the hypercrosslinked polymeric resin has an energetically heterogeneous surface. In addition, a simple mathematic model developed by Yoon and Nelson was applied to investigate the breakthrough behavior on a hypercrosslinked polymeric resin column at 303 K and the calculated breakthrough curves were in high agreement with corresponding experimental data.

Adsorption of trichloroethylene and benzene vapors onto hypercrosslinked polymeric resin.

Science.gov (United States)

Liu, Peng; Long, Chao; Li, Qifen; Qian, Hongming; Li, Aimin; Zhang, Quanxing

2009-07-15

In this research, the adsorption equilibria of trichloroethylene (TCE) and benzene vapors onto hypercrosslinked polymeric resin (NDA201) were investigated by the column adsorption method in the temperature range from 303 to 333 K and pressures up to 8 kPa for TCE, 12 kPa for benzene. The Toth and Dubinin-Astakov (D-A) equations were tested to correlate experimental isotherms, and the experimental data were found to fit well by them. The good fits and characteristic curves of D-A equation provided evidence that a pore-filling phenomenon was involved during the adsorption of TCE and benzene onto NDA-201. Moreover, thermodynamic properties such as the Henry's constant and the isosteric enthalpy of adsorption were calculated. The isosteric enthalpy curves varied with the surface loading for each adsorbate, indicating that the hypercrosslinked polymeric resin has an energetically heterogeneous surface. In addition, a simple mathematic model developed by Yoon and Nelson was applied to investigate the breakthrough behavior on a hypercrosslinked polymeric resin column at 303 K and the calculated breakthrough curves were in high agreement with corresponding experimental data.

Adsorption of trichloroethylene and benzene vapors onto hypercrosslinked polymeric resin

International Nuclear Information System (INIS)

Liu Peng; Long Chao; Li Qifen; Qian Hongming; Li Aimin; Zhang Quanxing

2009-01-01

In this research, the adsorption equilibria of trichloroethylene (TCE) and benzene vapors onto hypercrosslinked polymeric resin (NDA201) were investigated by the column adsorption method in the temperature range from 303 to 333 K and pressures up to 8 kPa for TCE, 12 kPa for benzene. The Toth and Dubinin-Astakov (D-A) equations were tested to correlate experimental isotherms, and the experimental data were found to fit well by them. The good fits and characteristic curves of D-A equation provided evidence that a pore-filling phenomenon was involved during the adsorption of TCE and benzene onto NDA-201. Moreover, thermodynamic properties such as the Henry's constant and the isosteric enthalpy of adsorption were calculated. The isosteric enthalpy curves varied with the surface loading for each adsorbate, indicating that the hypercrosslinked polymeric resin has an energetically heterogeneous surface. In addition, a simple mathematic model developed by Yoon and Nelson was applied to investigate the breakthrough behavior on a hypercrosslinked polymeric resin column at 303 K and the calculated breakthrough curves were in high agreement with corresponding experimental data.

Allylthioketone Mediated Free Radical Polymerization of Methacrylates

Directory of Open Access Journals (Sweden)

Feng Zhong

2017-11-01

Full Text Available By combination of high trapping free radical efficiency of the thioketone and resonance of the allylic radical, a new type of mediating agent, 1,3,3-triphenylprop-2-ene-1-thione (TPPT has been successfully synthesized, and then is used to study controlled free radical polymerization of methacrylates. Very stable TPPT radicals at the end of poly(methyl methacrylate (PMMA are detected in the polymerization of MMA using TPPT and AIBN as the control agent and initiator. The MALDI-TOF MS spectra are used to identify terminal groups of the resultant poly(glycidyl methacrylate (PGMA, and major component of the obtained polymer has the structure, (CH32(CNC-PGMA-C7H9O3. Chain extension reaction tests ascertain formation of the dead polymers during the polymer storage and purification process of the polymers. Owing to very slow fragmentation reaction of the TPPT-terminated polymethacrylate radical and addition reaction of this radical with a primary radical, the growing chain radicals are difficult to be regenerated, leading to an unobvious change of the molecular weight with monomer conversion. The molecular weights of polymers can be controlled by the ratios of monomer/initiator and TPPT/initiator. However, the first order kinetics of the polymerization and the polymers with narrow polydispersity are obtained, and these phenomena are discussed. This study provides useful information on how to design a better controlling agent.

Controlled Bioactive Molecules Delivery Strategies for Tendon and Ligament Tissue Engineering using Polymeric Nanofibers.

Science.gov (United States)

Hiong Teh, Thomas Kok; Hong Goh, James Cho; Toh, Siew Lok

2015-01-01

The interest in polymeric nanofibers has escalated over the past decade given its promise as tissue engineering scaffolds that can mimic the nanoscale structure of the native extracellular matrix. With functionalization of the polymeric nanofibers using bioactive molecules, localized signaling moieties can be established for the attached cells, to stimulate desired biological effects and direct cellular or tissue response. The inherently high surface area per unit mass of polymeric nanofibers can enhance cell adhesion, bioactive molecules loading and release efficiencies, and mass transfer properties. In this review article, the application of polymeric nanofibers for controlled bioactive molecules delivery will be discussed, with a focus on tendon and ligament tissue engineering. Various polymeric materials of different mechanical and degradation properties will be presented along with the nanofiber fabrication techniques explored. The bioactive molecules of interest for tendon and ligament tissue engineering, including growth factors and small molecules, will also be reviewed and compared in terms of their nanofiber incorporation strategies and release profiles. This article will also highlight and compare various innovative strategies to control the release of bioactive molecules spatiotemporally and explore an emerging tissue engineering strategy involving controlled multiple bioactive molecules sequential release. Finally, the review article concludes with challenges and future trends in the innovation and development of bioactive molecules delivery using polymeric nanofibers for tendon and ligament tissue engineering.

Immobilization/hybridization of amino-modified DNA on plasma-polymerized allyl chloride

International Nuclear Information System (INIS)

Zhang Zhihong; Feng Chuanliang

2007-01-01

The present work describes the fabrication and characterization of chloride-derivatized polymer coatings prepared by continuous wave (cw) plasma polymerization as adhesion layers in DNA immobilization/hybridization. The stability of plasma-polymerized allyl chloride (ppAC) in H 2 O was characterized by variation of the thickness of polymer films and its wettability was examined by water contact angle technique. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were used to study polymer matrix properties and oligonucleotide/DNA binding interaction. With the same carrier gas rate and process pressure, plasma polymers deposited at different input powers show various comparable immobilization properties; nevertheless, low input power plasma-polymerized films gives a lower sensitivity toward DNA binding than that from high input power plasma-deposited films. The following DNA immobilization on chloride-functionalized surfaces was found dependence on the macromolecular architecture of the plasma films. The hybridization between probe DNA and total mismatch target DNA shows no non-specific adsorption between target and ppAC

The distribution of InCl sub x compounds in model polymeric LEDs A combined low and high-energy ion beam analysis study

CERN Document Server

Reijme, M A; Simons, D P L; Schok, M; Ijzendoorn, L J V; Brongersma, H H; De Voigt, M J A

2002-01-01

A combination of low- and high-energy ion beam analysis techniques was used to determine the distribution of indium chloride compounds in model polymeric light-emitting diodes (p-LEDs). Parts of polymeric LEDs (polydialkoxyphenylenevinylene (OC sub 1 C sub 1 sub 0 -PPV) on indium-tin-oxide (ITO) substrates) were exposed to a HCl/Ar flow to simulate the processes occurring during conversion of precursor PPVs and acid treatment of polymers. Samples with variable exposure times as well as pristine samples were studied with Rutherford backscattering spectrometry (RBS), low energy ion scattering (LEIS), X-ray photoelectron spectroscopy (XPS) and particle induced X-ray emission (PIXE). The RBS measurements show that after HCl exposure indium is distributed throughout the OC sub 1 C sub 1 sub 0 -PPV layer. LEIS and XPS measurements indicate that the indium and chlorine are present at the outermost surface of the OC sub 1 C sub 1 sub 0 -PPV layer. PIXE measurements in combination with the RBS data demonstrate that th...

Isospecific propylene polymerization with in situ generated bis(phenoxy-amine)zirconium and hafnium single site catalysts.

Science.gov (United States)

Makio, Haruyuki; Prasad, Aitha Vishwa; Terao, Hiroshi; Saito, Junji; Fujita, Terunori

2013-07-07

Bis(phenoxy-imine) Zr and Hf complexes were activated with (i)Bu3Al or (i)Bu2AlH in conjunction with Ph3CB(C6F5)4 and tested as catalysts for propylene polymerization with emphasis on the enantioselectivity of the isospecific species and the single site polymerization characteristics. The isoselective species was identified as the in situ generated bis(phenoxy-amine) complex whose isoselectivity was sensitive to subtle changes in ligand structure. By employing specific substituents at certain key positions the isotacticity reached an extremely high level comparable to high-end commercial isotactic polypropylenes (Tm > 160 °C). Single site polymerization characteristics depended upon the efficiency and selectivity of the in situ imine reduction which is sensitive to the substituent on the imine nitrogen and the reaction conditions. By using (i)Bu2AlH as a reducing agent, quantitative imine reduction can be achieved with a stoichiometric amount of the reducing agent. This lower alkylaluminum loading is beneficial for the catalyst and significantly enhances the polymerization activity and the molecular weight of the resultant polymer.

Polymeric micelles for ocular drug delivery: From structural frameworks to recent preclinical studies.

Science.gov (United States)

Mandal, Abhirup; Bisht, Rohit; Rupenthal, Ilva D; Mitra, Ashim K

2017-02-28

Effective intraocular drug delivery poses a major challenge due to the presence of various elimination mechanisms and physiological barriers that result in low ocular bioavailability after topical application. Over the past decades, polymeric micelles have emerged as one of the most promising drug delivery platforms for the management of ocular diseases affecting the anterior (dry eye syndrome) and posterior (age-related macular degeneration, diabetic retinopathy and glaucoma) segments of the eye. Promising preclinical efficacy results from both in-vitro and in-vivo animal studies have led to their steady progression through clinical trials. The mucoadhesive nature of these polymeric micelles results in enhanced contact with the ocular surface while their small size allows better tissue penetration. Most importantly, being highly water soluble, these polymeric micelles generate clear aqueous solutions which allows easy application in the form of eye drops without any vision interference. Enhanced stability, larger cargo capacity, non-toxicity, ease of surface modification and controlled drug release are additional advantages with polymeric micelles. Finally, simple and cost effective fabrication techniques render their industrial acceptance relatively high. This review summarizes structural frameworks, methods of preparation, physicochemical properties, patented inventions and recent advances of these micelles as effective carriers for ocular drug delivery highlighting their performance in preclinical studies. Copyright © 2017 Elsevier B.V. All rights reserved.

Scale-up of microwave-assisted polymerizations in continuous-flow mode : cationic ring-opening polymerization of 2-ethyl-2-oxazoline

NARCIS (Netherlands)

Paulus, R.M.; Erdmenger, T.; Becer, C.R.; Hoogenboom, R.; Schubert, U.S.

2007-01-01

Microwave-assisted polymerizations is a growing field of interest because the use of microwave irradiation instead of thermal heating was demonstrated to result in faster, cleaner, and higher yielding reactions. To overcome the one-at-a-time nature of preparing polymerizations in single microwave

Fiscal 1994 technological survey report. Research study on polymer materials by precision polymerization; 1994 nendo seimitsu jugo kobunshi zairyo ni kansuru chosa kenkyu hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1995-03-01

In the paradigm that propelled polymer chemistry, there are involved the establishment of polymer concept, engineering plastics, regulation of higher ordered structure, and precision polymerization. The first two produced the polymer chemistry era in the 20th century. The regulation of higher ordered structure and the precision polymerization are the fundamental technologies supporting the polymer chemistry of the 21st century. The precision polymerization is a technology for regulating the stereospecificity, sequential structure, and molecular weight of polymers by regulating atoms and molecules and is referred to the following important techniques to be concrete. In the precision addition polymerization, stereospecific regulation and purification of active site to give living polymers are required while, in the precision condensation polymerization, regulation of condensation probability process to be secondary Marcov chain is necessary, as is the establishment of non-defect condensation condition avoiding high temperature deterioration and the like. In the biomimetic precision polymerization, key issues are the method of incorporating molecular recognition control and sequential structure control by living organs into an industrial process. If the higher ordered structure can be regulated by the precision polymerization, it is possible to obtain numerous high performance/high functional materials such as superconductors. (NEDO)

Synthesis and butadiene polymerization behaviors of cationic cobalt-based catalyst

Directory of Open Access Journals (Sweden)

Li Liu

2017-01-01

Full Text Available A series of cationic cobalt-based compounds bearing different neutral N-bearing ligands (1,10-phenanthroline, bipyridine, benzimidazole, terpyridine and anionic ligands (trifluoromethanesulfonate, methanesulfonate were synthesized and the simple compound, Co(Phen2Cl2, was also prepared as a reference compound. All the compounds were characterized along with infrared spectra analysis and some of them were further confirmed by single crystal X-ray crystallographic analysis. Upon activation with ethylaluminum sesquichloride, these cationic cobalt(II compounds showed high catalytic activities for butadiene polymerization. The detailed investigations were carried out to disclose the influence of various polymerization conditions, sterical and electronic parameters of the ligands on their performing activities of the compounds.

Biomimetic polymeric membranes for water treatment

DEFF Research Database (Denmark)

Habel, Joachim Erich Otto

This project is about the interplay of the three major components of aquaporin based biomimetic polymeric membranes (ABPMs): Aquaporins (AQPs), amphiphilic block copolymers, serving as a vesicular matrix for the hydrophobic AQP exterior (proteopolymersomes) and a polymeric membrane as embedment....... The interplay of proteopolymersomes and polymeric mesh support (in this case polyethersulfone, PES) was examined via integration of proteopolymersomes in an active layer (AL) formed by interfacial polymerisation between a linker molecule in aqueous phase and another in organic phase on top of the PES....... The resulting thin-film composite (TFC) membrane was analyzed via cross-flow forward osmosis (FO), scanning electron microscopy (SEM), fourier-transformed infrared spectroscopy (FTIR), as well as in the non-supported form over FTIR and a specialized microfluidic visualization approach. Where no clear dierences...

Ring-Expansion/Contraction Radical Crossover Reactions of Cyclic Alkoxyamines: A Mechanism for Ring Expansion-Controlled Radical Polymerization

Directory of Open Access Journals (Sweden)

Atsushi Narumi

2018-06-01

Full Text Available Macrocyclic polymers present an important class of macromolecules, displaying the reduced radius of gyration or impossibility to entangle. A rare approach for their synthesis is the ring expansion-controlled radical “vinyl” polymerization, starting from a cyclic alkoxyamine. We here describe ring-expansion radical crossover reactions of cyclic alkoxyamines which run in parallel to chain-propagation reactions in the polymerization system. The radical crossover reactions extensively occurred at 105–125 °C, eventually producing high molecular weight polymers with multiple inherent dynamic covalent bonds (NOC bonds. A subsequent ring-contraction radical crossover reaction and the second ring-expansion radical crossover reaction are also described. The major products for the respective three stages were shown to possess cyclic morphologies by the molecular weight profiles and the residual ratios for the NOC bonds (φ in %. In particular, the high φ values ranging from ca. 80% to 98% were achieved for this cyclic alkoxyamine system. This result verifies the high availability of this system as a tool demonstrating the ring-expansion “vinyl” polymerization that allows them to produce macrocyclic polymers via a one-step vinyl polymerization.

Operation voltage behavior of organic light emitting diodes with polymeric buffer layers doped by weak electron acceptor

Energy Technology Data Exchange (ETDEWEB)

Jeon, Hyeon Soo; Cho, Sang Hee [Department of Information Display and Advanced Display Research Center, Kyung Hee University, Seoul 130-701 (Korea, Republic of); Seo, Jaewon; Park, Yongsup [Department of Physics, Kyung Hee University, Seoul 130-701 (Korea, Republic of); Suh, Min Chul, E-mail: mcsuh@khu.ac.kr [Department of Information Display and Advanced Display Research Center, Kyung Hee University, Seoul 130-701 (Korea, Republic of)

2013-11-01

We present polymeric buffer materials based on poly[2,7-(9,9-dioctyl-fluorene)-co-(1,4-phenylene -((4-sec-butylphenyl)imino)-1,4-phenylene)] (TFB) for highly efficient solution processed organic light emitting diodes (OLEDs). Doped TFB with 9,10-dicyanoanthracene, a weak electron acceptor results in significant improvement of current flow and driving voltage. Maximum current- and power-efficiency value of 12.6 cd/A and 18.1 lm/W are demonstrated from phosphorescent red OLEDs with this doped polymeric anode buffer system. - Highlights: • Polymeric buffer materials for organic light emitting diodes (OLEDs). • Method to control hole conductivity of polymeric buffer layer in OLED device. • Enhanced current density of buffer layers upon 9,10-dicyanoanthracene (DCA) doping. • Comparison of OLED devices having polymeric buffer layer with or without DCA. • Effect on operating voltage by doping DCA in the buffer layer.

Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases

KAUST Repository

Ntetsikas, Konstantinos

2017-10-23

The anionic polymerization of styrene and 1,3-butadiene in the presence of phosphazene bases (t-BuP4, t-BuP2 and t-BuP1), in benzene at room temperature, was studied. When t-BuP1 was used, the polymerization proceeded in a controlled manner, whereas the obtained homopolymers exhibited the desired molecular weights and narrow polydispersity (Ð < 1.05). In the case of t-BuP2, homopolymers with higher than the theoretical molecular weights and relatively low polydispersity were obtained. On the other hand, in the presence of t-BuP4, the polymerization of styrene was uncontrolled due to the high reactivity of the formed carbanion. The kinetic studies from the polymerization of both monomers showed that the reaction rate follows the order of [t-BuP4]/[sec-BuLi] >>> [t-BuP2]/[sec-BuLi] >> [t-BuP1]/[sec-BuLi] > sec-BuLi. Furthermore, the addition of t-BuP2 and t-BuP1 prior the polymerization of 1,3-butadiene allowed the synthesis of polybutadiene with a high 1,2-microstructure (~45 wt %), due to the delocalization of the negative charge. Finally, the one pot synthesis of well-defined polyester-based copolymers [PS-b-PCL and PS-b-PLLA, PS: Polystyrene, PCL: Poly(ε-caprolactone) and PLLA: Poly(L-lactide)], with predictable molecular weights and a narrow molecular weight distribution (Ð < 1.2), was achieved by sequential copolymerization in the presence of t-BuP2 and t-BuP1.

Comparison between rice husk ash and commercial silica as filler in polymeric composites

International Nuclear Information System (INIS)

Fernandes, I.J.; Calheiro, D.; Santos, E.C.A. dos; Oliveira, R.; Rocha, T.L.A.C.; Moraes, C.A.M.

2014-01-01

The use of rice husk ash (RHA) as filler in polymeric materials has been studied in different polymers. Research reported that RHA may successfully replace silica. The silica production process using ore demands high energy input and produces considerable amounts of waste. Therefore, the replacement of silica by RHA may be economically and environmentally advantageous, reducing environmental impact and adding value to a waste material. In this context, this study characterizes and compares RHA of different sources (travelling grate reactor and fluidized bed reactor) with commercially available silicas to assess performance as filler in polymeric materials. Samples were characterized by X-ray fluorescence, loss on ignition, X-ray diffraction, grain size, specific surface area and specific weight. The results show that RHA may be used as a filler in several polymeric materials.(author)

Biomimetic PEGylation of carbon nanotubes through surface-initiated RAFT polymerization.

Science.gov (United States)

Shi, Yingge; Zeng, Guanjian; Xu, Dazhuang; Liu, Meiying; Wang, Ke; Li, Zhen; Fu, Lihua; Zhang, Qingsong; Zhang, Xiaoyong; Wei, Yen

2017-11-01

Carbon nanotubes (CNTs) are a type of one-dimensional carbon nanomaterials that possess excellent physicochemical properties and have been potentially utilized for a variety of applications. Surface modification of CNTs with polymers is a general route to expand and improve the performance of CNTs and has attracted great research interest over the past few decades. Although many methods have been developed previously, most of these methods still showed some disadvantages, such as low efficiency, complex experimental procedure and harsh reaction conditions etc. In this work, we reported a practical and novel way to fabricate CNTs based polymer composites via the combination of mussel inspired chemistry and reversible addition fragmentation chain transfer (RAFT) polymerization. First, the amino group was introduced onto the surface of CNTs via self-polymerization of dopamine. Then, chain transfer agent can be immobilized on the amino groups functionalized CNTs to obtain CNT-PDA-CTA, which can be utilized for surface-initiated RAFT polymerization. A water soluble and biocompatible monomer poly(ethylene glycol) monomethyl ether methacrylate (PEGMA) was adopted to fabricate pPEGMA functionalized CNTs through RAFT polymerization. The successful preparation of CNTs based polymer composites (CNT-pPEGMA) was confirmed by transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and X-ray photoelectron spectroscopy in details. The CNT-pPEGMA showed good dispersibility and desirable biocompatibility, making them highly potential for biomedical applications. More importantly, a large number of CNTs based polymer composites could also be fabricated through the same strategy when different monomers were used due to the good monomer adaptability of RAFT polymerization. Therefore, this strategy should be a general method for preparation of various multifunctional CNTs based polymer composites. Copyright © 2017 Elsevier B.V. All rights

Post polymerization cure shape memory polymers

Energy Technology Data Exchange (ETDEWEB)

Wilson, Thomas S.; Hearon, II, Michael Keith; Bearinger, Jane P.

2017-01-10

This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

Post polymerization cure shape memory polymers

Science.gov (United States)

Wilson, Thomas S; Hearon, Michael Keith; Bearinger, Jane P

2014-11-11

This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

Simulating Controlled Radical Polymerizations with mcPolymer—A Monte Carlo Approach

Directory of Open Access Journals (Sweden)

Georg Drache

2012-07-01

Full Text Available Utilizing model calculations may lead to a better understanding of the complex kinetics of the controlled radical polymerization. We developed a universal simulation tool (mcPolymer, which is based on the widely used Monte Carlo simulation technique. This article focuses on the software architecture of the program, including its data management and optimization approaches. We were able to simulate polymer chains as individual objects, allowing us to gain more detailed microstructural information of the polymeric products. For all given examples of controlled radical polymerization (nitroxide mediated radical polymerization (NMRP homo- and copolymerization, atom transfer radical polymerization (ATRP, reversible addition fragmentation chain transfer polymerization (RAFT, we present detailed performance analyses demonstrating the influence of the system size, concentrations of reactants, and the peculiarities of data. Different possibilities were exemplarily illustrated for finding an adequate balance between precision, memory consumption, and computation time of the simulation. Due to its flexible software architecture, the application of mcPolymer is not limited to the controlled radical polymerization, but can be adjusted in a straightforward manner to further polymerization models.

Supramolecular intermediates in the synthesis of polymeric carbon nitride from melamine cyanurate

International Nuclear Information System (INIS)

Dante, Roberto C.; Sánchez-Arévalo, Francisco M.; Chamorro-Posada, Pedro; Vázquez-Cabo, José; Huerta, Lazaro; Lartundo-Rojas, Luis; Santoyo-Salazar, Jaime

2015-01-01

The adduct of melamine and cyanuric acid (MCA) was used in past research to produce polymeric carbon nitride and precursors. The reaction yield was considerably incremented by the addition of sulfuric acid. The polymeric carbon nitride formation occurs around 450 °C at temperatures above the sublimation of the adduct components, which occurs around 400 °C. In this report the effect of sulfuric acid on MCA was investigated. It was found that the MCA rosette supramolecular channel structures behave as a solid solvent able to host small molecules, such as sulfuric acid, inside these channels and interact with them. Therefore, the sulfuric acid effect was found to be close to that of a solute that causes a temperature increment of the “solvent sublimation” enough to allowing the formation of polymeric carbon nitride to occur. Sulfate ions are presumably hosted in the rosette channels of MCA as shown by simulations. - Graphical abstract: The blend of melamine cyanurate and sulfuric acid behaves like a solution so that melamine cyanurate decomposition is shifted to temperatures high enough to react and form polymeric carbon nitride. - Highlights: • The adduct of melamine and cyanuric acid behaves as a solid solvent. • The blend of sulfuric acid and melamine cyanurate behaves like a solution. • Melamine cyanurate decomposition is shifted to higher temperatures by sulfuric acid. • The formation of polymeric carbon nitride occurs for these higher temperatures

Supramolecular intermediates in the synthesis of polymeric carbon nitride from melamine cyanurate

Energy Technology Data Exchange (ETDEWEB)

Dante, Roberto C., E-mail: rcdante@yahoo.com [Facultad de Mecánica, Escuela Politécnica Nacional (EPN), Ladrón de Guevara E11-253, Quito (Ecuador); Sánchez-Arévalo, Francisco M. [Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de Mexico, Apdo. Postal 70-360, Cd. Universitaria, Mexico D.F. 04510 (Mexico); Chamorro-Posada, Pedro [Dpto. de Teoría de la Señal y Comunicaciones e IT, Universidad de Valladolid, ETSI Telecomunicación, Paseo Belén 15, 47011 Valladolid (Spain); Vázquez-Cabo, José [Dpto. de Teoría de la Señal y Comunicaciones, Universidad de Vigo, ETSI Telecomunicación, Lagoas Marcosende s/n, Vigo (Spain); Huerta, Lazaro [Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de Mexico, Apdo. Postal 70-360, Cd. Universitaria, Mexico D.F. 04510 (Mexico); Lartundo-Rojas, Luis [Centro de Nanociencias y Micro y Nanotecnologías—IPN, Luis Enrique Erro s/n, U. Prof. Adolfo López Mateos, 07738 Ciudad de Mexico, Distrito Federal (Mexico); Santoyo-Salazar, Jaime [Departamento de Física, Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional, CINVESTAV-IPN, Apdo. Postal 14-740, Mexico D.F. 07360 (Mexico); and others

2015-03-15

The adduct of melamine and cyanuric acid (MCA) was used in past research to produce polymeric carbon nitride and precursors. The reaction yield was considerably incremented by the addition of sulfuric acid. The polymeric carbon nitride formation occurs around 450 °C at temperatures above the sublimation of the adduct components, which occurs around 400 °C. In this report the effect of sulfuric acid on MCA was investigated. It was found that the MCA rosette supramolecular channel structures behave as a solid solvent able to host small molecules, such as sulfuric acid, inside these channels and interact with them. Therefore, the sulfuric acid effect was found to be close to that of a solute that causes a temperature increment of the “solvent sublimation” enough to allowing the formation of polymeric carbon nitride to occur. Sulfate ions are presumably hosted in the rosette channels of MCA as shown by simulations. - Graphical abstract: The blend of melamine cyanurate and sulfuric acid behaves like a solution so that melamine cyanurate decomposition is shifted to temperatures high enough to react and form polymeric carbon nitride. - Highlights: • The adduct of melamine and cyanuric acid behaves as a solid solvent. • The blend of sulfuric acid and melamine cyanurate behaves like a solution. • Melamine cyanurate decomposition is shifted to higher temperatures by sulfuric acid. • The formation of polymeric carbon nitride occurs for these higher temperatures.

Non-equilibrium supramolecular polymerization.

Science.gov (United States)

Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M

2017-09-18

Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term "non-equilibrium self-assembly" by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.

A Review on Surface Stress-Based Miniaturized Piezoresistive SU-8 Polymeric Cantilever Sensors

Science.gov (United States)

Mathew, Ribu; Ravi Sankar, A.

2018-06-01

In the last decade, microelectromechanical systems (MEMS) SU-8 polymeric cantilevers with piezoresistive readout combined with the advances in molecular recognition techniques have found versatile applications, especially in the field of chemical and biological sensing. Compared to conventional solid-state semiconductor-based piezoresistive cantilever sensors, SU-8 polymeric cantilevers have advantages in terms of better sensitivity along with reduced material and fabrication cost. In recent times, numerous researchers have investigated their potential as a sensing platform due to high performance-to-cost ratio of SU-8 polymer-based cantilever sensors. In this article, we critically review the design, fabrication, and performance aspects of surface stress-based piezoresistive SU-8 polymeric cantilever sensors. The evolution of surface stress-based piezoresistive cantilever sensors from solid-state semiconductor materials to polymers, especially SU-8 polymer, is discussed in detail. Theoretical principles of surface stress generation and their application in cantilever sensing technology are also devised. Variants of SU-8 polymeric cantilevers with different composition of materials in cantilever stacks are explained. Furthermore, the interdependence of the material selection, geometrical design parameters, and fabrication process of piezoresistive SU-8 polymeric cantilever sensors and their cumulative impact on the sensor response are also explained in detail. In addition to the design-, fabrication-, and performance-related factors, this article also describes various challenges in engineering SU-8 polymeric cantilevers as a universal sensing platform such as temperature and moisture vulnerability. This review article would serve as a guideline for researchers to understand specifics and functionality of surface stress-based piezoresistive SU-8 cantilever sensors.[Figure not available: see fulltext.

On reactions of polymerization of p-element hydroxides in aqueous solutions

International Nuclear Information System (INIS)

Tikavyj, V.F.; Lesnikovich, A.I.

1978-01-01

The tendency of p-element hydroxides towards polymerization in aqueous solutions has been considered with respect to their location in the Periodic Table. Stable hydroxides of d-elements are practically all polymerized; among s-elements only berillium and magnesium hydroxides polymerize as the least dissociated ones. Hydroxides of the elements located to the right of the 4 Group and above the 5-th Period do not polymerize in aqueous solutions. The structure and tendency towards polymerization of In, Te, and I compounds have been studied. The tendency to polymerization of all hydroxides of p-elements located below the 4-th Period is explained from the standpoint of electron structure and the simplest thermodynamic analysis (entropy, enthalpy)

Radiation induced solid-state polymerization of long-chain acrylates containing fluorocarbon chain

International Nuclear Information System (INIS)

Shibasaki, Y.; Zhu, Zhi-Qin

1995-01-01

γ-Ray irradiation post-polymerizations of long-chain acrylates containing fluorocarbon chain, H(CF 2 ) 10 CH 2 OCOCH=CH 2 and H(CF 2 ) 8 CH 2 OCOCH=CH 2 , were investigated and also the structures and thermal properties of comb-like polymers obtained were studied. It was found that these monomers exhibited very high polymerizability at wide temperature ranges around the melting points. Because the fluorocarbon chains are less flexible and thicker than the hydrocarbon chains, it can be expected that the aggregation force among the monomer molecules is strong and the conformational freedom of functional group for polymerization is large. According to the DSC and the X-ray diffraction measurements of the comb-like polymers obtained, the fluorocarbon chains are aggregated in a mode of hexagonal packing in the lamellar crystals. This situation can be considered as an optimum condition for the γ-ray irradiation post-polymerization. (author)

Fabrication and manipulation of polymeric magnetic particles with magnetorheological fluid

International Nuclear Information System (INIS)

Rodríguez-López, Jaime; Shum, Ho Cheung; Elvira, Luis; Montero de Espinosa, Francisco; Weitz, David A.

2013-01-01

Polymeric magnetic microparticles have been created using a microfluidic device via ultraviolet (UV) polymerization of double emulsions, resulting in cores of magnetorheological (MR) fluids surrounded by polymeric shells. We demonstrate that the resultant particles can be manipulated magnetically to achieve triggered rupture of the capsules. This illustrates the great potential of our capsules for triggered release of active ingredients encapsulated in the polymeric magnetic microparticles. - Highlights: ► Polymeric microparticles encapsulating MR fluids have been fabricated. ► A double-emulsion-templated approach using microfluidic techniques has been used. ► The monodisperse microparticles obtained are easily manipulated under magnetic field. ► These microparticles have great potential for encapsulation-and-release applications.

Innovative cellular distance structures from polymeric and metallic threads

Science.gov (United States)

Wieczorek, F.; Trümper, W.; Cherif, C.

2017-10-01

Knitting allows a high individual adaptability of the geometry and properties of flat-knitted spacer fabrics. This offers advantages for the specific adjustment of the mechanical properties of innovative composites based on highly viscous matrix systems such as bone cement, elastomer or foam and cellular reinforcing structures made from e. g. polymeric monofilaments or metallic wires. The prerequisite is the availability of binding solutions for highly productive production of functional, cellular, self-stabilized spacer flat knitted fabrics as supporting and functionalized structures.

Ternary hybrid polymeric nanocomposites through grafting of polystyrene on graphene oxide-TiO{sub 2} by surface initiated atom transfer radical polymerization (SI-ATRP)

Energy Technology Data Exchange (ETDEWEB)

Kumar, Arvind; Bansal, Ankushi; Behera, Babita; Jain, Suman L.; Ray, Siddharth S., E-mail: ssray@iip.res.in

2016-04-01

A ternary hybrid of graphene oxide-titania-polystyrene (GO-TiO{sub 2}-PS) nanocomposite is developed where polystyrene composition is regulated by controlling growth of polymer chains and nanoarchitectonics is discussed. Graphene Oxide-TiO{sub 2} (GO-TiO{sub 2}) nanocomposite is prepared by in-situ hydrothermal method and the surface is anchored with α-bromoisobutyryl bromide to activate GO-TiO{sub 2} as initiator for polymerization. In-situ grafting of polystyrene through surface initiated atom transfer radical polymerization (SI- ATRP) on this Br-functionalized nano-composite initiator yields GO-TiO{sub 2}-PS ternary hybrid. Varying the monomer amount and keeping the concentration of initiator constant, polystyrene chain growth is regulated with narrow poly-dispersivity to achieve desired composition. This composite is well characterized by various analytical techniques like FTIR, XRD, DSC, SEM, TEM, and TGA. - Highlights: • Nanocomposite of ternary hybrid of GO-TiO{sub 2} with polystyrene. • PS is surface grafted on GO-TiO{sub 2}. • Polymer chain lengths are well regulated by SI-ATRP living polymerization. • Thermal stability of this hybrid is relatively high.

Polymeric Cantilever Arrays for Biosensing Applications

DEFF Research Database (Denmark)

Calleja, M.; Tamayo, J.; Johansson, Alicia

2003-01-01

We report the fabrication of arrays of polymeric cantilevers for biochemistry applications. The cantilevers are fabricated in the polymer SU-8. The use of a polymer as the component material for the cantilevers provides the sensors with very high sensitivity due to convenient mechanical material...... properties. The fabrication process is based on spin coating of the photosensitive polymer and near-ultraviolet exposure. The method allows obtaining well-controlled and uniform mechanical properties of the cantilevers. The elastic constant of the cantilevers was measured, and their dynamic response...

Comparison of techniques for the determination of conversion during suspension polymerization reactions

Directory of Open Access Journals (Sweden)

J. C. Santos

2008-06-01

Full Text Available The determination of conversion during suspension polymerization reactions is not an easy task due to the heterogeneity of the reaction medium and the tendency of particles to agglomerate rapidly when stirring is stopped. Usually, bulk polymerization in ampoules is employed to study the kinetics of suspension polymerization reactions. In this work, a comparison of different techniques for the determination of conversion during suspension polymerization reactions is presented. Results showed a good agreement between the conversion obtained by gravimetry during styrene suspension polymerization and on-line conversion monitoring data using fiber-optic based Raman Spectroscopy. Nevertheless, the polymerization rate of styrene bulk polymerization carried out in ampoules was higher than the real reaction rate of styrene suspension polymerization due to slightly higher reaction temperatures. Simulation results using the experimental temperature data in a mathematical model confirmed these results.

Graphene-coated polymeric anion exchangers for ion chromatography

Energy Technology Data Exchange (ETDEWEB)

Zhang, Kai; Cao, Minyi; Lou, Chaoyan [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China); Wu, Shuchao, E-mail: wushch2002@163.com [Zhejiang Institute of Geology and Mineral Resources, Hangzhou 310007 (China); Zhang, Peimin [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China); Zhi, Mingyu [Hangzhou Vocational & Technical College, Hangzhou, 310018 (China); Zhu, Yan, E-mail: zhuyan@zju.edu.cn [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China)

2017-06-01

Carbonaceous stationary phases have gained much attention for their peculiar selectivity and robustness. Herein we report the fabrication and application of a graphene-coated polymeric stationary phase for anion exchange chromatography. The graphene-coated particles were fabricated by a facile evaporation-reduction method. These hydrophilic particles were proven appropriate substrates for grafting of hyperbranched condensation polymers (HBCPs) to make pellicular anion exchangers. The new phase was characterized by zeta potentials, Fourier transform infrared spectroscopy, thermogravimetry and scanning electron microscope. Frontal displacement chromatography showed that the capacities of the anion exchangers were tuned by both graphene amount and HBCPs layer count. The chromatographic performance of graphene-coated anion exchangers was demonstrated with separation of inorganic anions, organic acids, carbohydrates and amino acids. Good reproducibility was obtained by consecutive injections, indicating high chemical stability of the coating. - Highlights: • Graphene-coated polymeric particles were fabricated by a facile method. • Hyperbranched condensation polymers (HBCPs) were grafted from graphene-coated particles to make anion exchangers. • Graphene amount and HBCPs layer count had significant effects on the anion exchange capacities. • Separation of diverse anionic analytes on the anion exchangers was demonstrated. • The prepared anion exchangers exhibited high stability.

Conjugated Polymers Via Direct Arylation Polymerization in Continuous Flow: Minimizing the Cost and Batch-to-Batch Variations for High-Throughput Energy Conversion.

Science.gov (United States)

Gobalasingham, Nemal S; Carlé, Jon E; Krebs, Frederik C; Thompson, Barry C; Bundgaard, Eva; Helgesen, Martin

2017-11-01

Continuous flow methods are utilized in conjunction with direct arylation polymerization (DArP) for the scaled synthesis of the roll-to-roll compatible polymer, poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(4,7-di(thiophen-2-yl)-benzo[c][1,2,5]thiadiazole)] (PPDTBT). PPDTBT is based on simple, inexpensive, and scalable monomers using thienyl-flanked benzothiadiazole as the acceptor, which is the first β-unprotected substrate to be used in continuous flow via DArP, enabling critical evaluation of the suitability of this emerging synthetic method for minimizing defects and for the scaled synthesis of high-performance materials. To demonstrate the usefulness of the method, DArP-prepared PPDTBT via continuous flow synthesis is employed for the preparation of indium tin oxide (ITO)-free and flexible roll-coated solar cells to achieve a power conversion efficiency of 3.5% for 1 cm 2 devices, which is comparable to the performance of PPDTBT polymerized through Stille cross coupling. These efforts demonstrate the distinct advantages of the continuous flow protocol with DArP avoiding use of toxic tin chemicals, reducing the associated costs of polymer upscaling, and minimizing batch-to-batch variations for high-quality material. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phosphazene-promoted anionic polymerization

KAUST Repository

Zhao, Junpeng; Hadjichristidis, Nikolaos; Gnanou, Yves

2014-01-01

.e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

Polymerization Using Phosphazene Bases

KAUST Repository

Zhao, Junpeng; Hadjichristidis, Nikolaos; Schlaad, Helmut

2015-01-01

. In this chapter, the general features of phosphazenepromoted/catalyzed polymerizations and the applications in macromolecular engineering (synthesis of functionalized polymers, block copolymers, and macromolecular architectures) are discussed with challenges

Radiation-induced polymerization monitored in situ by time-resolved fluorescence of probe molecules in methyl methacrylate

International Nuclear Information System (INIS)

Frahn, Mark S.; Abellon, Ruben D.; Luthjens, Leonard H.; Vermeulen, Martien J.W.; Warman, John M.

2003-01-01

A technique is presented for monitoring radiation-induced polymerizations in situ based on the measurement of the fluorescence lifetime of molecular probes dissolved in the polymerizing medium. This method is illustrated with results on methyl methacrylate (MMA) using two fluorogenic probe molecules; N-(2-anthracene)methacrylamide (AnMA) and maleimido-fluoroprobe (MFP), a molecule which has a highly dipolar excited state

Chemical characterization of polymeric surge arresters and insulators used in high voltage lines; Caracterizacao quimica de para-raios e isoladores utilizados em linhas de alta tensao

Energy Technology Data Exchange (ETDEWEB)

Oliveira Junior, Joao B. de; Castro Junior, Joao B. de; Silva, Maria Elisa S.R. e; Freitas, Roberto F.S.; Sousa, Ricardo G. de [Lab. de Ciencia e Tecnologia de Polimeros, Dept. de Engenharia Quimica da EE.UFMG, Belo Horizonte, MG (Brazil); Souza, Breno P.G. de [CEMIG Distribuicao S/A, Belo Horizonte, MG (Brazil)], e-mail: bpgsouza@gmail.com

2011-07-01

In the last two decades, traditional porcelain and glass surge arresters and insulators, used in the electrical system, have been replaced by polymeric materials. For this type of application it is recommended that these devices have a high resistance to environmental stresses and impacts without suffering degradation process. Considering the environmental conditions these polymers are exposed to, when used for this purpose, studies of their chemical composition are needed. In this work, polymeric materials present in surge arresters and insulators used in electrical system were chemically characterized by Fourier Transform Infrared Spectroscopy (FTIR). FTIR analysis showed that the samples tested are made of poly(dimethylsiloxane) - PDMS (silicone) and additives such as alumina trihydrated [Al (OH)3] and calcium carbonate. (author)

Synthesis and Ring-Opening Metathesis Polymerization of Second-Generation Dendronized Poly(ether Monomers Initiated by Ruthenium Carbenes

Directory of Open Access Journals (Sweden)

Guzmán Pablo E.

2016-03-01

Full Text Available The Ring-Opening Metathesis Polymerization (ROMP of second-generation dendronized monomers is described. Using the highly active and fast-initiating third-generation ruthenium complex [(H2IMes(pyr2Cl2RuCHPh], moderate to high molecular weight polymers (430-2230 kDa are efficiently synthesized with low dispersities (Ð = 1.01-1.17. This study highlights the power of the metathesis approach toward polymer synthesis in a context where monomer structure can significantly impede polymerization.

Formulation and Characterization of Pyrazinamide Polymeric Nanoparticles for Pulmonary Tuberculosis: Efficiency for Alveolar Macrophage Targeting

OpenAIRE

Varma, J. N. Ravi; Kumar, T. Santosh; Prasanthi, B.; Ratna, J. Vijaya

2015-01-01

Pyrazinamide, a highly specific agent against Mycobacterium tuberculosis is used as first-line drug to treat tuberculosis. The current work aims to formulate polymeric nanoparticles based drug delivery system to sustain the release profile and reduce the dosing frequency of pyrazinamide. Further aim was to target the macrophages within body fluid. These polymeric nanoparticles were prepared by simultaneous double-emulsion (W/O/W) solvent evaporation/diffusion technique. The prepared dispersio...

Real time in situ spectroscopic characterization of radiation induced cationic polymerization of glycidyl ethers

International Nuclear Information System (INIS)

Mascioni, Matteo; Sands, James M.; Palmese, Giuseppe R.

2003-01-01

Radiation curable polymeric materials suffer from relatively poor mechanical properties. Moreover, the curing behavior of such systems (i.e. the exact relationship between chemical kinetics and key processing variables) is not fully understood. In order to design improved epoxy based electron beam (EB) curable systems, and in order to develop appropriate process models, a detailed knowledge of the kinetics of epoxy cationic polymerization induced by ultraviolet (UV) or EB irradiation is required. In this work, we present our development of a technique based on real time near infrared (RTIR) spectroscopy for performing in situ kinetic analysis of radiation induced cationic polymerization of epoxy systems. To our knowledge this is the first time such data have been collected and presented for high-energy EB (10 MeV) induced polymerization. A demonstration of the technique for deterministic evaluation of degree of cure is shown using model glycidyl ether (phenyl glycidyl ether and diglycidyl ether of bisphenol A) resins and isothermal curing conditions. The impact of initiation rate on polymerizations with UV and EB for the cationic initiator is directly evident by comparative analysis. The sensitivity of the RTIR method and ability to produce quantitative data evidence of reaction mechanisms is demonstrated. The type of data presented in this work forms the basis for cure models being developed

Laser microstructuring for fabricating superhydrophobic polymeric surfaces

Science.gov (United States)

Cardoso, M. R.; Tribuzi, V.; Balogh, D. T.; Misoguti, L.; Mendonça, C. R.

2011-02-01

In this paper we show the fabrication of hydrophobic polymeric surfaces through laser microstructuring. By using 70-ps pulses from a Q-switched and mode-locked Nd:YAG laser at 532 nm, we were able to produce grooves with different width and separation, resulting in square-shaped pillar patterns. We investigate the dependence of the morphology on the surface static contact angle for water, showing that it is in agreement with the Cassie-Baxter model. We demonstrate the fabrication of a superhydrophobic polymeric surface, presenting a water contact angle of 157°. The surface structuring method presented here seems to be an interesting option to control the wetting properties of polymeric surfaces.

Applications of polymeric micelles with tumor targeted in chemotherapy

International Nuclear Information System (INIS)

Ding Hui; Wang Xiaojun; Zhang Song; Liu Xinli

2012-01-01

Polymeric micelles (PMs) have gained more progress as a carrier system with the quick development of biological and nanoparticle techniques. In particular, PMs with smart targeting can deliver anti-cancer drugs directly into tumor cells at a sustained rate. PMs with core–shell structure (with diameters of 10 ∼ 100 nm) have been prepared by a variety of biodegradable and biocompatible polymers via a self-assembly process. The preparation of polymeric micelles with stimuli-responsive block copolymers or modification of target molecules on polymeric micelles’ surface are able to significantly improve the efficiency of drug delivery. Polymeric micelles, which have been considered as a novel promising drug carrier for cancer therapeutics, are rapidly evolving and being introduced in an attempt to overcome several limitations of traditional chemotherapeutics, including water solubility, tumor-specific accumulation, anti-tumor efficacy, and non-specific toxicity. This review describes the preparation of polymeric micelles and the targeted modification which greatly enhance the effects of chemotherapeutic agents.

Evaluation of supplementation of sucrose medium on the synthesis of Zymomonas mobilis bio-products - doi: 10.4025/actascibiolsci.v32i3.1519

Directory of Open Access Journals (Sweden)

Maria Antonia Pedrini Colabone Celligoi

2010-09-01

Full Text Available The effect of the variables pantothenic acid, yeast extract and sodium chloride, as well as the cell permeabilization technique, were investigated on the formation of levan, ethanol, sorbitol and biomass of Zymomonas mobilis, using a 24-1 fraction factorial design. Cell growth was determined by turbidimetry at 605 nm, relating it to a biomass with a dry weight calibration curve. Reducing sugars were quantified according to Somogyi and Nelson. Total sugars were quantified by the phenol-sulfuric acid method, sorbitol by HPLC and ethanol. The levan produced was precipitated by the addition of absolute ethanol and quantified in fructose units. In levan biosynthesis, the variable that had the largest contribution was cell condition. The results suggested that the factors that most affected biomass and ethanol formation were sodium chloride concentration and cell condition that affected negatively on production. For sorbitol, the variable that had a significant effect was permeabilization, which decreased its synthesis. Studies to amplify the range of established factors would be important.The effect of the variables pantothenic acid, yeast extract and sodium chloride, as well as the cell permeabilization technique, were investigated on the formation of levan, ethanol, sorbitol and biomass of Zymomonas mobilis, using a 24-1 fraction factorial design. Cell growth was determined by turbidimetry at 605 nm, relating it to a biomass with a dry weight calibration curve. Reducing sugars were quantified according to Somogyi and Nelson. Total sugars were quantified by the phenol-sulfuric acid method, sorbitol by HPLC and ethanol. The levan produced was precipitated by the addition of absolute ethanol and quantified in fructose units. In levan biosynthesis, the variable that had the largest contribution was cell condition. The results suggested that the factors that most affected biomass and ethanol formation were sodium chloride concentration and cell

Heterofunctional Glycopolypeptides by Combination of Thiol-Ene Chemistry and NCA Polymerization.

Science.gov (United States)

Krannig, Kai-Steffen; Schlaad, Helmut

2016-01-01

Glycopolypeptides are prepared either by the polymerization of glycosylated amino acid N-carboxyanhydrides (NCAs) or by the post-polymerization functionalization of polypeptides with suitable functional groups. Here we present a method for the in-situ functionalization and (co-) polymerization of allylglycine N-carboxyanhydride in a facile one-pot procedure, combining radical thiol-ene photochemistry and nucleophilic ring-opening polymerization techniques, to yield well-defined heterofunctional glycopolypeptides.

Polymerization Initiated at the Sidewalls of Carbon Nanotubes

Science.gov (United States)

Tour, James M.; Hudson, Jared L.

2011-01-01

A process has been developed for growing polymer chains via anionic, cationic, or radical polymerization from the side walls of functionalized carbon nanotubes, which will facilitate greater dispersion in polymer matrices, and will greatly enhance reinforcement ability in polymeric material.

Microtransfer printing of metal ink patterns onto plastic substrates utilizing an adhesion-controlled polymeric donor layer

International Nuclear Information System (INIS)

Park, Ji-Sub; Choi, Jun-Chan; Park, Min-Kyu; Bae, Jeong Min; Bae, Jin-Hyuk; Kim, Hak-Rin

2016-01-01

We propose a method for transfer-printed electrode patterns onto flexible/plastic substrates, specifically intended for metal ink that requires a high sintering temperature. Typically, metal-ink-based electrodes cannot be picked up for microtransfer printing because the adhesion between the electrodes and the donor substrate greatly increases after the sintering process due to the binding materials. We introduced a polymeric donor layer between the printed electrodes and the donor substrate and effectively reduced the adhesion between the Ag pattern and the polymeric donor layer by controlling the interfacial contact area. After completing a wet-etching process for the polymeric donor layer, we obtained Ag patterns supported on the fine polymeric anchor structures; the Ag patterns could be picked up onto the stamp surface even after the sintering process by utilizing the viscoelastic properties of the elastomeric stamp with a pick-up velocity control. The proposed method enables highly conductive metal-ink-based electrode patterns to be applied on thermally weak plastic substrates via an all-solution process. Metal electrodes transferred onto a film showed superior electrical and mechanical stability under the bending stress test required for use in printed flexible electronics. (paper)

Effect of leaching residual methyl methacrylate concentrations on in vitro cytotoxicity of heat polymerized denture base acrylic resin processed with different polymerization cycles

Directory of Open Access Journals (Sweden)

Canan Bural

2011-08-01

Full Text Available OBJECTIVES: Residual methyl methacrylate (MMA may leach from the acrylic resin denture bases and have adverse effects on the oral mucosa. This in vitro study evaluated and correlated the effect of the leaching residual MMA concentrations ([MMA]r on in vitro cytotoxicity of L-929 fibroblasts. MATERIAL AND METHODS: A total of 144 heat-polymerized acrylic resin specimens were fabricated using 4 different polymerization cycles: (1 at 74ºC for 9 h, (2 at 74ºC for 9 h and terminal boiling (at 100ºC for 30 min, (3 at 74ºC for 9 h and terminal boiling for 3 h, (4 at 74ºC for 30 min and terminal boiling for 30 min. Specimens were eluted in a complete cell culture medium at 37ºC for 1, 2, 5 and 7 days. [MMA]r in eluates was measured using high-performance liquid chromatography. In vitro cytotoxicity of eluates on L-929 fibroblasts was evaluated by means of cell proliferation using a tetrazolium salt XTT (sodium 3´-[1-phenyl-aminocarbonyl-3,4-tetrazolium]bis(4-methoxy-6-nitrobenzenesulphonic acid assay. Differences in [MMA]r of eluates and cell proliferation values between polymerization cycles were statistically analyzed by Kruskal-Wallis, Friedman and Dunn's multiple comparison tests. The correlation between [MMA]r of eluates and cell proliferation was analyzed by Pearson's correlation test (p<0.05. RESULTS: [MMA]r was significantly (p<0.001 higher in eluates of specimens polymerized with cycle without terminal boiling after elution of 1 and 2 days. Cell proliferation values for all cycles were significantly (p<0.01 lower in eluates of 1 day than those of 2 days. The correlation between [MMA]r and cell proliferation values was negative after all elution periods, showing significance (p<0.05 for elution of 1 and 2 days. MMA continued to leach from acrylic resin throughout 7 days and leaching concentrations markedly reduced after elution of 1 and 2 days. CONCLUSION: Due to reduction of leaching residual MMA concentrations, use of terminal boiling in

Radiation-induced cationic polymerization of limonene oxide, α-pinene oxide, and β-pinene oxide

International Nuclear Information System (INIS)

Aikins, J.A.; Williams, F.

1984-01-01

After suitable drying, the subject monomers in the form of neat liquids undergo radiation-induced polymerization with no apparent side reactions and high conversions to precipitatable polymers of low molecular weight. A cationic mechanism is evidenced by the strongly retarding effect of tri-n-propylamine on the polymerization rate. At 25 0 C, limonene oxide gives the highest polymerization rates, an average conversion of 36% per Mrad being obtained in comparison with values of 5.7 and 7.3% per Mrad for the α-pinene and β-pinene oxides, respectively. Similarly, the average anti DP/sub n/ decreases from 11.8 for the limonene oxide polymer to 5.6 and 4.0 for the α-pinene oxide and β-pinene oxide polymers, respectively. A high frequency of chain transfer to monomer is indicated in each case by the fact that the kinetic chain lengths are estimated to be on the order of a hundred times larger than the anti DP/sub n/ values. Structural characterization of the limonene oxide polymer by 1 H and 13 C NMR spectroscopy provides conclusive evidence that the polymerization proceeds by the opening of the epoxide ring to yield a 1,2-trans polyether. Similar NMR studies on the polymers formed from the α-pinene and β-pinene oxides show that in the polymerization of these monomers, the opening of the epoxide ring is generally accompanied by the concomitant ring opening of the cyclobutane ring structure to yield a gem-dimethyl group in the main chain. The detection of isopropenyl end groups in the pinene oxide polymers is also consistent with this mode of propagation being followed by chain (proton) transfer to monomer

Stereoselectivity in metallocene-catalyzed coordination polymerization of renewable methylene butyrolactones: From stereo-random to stereo-perfect polymers

KAUST Repository

Chen, Xia; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene You Xian

2012-01-01

Coordination polymerization of renewable α-methylene-γ-(methyl) butyrolactones by chiral C 2-symmetric zirconocene catalysts produces stereo-random, highly stereo-regular, or perfectly stereo-regular polymers, depending on the monomer and catalyst structures. Computational studies yield a fundamental understanding of the stereocontrol mechanism governing these new polymerization reactions mediated by chiral metallocenium catalysts. © 2012 American Chemical Society.

Stereoselectivity in metallocene-catalyzed coordination polymerization of renewable methylene butyrolactones: From stereo-random to stereo-perfect polymers

KAUST Repository

Chen, Xia

2012-05-02

Coordination polymerization of renewable α-methylene-γ-(methyl) butyrolactones by chiral C 2-symmetric zirconocene catalysts produces stereo-random, highly stereo-regular, or perfectly stereo-regular polymers, depending on the monomer and catalyst structures. Computational studies yield a fundamental understanding of the stereocontrol mechanism governing these new polymerization reactions mediated by chiral metallocenium catalysts. © 2012 American Chemical Society.

Investigations in the field of solid state polymerization Pt. 38

International Nuclear Information System (INIS)

Hardy, Gy.; Cser, F.; Nyitrai, K.; Fedorova, N.

1980-01-01

The stuctural and radiation chemical data of vinyl monomers with long chain paraffinic or cholesteric side groups are critically reviewed. Based on their structural and polymerization kinetical characteristics the monomers may be classified into three groups. Oblique layers are favourable for homogeneous topotactic polymerization. This is characterized by a low activation energy and a radiochemical efficiency very similar to that measured in liquid state polymerization. The tilted layers are not favourable for homogeneous topotactic polymerization. Allyl monomers yield polymers with higher molecular weights in the layer structure than in liquid states. (author)

Biocompatible Polymeric Materials Intended for Drug Delivery and Therapeutic Applications

DEFF Research Database (Denmark)

Hvilsted, Søren; Javakhishvili, Irakli; Bednarek, Melania

2007-01-01

of polymer blocks by “click chemistry”. An all polymerization strategy would imply preparing polymers by living/controlled techniques in such a manner that one block after polymerization can be converted to a macroinitiator enabling the second block to polymerize. The coupling strategy invariably inserts...... a linking unit, 1,4-triazol, resulting from the catalyzed, irreversible 1,3-dipolar cycloaddition reaction between an alkyne and an azide. Thus, this strategy necessitates the proper end functionalization of the polymeric building blocks. Fortunately the 1,4-triazol unit is FDA approved already existing...

Synthesis of click-reactive HPMA copolymers using RAFT polymerization for drug delivery applications

DEFF Research Database (Denmark)

Ebbesen, Morten F; Schaffert, D.H.; Crowley, Michael L

2013-01-01

This study describes a versatile strategy combining reversible addition fragmentation transfer (RAFT) polymerization and click chemistry to synthesize well-defined, reactive copolymers of N-(2-hydroxypropyl)methacrylamide (HPMA) for drug delivery applications. A novel azide containing monomer N-(3......-azidopropyl)methacrylamide (AzMA) was synthesized and copolymerized with HPMA using RAFT polymerization to provide p(HPMA-co-AzMA) copolymers with high control of molecular weight (∼10–54 kDa) and polydispersity (≤1.06). The utility of the side-chain azide functionality by Cu(I)-catalyzed azide...

Polymeric Nanogels Obtained by Radiation Technique

Energy Technology Data Exchange (ETDEWEB)

Ulanski, P.; Kadłubowski, A. K.; Olejnik,; Rokita, B.; Wach, R.; Rosiak, J. M. [Institute of Applied Radiation Chemistry, Technical University of Lodz, Lodz (Poland)

2009-07-01

Soft nanomaterials - polymeric nanogels and microgels - have made a fast and brilliant career, from an unwanted by-product of polymerization processes to an important and fashionable topic of interdisciplinary research in the fields of polymer chemistry and physics, materials science, pharmacy and medicine. Together with their larger analogues - macroscopic gels, most known in the form of water-swellable hydrogels - they have a broad field of actual and potential applications ranging from filler materials in coating industry to modern biomaterials.

Polymeric Nanogels Obtained by Radiation Technique

International Nuclear Information System (INIS)

Ulanski, P.; Kadłubowski, A.K.; Olejnik; Rokita, B.; Wach, R.; Rosiak, J.M.

2009-01-01

Soft nanomaterials - polymeric nanogels and microgels - have made a fast and brilliant career, from an unwanted by-product of polymerization processes to an important and fashionable topic of interdisciplinary research in the fields of polymer chemistry and physics, materials science, pharmacy and medicine. Together with their larger analogues - macroscopic gels, most known in the form of water-swellable hydrogels - they have a broad field of actual and potential applications ranging from filler materials in coating industry to modern biomaterials

Recent progress of atomic layer deposition on polymeric materials

Energy Technology Data Exchange (ETDEWEB)

Guo, Hong Chen; Ye, Enyi [Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 2 Fusionopolis Way, Innovis, #08-03, Singapore 138634 (Singapore); Li, Zibiao, E-mail: lizb@imre.a-star.edu.sg [Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 2 Fusionopolis Way, Innovis, #08-03, Singapore 138634 (Singapore); Han, Ming-Yong [Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 2 Fusionopolis Way, Innovis, #08-03, Singapore 138634 (Singapore); Loh, Xian Jun, E-mail: lohxj@imre.a-star.edu.sg [Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 2 Fusionopolis Way, Innovis, #08-03, Singapore 138634 (Singapore); Department of Materials Science and Engineering, National University of Singapore, Singapore 117574 (Singapore); Singapore Eye Research Institute, 20 College Road, Singapore 169856 (Singapore)

2017-01-01

As a very promising surface coating technology, atomic layer deposition (ALD) can be used to modify the surfaces of polymeric materials for improving their functions and expanding their application areas. Polymeric materials vary in surface functional groups (number and type), surface morphology and internal structure, and thus ALD deposition conditions that typically work on a normal solid surface, usually do not work on a polymeric material surface. To date, a large variety of research has been carried out to investigate ALD deposition on various polymeric materials. This paper aims to provide an in-depth review of ALD deposition on polymeric materials and its applications. Through this review, we will provide a better understanding of surface chemistry and reaction mechanism for controlled surface modification of polymeric materials by ALD. The integrated knowledge can aid in devising an improved way in the reaction between reactant precursors and polymer functional groups/polymer backbones, which will in turn open new opportunities in processing ALD materials for better inorganic/organic film integration and potential applications. - Highlights: • ALD deposition on different natural and synthetic polymer materials • Reaction mechanism based on the surface functional groups of polymers • Application of ALD-modified polymers in different fields.

Reduced Graphene Oxide-Hybridized Polymeric High-Internal Phase Emulsions for Highly Efficient Removal of Polycyclic Aromatic Hydrocarbons from Water Matrix.

Science.gov (United States)

Huang, Yipeng; Zhang, Wenjuan; Ruan, Guihua; Li, Xianxian; Cong, Yongzheng; Du, Fuyou; Li, Jianping

2018-03-27

Reduced graphene oxide (RGO)-hybridized polymeric high-internal phase emulsions (RGO/polyHIPEs) with an open-cell structure and hydrophobicity have been successfully prepared using 2-ethylhexyl acrylate and ethylene glycol dimethacrylate as the monomer and the cross-linker, respectively. The adsorption mechanism and performance of this RGO/polyHIPEs to polycyclic aromatic hydrocarbons (PAHs) were investigated. Adsorption isotherms of PAHs on RGO/polyHIPEs show that the saturated adsorption capacity is 47.5 mg/g and the equilibrium time is 8 h. Cycling tests show that the adsorption capacity of RGO/polyHIPEs remains stable in 10 adsorption-desorption cycles without observable structure change in RGO/polyHIPEs. Moreover, the PAH residues in water samples after being purified by RGO/polyHIPEs are lower than the limit values in drinking water set by the European Food Safety Authority. These results demonstrate that the RGO/polyHIPEs have great potentiality in PAH removal and water purification.

Study of sodium clay modification through polyaniline polymerization

International Nuclear Information System (INIS)

Saade, Wesley; Pinto, Camila P.; Becker, Daniela; Dalmolin, Carla

2015-01-01

The synthesis of hybrids nanocomposites, such as polyaniline/montmorillonite (Pani/MMT), combines the processability and electrical conductivity of this polymer with the mechanical properties of a ceramic material bringing a multitude of new possibilities for use in high-tech, consumer and industry. With this in mind, we sought to characterize and modify sodium clay through polymerization of polyaniline. The characterization was carried out by X-ray diffraction, infrared spectroscopy by Fourier transformed (FTIR) and spectroscopy by impedance. Through the XRD analysis, it could be inferred that there was a interplanar displacement from 12,4Å (pure sodium montmorillonite) to 15,6Å due to the cation exchange of Na + ions by the anilinium ions, allowing the polymerization interspersed with Pani MMT platelets. By FTIR analysis, presences of the characteristic functional groups of both compounds are detected in the synthesized nanocomposite. Through conductivity and impedance tests it is concluded that the addition of polyaniline decreases the resistive behavior of clay and the electrical conduction becomes possible. (author)

A novel donor-acceptor polymeric electrochromic material containing carbazole and 1,8-naphtalimide as subunit

Energy Technology Data Exchange (ETDEWEB)

Koyuncu, Fatma Baycan, E-mail: fatmabaycan@hotmail.co [Department of Chemistry, Faculty of Sciences and Arts, Canakkale Onsekiz Mart University, 17020 Canakkale (Turkey); Koyuncu, Sermet [Can Vocational School, Canakkale Onsekiz Mart University, 17400 Canakkale (Turkey); Ozdemir, Eyup, E-mail: eozdemir@comu.edu.t [Department of Chemistry, Faculty of Sciences and Arts, Canakkale Onsekiz Mart University, 17020 Canakkale (Turkey)

2010-07-01

We report here the synthesis of a novel polymeric electrochromic material containing carbazole (Cbz)-donor and 1,8-napthalimide-acceptor as subunit. The band gap E{sub g} was measured using UV-vis spectroscopy and compared with that obtained by cyclic voltammetry (CV). Due to intramolecular electron transfer from Cbz-donor to 1,8-napthalimide-acceptor, the fluorescence quenching was observed. When the spectro-electrochemical and electrochromic properties of polymer film were investigated, various tones of green color were obtained on the polymeric film. In the positive regime, the polymer film obtained thereby is dark green resulting from the association of carbazolylium cation radicals at oxidized state and then it can be bleached by electrochemical reduction. Besides, in the negative regime, yellowish green color of film converted to blue attributed to reduction of the 1,8-napthalimide moiety. Finally, the polymeric electrochromic exhibits multi-electrochromic behavior, high redox stability, high coloration efficiency and reasonable response time.

A novel donor-acceptor polymeric electrochromic material containing carbazole and 1,8-naphtalimide as subunit

International Nuclear Information System (INIS)

Koyuncu, Fatma Baycan; Koyuncu, Sermet; Ozdemir, Eyup

2010-01-01

We report here the synthesis of a novel polymeric electrochromic material containing carbazole (Cbz)-donor and 1,8-napthalimide-acceptor as subunit. The band gap E g was measured using UV-vis spectroscopy and compared with that obtained by cyclic voltammetry (CV). Due to intramolecular electron transfer from Cbz-donor to 1,8-napthalimide-acceptor, the fluorescence quenching was observed. When the spectro-electrochemical and electrochromic properties of polymer film were investigated, various tones of green color were obtained on the polymeric film. In the positive regime, the polymer film obtained thereby is dark green resulting from the association of carbazolylium cation radicals at oxidized state and then it can be bleached by electrochemical reduction. Besides, in the negative regime, yellowish green color of film converted to blue attributed to reduction of the 1,8-napthalimide moiety. Finally, the polymeric electrochromic exhibits multi-electrochromic behavior, high redox stability, high coloration efficiency and reasonable response time.

Electrocatalytic reduction of oxygen at vapor phase polymerized ...

African Journals Online (AJOL)

We successfully polymerized poly(3,4-ethylenedioxidethiophene) by vapor phase polymerization technique on rotating glassy carbon disk electrode. The catalytic activity of this electrode towards oxygen reduction reaction was investigated and showed remarkable activity. Rotating disk voltammetry was used to study the ...

Synthesis of Terpyridine-Terminated Polymers by Anionic Polymerization

NARCIS (Netherlands)

Guerrero-Sanchez, C.A.; Lohmeijer, B.G.G.; Meier, M.A.R.; Schubert, U.S.

2005-01-01

The synthesis of terpyridine-functionalized polystyrene was achieved by reacting 4‘-chloro-2,2‘:6‘,2‘ ‘-terpyridine (terminating agent) with "living" polymeric carbanions synthesized by anionic polymerization. The obtained polymers were characterized by gel permeation chromatography, nuclear

prepared via atom transfer radical polymerization, reverse atom

Indian Academy of Sciences (India)

Synthesis and characterization of poly(2-ethylhexyl acrylate) prepared via atom transfer radical polymerization, reverse atom transfer radical polymerization and ... Zydex Industries, 25-A Gandhi Oil Mill Compound, Gorwa, Vadodara 390 016, India; Rubber Technology Centre, Indian Institute of Technology Kharagpur, ...

On the synthesis of peptide imprinted polymers by a combined suspension-Epitope polymerization method

International Nuclear Information System (INIS)

Kotrotsiou, O.; Chaitidou, S.; Kiparissides, C.

2009-01-01

In the past, molecularly imprinted polymers (MIPs), prepared by free-radical bulk polymerization, have been used for the selective recognition of small biomolecules (i.e., amino acids and amino acid derivatives). Presently, there is a need for the synthesis of MIPs capable of recognizing larger biomolecules (i.e., peptides and proteins). Moreover, it is highly desirable the production of MIP microparticles with well-defined morphological characteristics (e.g., particle size distribution, porosity, etc.) via particulate polymerization techniques. In the present study, the synthesis of molecularly imprinted microparticles, produced via the suspension and inverse suspension polymerization methods, using the 'epitope approach', is reported. The hydrophobic (i.e., Boc-Trp-Trp-Trp) or hydrophilic (i.e., His-Phe) oligo-peptides were employed as template molecules. The potential of the combined suspension polymerization method with the 'epitope approach' for the production of MIP microparticles is demonstrated, as well as the specificity and selectivity characteristics of the MIP microparticles towards hydrophobic and hydrophilic oligo-peptides. The proposed method appears to be a very promising and efficient technique for separation of proteins.

Colloidal templating : a route towards controlled synthesis of functional polymeric nanoparticles

NARCIS (Netherlands)

Ali, S.I.

2010-01-01

Template-directed synthesis of polymeric nanoparticles offers better control over particle morphology, shape, structure, composition and properties compare to the conventional emulsion polymerization routes. For the production of anisotropic polymer-clay composite latex particles and polymeric

Recent Advances in Polymeric Materials Used as Electron Mediators and Immobilizing Matrices in Developing Enzyme Electrodes

Directory of Open Access Journals (Sweden)

Mambo Moyo

2012-01-01

Full Text Available Different classes of polymeric materials such as nanomaterials, sol-gel materials, conducting polymers, functional polymers and biomaterials have been used in the design of sensors and biosensors. Various methods have been used, for example from direct adsorption, covalent bonding, crossing-linking with glutaraldehyde on composites to mixing the enzymes or use of functionalized beads for the design of sensors and biosensors using these polymeric materials in recent years. It is widely acknowledged that analytical sensing at electrodes modified with polymeric materials results in low detection limits, high sensitivities, lower applied potential, good stability, efficient electron transfer and easier immobilization of enzymes on electrodes such that sensing and biosensing of environmental pollutants is made easier. However, there are a number of challenges to be addressed in order to fulfill the applications of polymeric based polymers such as cost and shortening the long laboratory synthetic pathways involved in sensor preparation. Furthermore, the toxicological effects on flora and fauna of some of these polymeric materials have not been well studied. Given these disadvantages, efforts are now geared towards introducing low cost biomaterials that can serve as alternatives for the development of novel electrochemical sensors and biosensors. This review highlights recent contributions in the development of the electrochemical sensors and biosensors based on different polymeric material. The synergistic action of some of these polymeric materials and nanocomposites imposed when combined on electrode during sensing is discussed.

New method to access hyperbranched polymers with uniform structure via one-pot polymerization of inimer in microemulsion.

Science.gov (United States)

Min, Ke; Gao, Haifeng

2012-09-26

A facile approach is presented for successful synthesis of hyperbranched polymers with high molecular weight and uniform structure by a one-pot polymerization of an inimer in a microemulsion. The segregated space in the microemulsion confined the inimer polymerization and particularly the polymer-polymer reaction within discrete nanoparticles. At the end of polymerization, each nanoparticle contained one hyperbranched polymer that had thousands of inimer units and low polydispersity. The hyperbranched polymers were used as multifunctional macroinitiators for synthesis of "hyper-star" polymers. When a degradable inimer was applied, the hyper-stars showed fast degradation into linear polymer chains with low molecular weight.

Bioactive Polymeric Materials for Tissue Repair

Directory of Open Access Journals (Sweden)

Diane R. Bienek

2017-01-01

Full Text Available Bioactive polymeric materials based on calcium phosphates have tremendous appeal for hard tissue repair because of their well-documented biocompatibility. Amorphous calcium phosphate (ACP-based ones additionally protect against unwanted demineralization and actively support regeneration of hard tissue minerals. Our group has been investigating the structure/composition/property relationships of ACP polymeric composites for the last two decades. Here, we present ACP’s dispersion in a polymer matrix and the fine-tuning of the resin affects the physicochemical, mechanical, and biological properties of ACP polymeric composites. These studies illustrate how the filler/resin interface and monomer/polymer molecular structure affect the material’s critical properties, such as ion release and mechanical strength. We also present evidence of the remineralization efficacy of ACP composites when exposed to accelerated acidic challenges representative of oral environment conditions. The utility of ACP has recently been extended to include airbrushing as a platform technology for fabrication of nanofiber scaffolds. These studies, focused on assessing the feasibility of incorporating ACP into various polymer fibers, also included the release kinetics of bioactive calcium and phosphate ions from nanofibers and evaluate the biorelevance of the polymeric ACP fiber networks. We also discuss the potential for future integration of the existing ACP scaffolds into therapeutic delivery systems used in the precision medicine field.

Preparation of immobilized enzyme membrane by radiation-cast-polymerization

International Nuclear Information System (INIS)

Kumakura, M.; Kaetsu, I.

1989-01-01

The preparation of immobilized enzyme membranes was studied by radiation cast-polymerization at low temperatures using cellulase enzyme, hydrophilic and hydrophobic monomers. The enzyme activity of the membranes was affected by monomer concentration, membrane thickness, and hydrophilicity of monomer, in which the membranes with 100 μm thickness from high monomer concentration (80%) had high enzyme activity, which was similar to that of the membranes with 1.0 mm thickness from low monomer concentration (20%). (author)

Phospholipid Adsorption Polymeric Materials for Detection of Xylazine and Metabolite in Blood and Urine

Directory of Open Access Journals (Sweden)

Xue Gao

2016-01-01

Full Text Available Polymers have been used in different areas. Recently, polymeric material is favored in analytical area due to its high performance and high consistency, which was used in sample pretreatment in this study. Xylazine poisoning is often seen in body fluid samples obtained from various accidents or suicides. However, the content of xylazine is difficult to detect precisely due to matrix effect in testing practices. In this paper, a method application for phospholipid adsorption polymeric materials to determine xylazine in blood and urine samples was proposed, developed, and validated. Compared with existing method, this method using polymeric pretreatment has a wider linear range of 2.0–2000.0 ng/mL for xylazine and its metabolite 2,6-dimethylaniline in both blood and urine and lower detection limits of 0.3 ng/mL for 2,6-dimethylaniline and xylazine in blood and 0.2 ng/mL for 2,6-dimethylaniline and xylazine in urine. Therefore, this method is suggested to be applied in testing practices by academic groups and commercial organizations.

Polymeric peptide pigments with sequence-encoded properties

Energy Technology Data Exchange (ETDEWEB)

Lampel, Ayala; McPhee, Scott A.; Park, Hang-Ah; Scott, Gary G.; Humagain, Sunita; Hekstra, Doeke R.; Yoo, Barney; Frederix, Pim W. J. M.; Li, Tai-De; Abzalimov, Rinat R.; Greenbaum, Steven G.; Tuttle, Tell; Hu, Chunhua; Bettinger, Christopher J.; Ulijn, Rein V.

2017-06-08

Melanins are a family of heterogeneous polymeric pigments that provide ultraviolet (UV) light protection, structural support, coloration, and free radical scavenging. Formed by oxidative oligomerization of catecholic small molecules, the physical properties of melanins are influenced by covalent and noncovalent disorder. We report the use of tyrosine-containing tripeptides as tunable precursors for polymeric pigments. In these structures, phenols are presented in a (supra-)molecular context dictated by the positions of the amino acids in the peptide sequence. Oxidative polymerization can be tuned in a sequence-dependent manner, resulting in peptide sequence–encoded properties such as UV absorbance, morphology, coloration, and electrochemical properties over a considerable range. Short peptides have low barriers to application and can be easily scaled, suggesting near-term applications in cosmetics and biomedicine.

Interfacial Polymerization of Polyaniline Nanofibers Grafted to Au Surfaces

National Research Council Canada - National Science Library

Sawall, D

2004-01-01

.... The in-situ polymerization technique of these PANI nanofibers in the presence of sulfonated polystyrene allowed for the growth of PANI 2-D nanostructures embedded in the polymerized sulfonated host...

Hydroxyapatite induces spontaneous polymerization of model self-etch dental adhesives.

Science.gov (United States)

Zhang, Ying; Wu, Ningjing; Bai, Xinyan; Xu, Changqi; Liu, Yi; Wang, Yong

2013-10-01

The objective of this study is to report for the first time the spontaneous polymerization phenomenon of self-etch dental adhesives induced by hydroxylapatite (HAp). Model self-etch adhesives were prepared by using a monomer mixture of bis[2-(methacryloyloxy)ethyl] phosphate (2MP) with 2-hydroxyethyl methacrylate (HEMA). The initiator system consisted of camphorquinone (CQ, 0.022 mmol/g) and ethyl 4-dimethylaminobenzoate (4E, 0.022-0.088 mmol/g). HAp (2-8 wt.%) was added to the neat model adhesive. In a dark environment, the polymerization was monitored in-situ using ATR/FT-IR, and the mechanical properties of the polymerized adhesives were evaluated using nanoindentation technique. Results indicated that spontaneous polymerization was not observed in the absence of HAp. However, as different amounts of HAp were incorporated into the adhesives, spontaneous polymerization was induced. Higher HAp content led to higher degree of conversion (DC), higher rate of polymerization (RP) and shorter induction period (IP). In addition, higher 4E content also elevated DC and RP and reduced IP of the adhesives. Nanoindentation result suggested that the Young's modulus of the polymerized adhesives showed similar dependence on HAp and 4E contents. In summary, interaction with HAp could induce spontaneous polymerization of the model self-etch adhesives. This result provides important information for understanding the initiation mechanism of the self-etch adhesives, and may be of clinical significance to strengthen the adhesive/dentin interface based on the finding. Copyright © 2013 Elsevier B.V. All rights reserved.

New methodology developed for the differential scanning calorimetry analysis of polymeric matrixes incorporating phase change materials

International Nuclear Information System (INIS)

Barreneche, Camila; Solé, Aran; Miró, Laia; Martorell, Ingrid; Cabeza, Luisa F; Fernández, A Inés

2012-01-01

Nowadays, thermal comfort needs in buildings have led to an increase in energy consumption of the residential and service sectors. For this reason, thermal energy storage is shown as an alternative to achieve reduction of this high consumption. Phase change materials (PCM) have been studied to store energy due to their high storage capacity. A polymeric material capable of macroencapsulating PCM was developed by the authors of this paper. However, difficulties were found while measuring the thermal properties of these materials by differential scanning calorimetry (DSC). The polymeric matrix interferes in the detection of PCM properties by DSC. To remove this interfering effect, a new methodology which replaces the conventional empty crucible used as a reference in the DSC analysis by crucibles composed of the polymeric matrix was developed. Thus, a clear signal from the PCM is obtained by subtracting the new full crucible signal from the sample signal. (paper)

Catalytic olefin polymerization with early transition metal compounds

OpenAIRE

Eshuis, Johan Jan Willem

1991-01-01

The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and arene oxidation. Traditionally, heterogeneous catalysts have been used for the production of large-scale commodity chemicals such as methanol and ammonia and in the production of high octane gasoline...

Facile synthesis of polymeric fluorescent organic nanoparticles based on the self-polymerization of dopamine for biological imaging.

Science.gov (United States)

Shi, Yingge; Jiang, Ruming; Liu, Meiying; Fu, Lihua; Zeng, Guangjian; Wan, Qing; Mao, Liucheng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2017-08-01

Polymeric fluorescent organic nanoparticles (polymer-FONs) have raised considerable research attention for biomedical applications owing to their advantages as compared with fluorescent inorganic nanoparticles and small organic molecules. In this study, we presented an efficient, facile and environment-friendly strategy to produce polymer-FONs, which relied on the self-polymerization of dopamine and polyethyleneimine (PEI) in rather mild conditions. To obtain the final polymer-FONs, aldehyde group-containing copolymers (named as poly(UA-co-PEGMA)) were synthesized by reversible addition-fragmentation chain-transfer polymerization using polyethylene glycol methyl ether methacrylate (PEGMA) and 1-undecen-10-al (UA) as monomers. The dopamine was conjugated onto poly(UA-co-PEGMA) through a multicomponent reaction between UA and dopamine to obtain poly(UA-co-PEGMA)-DA, which was further utilized for preparation of polymer-FONs through self-polymerization of dopamine and PEI. 1 H nuclear magnetic resonance, Fourier transform infrared spectroscopy, transmission electron microscopy and fluorescence spectroscopy were employed to characterize the structure, morphology, compositions and optical properties of these polymer-FONs. Cell viability and cell uptake behavior results suggested that these polymer-FONs possess good biocompatibility and can be potentially utilized for biomedical applications. More importantly, the method can be also applied to fabricate many other multifunctional polymer-FONs with great potential for biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Modelling the Load Torques of Electric Drive for Polymerization Process

Directory of Open Access Journals (Sweden)

Andrzej Popenda

2007-01-01

Full Text Available The problems of mathematical modelling the load torques on shaft of driving motor designed for applications in polymerization reactors are presented in the paper. The real load of polymerization drive is determined as a function of angular velocity. Mentioned function results from friction in roll-formed slide bearing as well as from friction of ethylene molecules with mixer arms in polymerization reactor chamber. Application of mathematical formulas concerning the centrifugal ventilator is proposed to describe the mixer in reactor chamber. The analytical formulas describing the real loads of polymerization drive are applied in mathematical modelling the power unit of polymerization reactor with specially designed induction motor. The numerical analysis of transient states was made on the basis of formulated mathematical model. Examples of transient responses and trajectories resulting from analysis are presented in the paper.

Radiation initiated polymerization of trioxane and stabilization of polyoxymethylene

International Nuclear Information System (INIS)

Rao, M.H.; Ramanan, G.; Kunjappu, J.T.; Rao, K.N.

1990-01-01

Gamma ray induced polymerization of trioxane from an indigenous source (M/s. Nuchem Plastics, Faridabad) has been investigated by both in-source and post polymerization techniques. Impurity levels in the trioxane samples are determined and compared with those in an imported material. Critical evaluation of the results of its purification by different methods, viz. treatment with molecular sieves, crystallization from solvents and their variations, has been carried out prior to optimising the conditions of polymerization. A novel but simple purification procedure employing benzene as the solvent which is found to form a ternary azeotrope with trioxane and water has been developed. The effect of these purification methods on the polymerization efficiency and their dependence on the molecular weight of the polymer formed are also discussed. Experimental details of polymerizing trioxane in 10 kg scale are also described. To improve upon the thermal stabilty of the polyoxymethylene thus formed, protection of the free hydroxyl end groups (end-capping) has been achieved by an acetylation procedure using acetic anhydride in presence of catalytic amounts of sodium acetate. (author). 11 tabs., 4 figs

Comparison of potentials for polymeric liquids

International Nuclear Information System (INIS)

Jung, Hae Young

2002-01-01

Many theories for polymeric liquids are based on the concepts of cell, hole, free volume of lattice etc. In this theories, van der Waals potential, Lennard-Jones 6-12 potential and their modified potentials are commonly used. In this work, Mie(p,6)potential was applied to the Continuous Lattice Fluid Theory (which extends the discrete lattices of Lattice Fluid Theory to classically continuous lattices) and Dee-Walsch's Cell Theory (which modifies Flory's Equation of State Theory). Both of them are known to be successful theories for polymeric liquids. Thus, PVT values changing with p (the exponent in the repulsion potential) were calculated and compared with experimental values. And, calculated values of Lattice Fluid theory, Flory's Equation of State Theory and Cho-Sanchez Theory using perturbation method were also compared. Through the calculated results, van der Waals potential, Lennard-Jones 6-12 potential and Mie(p,6) potential for polymeric liquids were compared with each other

Numerical study of the thermal degradation of isotropic and anisotropic polymeric materials

Energy Technology Data Exchange (ETDEWEB)

Soler, E. [Departamento de Lenguajes y Ciencias de la Computacion, ETSI Informatica, Universidad de Malaga, 29071 Malaga (Spain); Ramos, J.I. [Room I-320-D, ETS Ingenieros Industriales, Universidad de Malaga, Plaza El Ejido, s/n, 29013 Malaga (Spain)

2005-08-01

The thermal degradation of two-dimensional isotropic, orthotropic and anisotropic polymeric materials is studied numerically by means of a second-order accurate (in both space and time) linearly implicit finite difference formulation which results in linear algebraic equations at each time step. It is shown that, for both isotropic and orthotropic composites, the monomer mass diffusion tensor plays a role in initiating the polymerization kinetics, the formation of a polymerization kernel and the initial front propagation, whereas the later stages of the polymerization are nearly independent of the monomer mass diffusion tensor. In anisotropic polymeric composites, it has been found that the monomer mass diffusion tensor plays a paramount role in determining the initial stages of the polymerization and the subsequent propagation of the polymerization front, the direction and speed of propagation of which are found to be related to the principal directions of both the monomer mass and the heat diffusion tensors. It is also shown that the polymerization time and temperatures depend strongly on the anisotropy of the mass and heat diffusion tensors. (authors)

Radiation Induced Polymerization of Pyrrole

International Nuclear Information System (INIS)

Sarada Idris; Ratnam, C.T.; Ahmad Ashrif Abu Bakar

2016-01-01

We demonstrate the polymerization of pyrrole by gamma irradiation. The pyrrole films were exposed to gamma ray from cobalt 60 source at doses ranging from 0 to 150 kGy. The films were subjected to structural and morphological analyses by using FTIR, SEM and AFM techniques. Similar studies were also made on pristine pyrrole film which serve as control. Results revealed that pyrrole has been successfully polymerized through irradiation induced reactions. The SEM images depicted the formation of cauliflower shape upon gamma irradiation. The structural changes of pyrrole also evidenced by FTIR spectra. Surface topography and roughness of pyrrole before and after gamma irradiation found to show significant differences. (author)

In situ 1H NMR studies of high-temperature nitroxide-mediated polymerization of n-butyl acrylate

NARCIS (Netherlands)

Hlalele, L.; Klumperman, L.

2011-01-01

This paper presents results on the independence of the rate of polymerization of n-butyl acrylate (n-BA) toward initial concentration of the alkoxyamine initiator. The alkoxyamine, 2-methyl-2-[N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminooxy]propionic acid (MAMA-DEPN), was used to

Positron Annihilation Spectroscopy as a Novel Interfacial Probe for Thin Polymeric Films and Nano-Composites

Science.gov (United States)

Awad, Somia; Chen, Hongmin; Maina, Grace; Lee, L. James; Gu, Xiaohong; Jean, Y. C.

2010-03-01

Positron annihilation spectroscopy (PAS) has been developed as a novel probe to characterize the sub-nanometer defect, free volume, profile from the surface, interfaces, and to the bulk in polymeric materials when a variable mono-energy slow positron beam is used. Free-volume hole sizes, fractions, and distributions are measurable as a function of depth at the high precision. PAS has been successfully used to study the interfacial properties of polymeric nanocomposites at different chemical bonding. In nano-scale thin polymeric films, such as in PS/SiO2, and PU/ZnO, significant variations of Tg as a function of depth and of wt% oxide are observed. Variations of Tg are dependent on strong or weak interactions between polymers and nano-scale oxides surfaces.

In situ stabilizer formation from methacrylic acid macromonomers in emulsion polymerization

NARCIS (Netherlands)

Schreur-Piet, Ingeborg; Heuts, Johan P.A.

2017-01-01

Oligomers of methacrylic acid containing a propenyl ω-endgroup (i.e. MAA-macromonomers) were synthesized by cobalt-mediated catalytic chain transfer polymerization and used as precursors to stabilizers in emulsion polymerization. It was found that only in those polymerizations in which these

Characterization of Plasma-Polymerized Fused Polycyclic Compounds for Binding Conducting Polymers

DEFF Research Database (Denmark)

Winther-Jensen, Bjørn; Norrman, Kion; Kingshott, Peter

2005-01-01

with hydrogen in the position which is able to co-polymerize with thiophene derivatives polymerized by conventional oxidative polymerization, thereby forming a conducting thiophene polymer bonded to the substrate. The durability of the surface modification procedure is demonstrated by micropatterning of PEDT...

Polymeric biomaterials structure and function, v.1

CERN Document Server

Dumitriu, Severian

2013-01-01

Biomaterials have had a major impact on the practice of contemporary medicine and patient care. Growing into a major interdisciplinary effort involving chemists, biologists, engineers, and physicians, biomaterials development has enabled the creation of high-quality devices, implants, and drug carriers with greater biocompatibility and biofunctionality. The fast-paced research and increasing interest in finding new and improved biocompatible or biodegradable polymers has provided a wealth of new information, transforming this edition of Polymeric Biomaterials into a two-volume set. This volume

Research and development of a technology to create original high-function materials in fiscal 1998 (development of precision structure controlling materials by improving petroleum refining). Report on achievements in research and development of precision catalytic polymerization; 1998 nendo dokusoteki kokino zairyo sosei gijutsu no kenkyu kaihatsu seika hokokusho. Sekiyu seisei kodoka seimitsu kozo seigyo zairyo kaihatsu (seimitsu shokubai jugo no kenkyu kaihatsu)

Energy Technology Data Exchange (ETDEWEB)

NONE

1999-03-01

Research and development on precision catalytic polymerization aims at developing polymerizing catalysts that can control arbitrarily the molecular weight and three-dimensional regularity by which rapid enhancement can be expected in performance of additional polymerization type polymers, and the primary structure of terminal groups. Works are being done on two sub-themes of ultimate additional polymerization and orientation catalyst polymerization. The research and development of the ultimate additional polymerization included structural control in polymerization reaction in vinyl chloride, vinylester and acrylic monomers, radical polymerization with precision orientation control, anionic polymerization with precision structural control, and precision polymerization utilizing asymmetric metal porphyrin complexes. In the research and development of the orientation catalyst polymerization, the orientation catalyst polymerization was researched and developed, elementary reaction of metallocene was elucidated, high-performance carrier catalysts were developed, advanced function polymers were synthesized at high precision based on metathesis, and improvement of functions of polyolefin was researched and developed. Surveys and studies were carried out on fundamental technologies common to the above two themes re-commissioned to five universities. (NEDO)

Complex Macromolecular Architectures by Living Cationic Polymerization

KAUST Repository

Alghamdi, Reem D.

2015-05-01

Poly (vinyl ether)-based graft polymers have been synthesized by the combination of living cationic polymerization of vinyl ethers with other living or controlled/ living polymerization techniques (anionic and ATRP). The process involves the synthesis of well-defined homopolymers (PnBVE) and co/terpolymers [PnBVE-b-PCEVE-b-PSiDEGVE (ABC type) and PSiDEGVE-b-PnBVE-b-PSiDEGVE (CAC type)] by sequential living cationic polymerization of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiDEGVE), using mono-functional {[n-butoxyethyl acetate (nBEA)], [1-(2-chloroethoxy) ethyl acetate (CEEA)], [1-(2-(2-(t-butyldimethylsilyloxy)ethoxy) ethoxy) ethyl acetate (SiDEGEA)]} or di-functional [1,4-cyclohexanedimethanol di(1-ethyl acetate) (cHMDEA), (VEMOA)] initiators. The living cationic polymerizations of those monomers were conducted in hexane at -20 0C using Et3Al2Cl3 (catalyst) in the presence of 1 M AcOEt base.[1] The PCEVE segments of the synthesized block terpolymers were then used to react with living macroanions (PS-DPE-Li; poly styrene diphenyl ethylene lithium) to afford graft polymers. The quantitative desilylation of PSiDEGVE segments by n-Bu4N+F- in THF at 0 °C led to graft co- and terpolymers in which the polyalcohol is the outer block. These co-/terpolymers were subsequently subjected to “grafting-from” reactions by atom transfer radical polymerization (ATRP) of styrene to afford more complex macromolecular architectures. The base assisted living cationic polymerization of vinyl ethers were also used to synthesize well-defined α-hydroxyl polyvinylether (PnBVE-OH). The resulting polymers were then modified into an ATRP macro-initiator for the synthesis of well-defined block copolymers (PnBVE-b-PS). Bifunctional PnBVE with terminal malonate groups was also synthesized and used as a precursor for more complex architectures such as H-shaped block copolymer by “grafting-from” or �

Equilibrium polymerization of cyclic carbonate oligomers. III. Chain branching and the gel transition

Science.gov (United States)

Ballone, P.; Jones, R. O.

2002-10-01

Ring-opening polymerization of cyclic polycarbonate oligomers, where monofunctional active sites act on difunctional monomers to produce an equilibrium distribution of rings and chains, leads to a "living polymer." Monte Carlo simulations [two-dimensional (2D) and three-dimensional (3D)] of the effects of single [J. Chem. Phys. 115, 3895 (2001)] and multiple active sites [J. Chem. Phys. 116, 7724 (2002)] are extended here to trifunctional active sites that lead to branching. Low concentrations of trifunctional particles c3 reduce the degree of polymerization significantly in 2D, and higher concentrations (up to 32%) lead to further large changes in the phase diagram. Gel formation is observed at high total density and sizable c3 as a continuous transition similar to percolation. Polymer and gel are much more stable in 3D than in 2D, and both the total density and the value of c3 required to produce high molecular weight aggregates are reduced significantly. The degree of polymerization in high-density 3D systems is increased by the addition of trifunctional monomers and reduced slightly at low densities and low c3. The presence of branching makes equilibrium states more sensitive (in 2D and 3D) to changes in temperature T. The stabilities of polymer and gel are enhanced by increasing T, and—for sufficiently high values of c3—there is a reversible polymer-gel transformation at a density-dependent floor temperature.

21 CFR 872.6070 - Ultraviolet activator for polymerization.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ultraviolet activator for polymerization. 872.6070 Section 872.6070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES... ultraviolet radiation intended to polymerize (set) resinous dental pit and fissure sealants or restorative...

Syntheses and Post-Polymerization Modifications of Well-Defined Styrenic Polymers Containing Three-Membered Heterocyclic Functionalities

Science.gov (United States)

McLeod, David Charles

Macromolecules that contain electrophilic moieties, such as benzyl halides, activated esters, and epoxides, will readily undergo efficient nucleophilic substitution reactions with a wide variety of compounds under mild conditions, and are therefore ideally suited to act as "universal" precursors to functional materials. Epoxide-containing polymers derived from the radical polymerization of commercially-available glycidyl methacrylate are often employed in this role; however, methacrylic polymers suffer from certain limitations as a result of the incorporated ester groups, which are not stabile in the presence of strong nucleophiles, acids, bases, or esterase enzymes. Styrenic polymers that do not contain labile carbonyl moieties are usually the precursors of choice when high chemical stability is desired in the end product, but the production of functional materials from epoxide-containing styrenic polymers is relatively unexplored. In this dissertation, improved methods were developed for synthesizing 4-vinylphenyloxirane (4VPO) and 4-vinylphenyl glycidyl ether (4VPGE), two of the better-known epoxide-containing styrenic monomers, in high-yield and purity. Well-defined, epoxide-containing styrenic polymers with targeted molecular weights, narrow molecular weight distributions, and controlled architectures (specifically, linear and star-shaped homopolymers, as well as linear block copolymers with styrene) were produced from 4VPO and 4VPGE for the first time using reversible-deactivation radical polymerization techniques, such as low-catalyst-concentration atom transfer radical polymerization (LCC ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. The robust nature and utility of poly4VPO and poly4VPGE were then demonstrated by the efficient, ring-opening modification of the pendant epoxide groups with a structurally- and functionally-diverse array of alcohols under acidic conditions at ambient temperature. The macromolecular

Solid-State Polymerization of Acetylene under Pressure: {ital Ab Initio} Simulation

Energy Technology Data Exchange (ETDEWEB)

Bernasconi, M.; Parrinello, M. [Max-Planck-Institut fuer Festkoerperforschung, Heisenbergstr.1, D-70569 Stuttgart (Germany); Bernasconi, M. [Istituto Nazionale Fisica della Materia and Dipartimento di Fisica, Universita di Milano, Via Celoria 16, 20133 Milano (Italy); Chiarotti, G.; Focher, P.; Tosatti, E. [Istituto Nazionale Fisica della Materia and International School for Advanced Studies, Via Beirut 4, I-34014 Trieste (Italy); Tosatti, E. [International Centre for Theoretical Physics (ICTP), P.O.Box 586, I-34014 Trieste (Italy)

1997-03-01

We have simulated by {ital ab initio} constant pressure molecular dynamics the solid-state polymerization of acetylene recently observed experimentally in the pressure range 3.5{endash}14 GPa. We have found a massive polymerization only at much higher pressure (25 GPa). However, we have also found that a triplet exciton self-trapped on a single, {ital cis}-bent molecule in crystalline acetylene is a very effective polymerization seed at lower pressure ({lt}9GPa), much closer to the experimental threshold. Therefore, we propose that the polymerization observed experimentally is possibly catalyzed by a similar seed. We predict that injection of triplet excitons would greatly enhance the polymerization rate. {copyright} {ital 1997} {ital The American Physical Society}

Synthesis of nanosized (polymerization in miniemulsion employing in situ surfactant formation.

Science.gov (United States)

Guo, Yi; Zetterlund, Per B

2011-10-18

A novel method for synthesis of ultrafine polymeric nanoparticles of diameters less than 20 nm has been developed. The method is based on miniemulsion polymerization exploiting combination of the in situ surfactant generation approach (whereby the surfactant is formed at the oil-water interface by reaction between an organic acid and a base) and ultrasonication. Conventional radical polymerization and nitroxide-mediated radical polymerization of styrene have been conducted in miniemulsion using oleic acid/potassium hydroxide, demonstrating that particles with diameters less than 20 nm can be obtained by this approach at surfactant contents much lower than traditionally required in microemulsion polymerizations. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of cytotoxicity of polypyrrole nanoparticles synthesized by oxidative polymerization

Energy Technology Data Exchange (ETDEWEB)

Vaitkuviene, Aida [Department of Physical Chemistry, Faculty of Chemistry, Vilnius University, Naugarduko 24, LT-03225 Vilnius (Lithuania); Department of Stem Cell Biology, State Research Institute Center for Innovative Medicine, Zygimantu 9, LT-01102 Vilnius (Lithuania); Kaseta, Vytautas [Department of Stem Cell Biology, State Research Institute Center for Innovative Medicine, Zygimantu 9, LT-01102 Vilnius (Lithuania); Voronovic, Jaroslav [Department of Physical Chemistry, Faculty of Chemistry, Vilnius University, Naugarduko 24, LT-03225 Vilnius (Lithuania); Ramanauskaite, Giedre; Biziuleviciene, Gene [Department of Stem Cell Biology, State Research Institute Center for Innovative Medicine, Zygimantu 9, LT-01102 Vilnius (Lithuania); Ramanaviciene, Almira [NanoTechnas–Center of Nanotechnology and Material Science at Department of Analytical and Environmental Chemistry, Faculty of Chemistry, Vilnius University, Naugarduko 24, 03225 Vilnius (Lithuania); Ramanavicius, Arunas, E-mail: Arunas.Ramanavicius@chf.vu.lt [Department of Physical Chemistry, Faculty of Chemistry, Vilnius University, Naugarduko 24, LT-03225 Vilnius (Lithuania); Laboratory of BioNanoTechnology, Department of Materials Science and Electronics, Institute of Semiconductor Physics, State Scientific Research Institute Centre for Physical Sciences and Technology, A. Gostauto 11, LT-01108 Vilnius (Lithuania)

2013-04-15

Highlights: ► Polypyrrole nanoparticles synthesized by environmentally friendly polymerization at high concentrations are cytotoxic. ► Primary mouse embryonic fibroblast, mouse hepatoma and human T lymphocyte Jurkat cell lines were treated by Ppy nanoparticles. ► Polypyrrole nanoparticles at high concentrations inhibit cell proliferation. -- Abstract: Polypyrrole (Ppy) is known as biocompatible material, which is used in some diverse biomedical applications and seeming to be a very promising for advanced biotechnological applications. In order to increase our understanding about biocompatibility of Ppy, in this study pure Ppy nanoparticles (Ppy-NPs) of fixed size and morphology were prepared by one-step oxidative polymerization and their cyto-compatibility was evaluated. The impact of different concentration of Ppy nanoparticles on primary mouse embryonic fibroblasts (MEF), mouse hepatoma cell line (MH-22A), and human T lymphocyte Jurkat cell line was investigated. Cell morphology, viability/proliferation after the treatment by Ppy nanoparticles was evaluated. Obtained results showed that Ppy nanoparticles at low concentrations are biocompatible, while at high concentrations they became cytotoxic for Jurkat, MEF and MH-22A cells, and it was found that cytotoxic effect is dose-dependent.

Spectroscopic Investigation of Composite Polymeric and Monocrystalline Systems with Ionic Conductivity

Directory of Open Access Journals (Sweden)

Darya V. Radziuk

2011-03-01

Full Text Available The conductivity mechanism is studied in the LiCF3SO3-doped polyethylene oxide by monitoring the vibrations of sulfate groups and mobility of Li+ ion along the polymeric chain at different EO/Li molar ratios in the temperature range from 16 to 90 °С. At the high EO/Li ratio (i.e., 30, the intensity of bands increases and a triplet appears at 1,045 cm−1, indicating the presence of free anions, ionic pairs and aggregates. The existence of free ions in the polymeric electrolyte is also proven by the red shift of bands in Raman spectra and a band shift to the low frequency Infra-red region at 65 < T < 355 °С. Based on quantum mechanical modeling, (method MNDO/d, the energies (minimum and maximum correspond to the most probable and stable positions of Li+ along the polymeric chain. At room temperature, Li+ ion overcomes the intermediate state (minimum energy through non-operating transitions (maximum energy due to permanent intrapolymeric rotations (rotation of C, H and O atoms around each other. In solid electrolyte (Li2SO4 the mobility of Li+ ions increases in the temperature range from 20 to 227 °С, yielding higher conductivity. The results of the present work can be practically applied to a wide range of compact electronic devices, which are based on polymeric or solid electrolytes.

Mechanism and kinetics of addition polymerizations

CERN Document Server

Kucera, M

1991-01-01

This volume presents an up-to-date survey of knowledge concerning addition type polymerizations. It contains nine chapters, each of which covers a particular basic term. Whenever necessary, the phenomena are discussed from the viewpoint of both stationary and non-stationary state of radical, ionic (i.e. anionic and cationic) and coordination polymerization. Special attention has been paid to the propagation process. It provides not only a general overview but also information on important special cases (theoretical conditions of propagation, influence of external factors, controlled propagatio

Preparation of Bottlebrush Polymers via a One-Pot Ring-Opening Polymerization (ROP) and Ring-Opening Metathesis Polymerization (ROMP) Grafting-Through Strategy.

Science.gov (United States)

Radzinski, Scott C; Foster, Jeffrey C; Matson, John B

2016-04-01

Bottlebrush polymers are synthesized using a tandem ring-opening polymerization (ROP) and ring-opening metathesis polymerization (ROMP) strategy. For the first time, ROP and ROMP are conducted sequentially in the same pot to yield well-defined bottlebrush polymers with molecular weights in excess of 10(6) Da. The first step of this process involves the synthesis of a polylactide macromonomer (MM) via ROP of d,l-lactide initiated by an alcohol-functionalized norbornene. ROMP grafting-through is then carried out in the same pot to produce the bottlebrush polymer. The applicability of this methodology is evaluated for different MM molecular weights and bottlebrush backbone degrees of polymerization. Size-exclusion chromatographic and (1)H NMR spectroscopic analyses confirm excellent control over both polymerization steps. In addition, bottlebrush polymers are imaged using atomic force microscopy and stain-free transmission electron microscopy on graphene oxide. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of solubility parameter of monomers on electron beam induced graft-polymerization onto polyethylene films

International Nuclear Information System (INIS)

Mori, Koji; Koshiishi, Kenji; Masuhara, Ken-ichi

1991-01-01

Electron beam induced graft-polymerization by the mutual irradiation technique of monomers with different solubility parameters δ onto low density polyethylene films (LDPE) and high density polyethylene films (HDPE) were investigated at high dose rates (25 Mrad per second). Graft-polymerization mechanisms were discussed on the basis of grafting rates, surface tensions, atomic ratios of surface by XPS, and SEM images of the grafted films. Grafting rates decreased with increasing δ of monomers, and grafting rates onto LDPE were larger than those onto HDPE. Graft chain contents on surface, which were evaluated in terms of surface tensions and atomic ratios of the surface, increased with increasing δ of monomers, and graft chain contents on surface of HDPE were higher than those of LDPE. It is assumed that mutual solubility of PE and monomers, i.e., infiltration of monomers into PE during graft-polymerization influence grafting rates and graft sites in films. In case of high mutual solubility, grafting rates were large and graft sites spread from the surface into bulk. On the other hand, in case of low mutual solubility, grafting rates were small and graft sites localized on the surface of films. (author)

Effect of Mn doped-titania on the activity of metallocene catalyst by in situ ethylene polymerization

KAUST Repository

Abdul Kaleel, S. H.

2012-09-01

Ethylene polymerization was carried out using highly active metallocene catalysts (Cp 2ZrCl 2 and Cp 2TiCl 2) in combination with methylalumoxane. Titanium(IV) oxide containing 1% Mn as dopant was used as nanofillers. The influence of filler concentration, reaction temperature and pressure on the catalytic activity and polymer properties was investigated. There was a fourfold increase in the activity of zirconocene catalyst by addition of doped-titania. The morphology indicates that the doped-titania nanoparticles have a nucleus effect on the polymerization and caused a homogeneous PE shell around them. The optimum condition for polymerization was found to be 30°C. © 2012 The Korean Society of Industrial and Engineering Chemistry.

Reversible and Irreversible Binding of Nanoparticles to Polymeric Surfaces

Directory of Open Access Journals (Sweden)

Wolfgang H. Binder

2009-01-01

Full Text Available Reversible and irreversible binding of CdSe-nanoparticles and nanorods to polymeric surfaces via a strong, multiple hydrogen bond (= Hamilton-receptor/barbituric acid is described. Based on ROMP-copolymers, the supramolecular interaction on a thin polymer film is controlled by living polymerization methods, attaching the Hamilton-receptor in various architectures, and concentrations. Strong binding is observed with CdSe-nanoparticles and CdSe-nanorods, whose surfaces are equipped with matching barbituric acid-moieties. Addition of polar solvents, able to break the hydrogen bonds leads to the detachment of the nanoparticles from the polymeric film. Irreversible binding is observed if an azide/alkine-“click”-reaction is conducted after supramolecular recognition of the nanoparticles on the polymeric surface. Thus reversible or irreversible attachment of the nanosized objects can be achieved.

Research and development of basic technologies for next generation industries, 'high crystalline polymeric material'. Evaluation on second term research and development; Jisedai sangyo kiban gijutsu kenkyu kaihatsu. Kokesshosei kobunshi zairyo (dainiki kenkyu kaihatsu kenkyu)

Energy Technology Data Exchange (ETDEWEB)

NONE

1988-03-01

This research and development is intended to establish a basic technology related to high crystalline polymeric material that has dynamic properties comparable to metallic materials by single polymeric material as a structural material. Thick and large high-elasticity molded forms were obtained by searching poly-arylate material, and by developing such processing technologies as high-pressure injection molding, composite injection molding, and elongation fluidity molding. High-elasticity molded forms with uniform internal orientation were obtained by heating and molding liquid crystal polymers under high magnetic field. Solution molding was performed on a molecular composite consisting of rigid chains and soft chains, which was laminated and bonded to have obtained an isotropic form with as high elasticity as 54 GPa. In addition, high pressure powder formation of cross-linked polymers of di-acetylene system provided an isotropic form with sound wave elasticity of 23 GPa.

Surface Initiated Polymerizations via e-ATRP in Pure Water

Directory of Open Access Journals (Sweden)

Seyed Schwan Hosseiny

2013-10-01

Full Text Available Here we describe the combined process of surface modification with electrochemical atom transfer radical polymerization (e-ATRP initiated from the surface of a modified gold-electrode in a pure aqueous solution without any additional supporting electrolyte. This approach allows for a very controlled growth of the polymer chains leading towards a steady increase in film thickness. Electrochemical quartz crystal microbalance displayed a highly regular increase in surface confined mass only after the addition of the pre-copper catalyst which is reduced in situ and transformed into the catalyst. Even after isolation and washing of the modified electrode surface, reinitiation was achieved with retention of the controlled electrochemical ATRP reaction. This reinitiation after isolation proves the livingness of the polymerization. This approach has interesting potential for smart thin film materials and offers also the possibility of post-modification via additional electrochemical induced reactions.

Patterned, highly stretchable and conductive nanofibrous PANI/PVDF strain sensors based on electrospinning and in situ polymerization

Science.gov (United States)

Yu, Gui-Feng; Yan, Xu; Yu, Miao; Jia, Meng-Yang; Pan, Wei; He, Xiao-Xiao; Han, Wen-Peng; Zhang, Zhi-Ming; Yu, Liang-Min; Long, Yun-Ze

2016-01-01

A facile fabrication strategy via electrospinning and followed by in situ polymerization to fabricate a patterned, highly stretchable, and conductive polyaniline/poly(vinylidene fluoride) (PANI/PVDF) nanofibrous membrane is reported. Owing to the patterned structure, the nanofibrous PANI/PVDF strain sensor can detect a strain up to 110%, for comparison, which is 2.6 times higher than the common nonwoven PANI/PVDF mat and much larger than the previously reported values (usually less than 15%). Meanwhile, the conductivity of the patterned strain sensor shows a linear response to the applied strain in a wide range from 0% to about 85%. Additionally, the patterned PANI/PVDF strain sensor can completely recover to its original electrical and mechanical values within a strain range of more than 22%, and exhibits good durability over 10 000 folding-unfolding tests. Furthermore, the strain sensor also can be used to detect finger motion. The results demonstrate promising application of the patterned nanofibrous membrane in flexible electronic fields.A facile fabrication strategy via electrospinning and followed by in situ polymerization to fabricate a patterned, highly stretchable, and conductive polyaniline/poly(vinylidene fluoride) (PANI/PVDF) nanofibrous membrane is reported. Owing to the patterned structure, the nanofibrous PANI/PVDF strain sensor can detect a strain up to 110%, for comparison, which is 2.6 times higher than the common nonwoven PANI/PVDF mat and much larger than the previously reported values (usually less than 15%). Meanwhile, the conductivity of the patterned strain sensor shows a linear response to the applied strain in a wide range from 0% to about 85%. Additionally, the patterned PANI/PVDF strain sensor can completely recover to its original electrical and mechanical values within a strain range of more than 22%, and exhibits good durability over 10 000 folding-unfolding tests. Furthermore, the strain sensor also can be used to detect finger

Polymeric bionanocomposite cast thin films with in situ laccase-catalyzed polymerization of dopamine for biosensing and biofuel cell applications.

Science.gov (United States)

Tan, Yueming; Deng, Wenfang; Li, Yunyong; Huang, Zhao; Meng, Yue; Xie, Qingji; Ma, Ming; Yao, Shouzhuo

2010-04-22

We report here on the facile preparation of polymer-enzyme-multiwalled carbon nanotubes (MWCNTs) cast films accompanying in situ laccase (Lac)-catalyzed polymerization for electrochemical biosensing and biofuel cell applications. Lac-catalyzed polymerization of dopamine (DA) as a new substrate was examined in detail by UV-vis spectroscopy, cyclic voltammetry, quartz crystal microbalance, and scanning electron microscopy. Casting the aqueous mixture of DA, Lac and MWCNTs on a glassy carbon electrode (GCE) yielded a robust polydopamine (PDA)-Lac-MWCNTs/GCE that can sense hydroquinone with 643 microA mM(-1) cm(-2) sensitivity and 20-nM detection limit (S/N = 3). The DA substrate yielded the best biosensing performance, as compared with aniline, o-phenylenediamine, or o-aminophenol as the substrate for similar Lac-catalyzed polymerization. Casting the aqueous mixture of DA, glucose oxidase (GOx), Lac, and MWCNTs on a Pt electrode yielded a robust PDA-GOx-Lac-MWCNTs/Pt electrode that exhibits glucose-detection sensitivity of 68.6 microA mM(-1) cm(-2). In addition, 2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS) was also coimmobilized to yield a PDA-Lac-MWCNTs-ABTS/GCE that can effectively catalyze the reduction of O(2), and it was successfully used as the biocathode of a membraneless glucose/O(2) biofuel cell (BFC) in pH 5.0 Britton-Robinson buffer. The proposed biomacromolecule-immobilization platform based on enzyme-catalyzed polymerization may be useful for preparing many other multifunctional polymeric bionanocomposites for wide applications.

Radiation polymerization of 2-hydroxyethyl methacrylate-vinyl pyrrolidone-water system

International Nuclear Information System (INIS)

Kumakura, M.; Kaetsu, I.

1988-01-01

Polymerization was studied using mixtures of 2-hydroxyethyl methacrylate(HEMA)-water, vinyl pyrrolidone(NVP)-water and 2-hydroxyethyl methacrylate-vinyl pyrrolidone-water. The mixtures were irradiated with gamma radiation from a 60 Co source. Irradiation was carried out at temperatures of 0, -24, -45, -63, -78, and -196 degC. The dependence was studied of the polymerization rate on temperature during irradiation for the individual mixtures, as were the effect of monomer composition on the polymerization of the HEMA-NVP-water system at 0 degC, the effect of water on NVP polymerization and the relationship between water absorption and the composition of the monomer. (E.S.). 4 figs., 6 refs

49 CFR 173.221 - Polymeric beads, expandable and Plastic molding compound.

Science.gov (United States)

2010-10-01

... 49 Transportation 2 2010-10-01 2010-10-01 false Polymeric beads, expandable and Plastic molding... Than Class 1 and Class 7 § 173.221 Polymeric beads, expandable and Plastic molding compound. (a) Non-bulk shipments of Polymeric beads (or granules), expandable, evolving flammable vapor and Plastic...

TRANSITION METAL CATALYSIS IN CONTROLLED RADICAL POLYMERIZATION: ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

Science.gov (United States)

Novel and diversified macromolecular structures, which include polymers with designed topologies (top), compostions (middle), and functionalities (bottom), can be prepared by atom transfer radical polymerization processes. These polymers can be synthesized from a large variety of...

Mechanism of isotactic styrene polymerization with a C 6F 5-substituted bis(phenoxyimine) titanium system

KAUST Repository

Caporaso, Lucia; Loria, Marianna; Mazzeo, Mina; Michiue, Kenji; Nakano, Takashi; Fujita, Terunori; Cavallo, Luigi

2012-01-01

We report a combined, experimental and theoretical, study of styrene polymerization to clarify the regio- and stereocontrol mechanism operating with a C 6F 5-substituted bis(phenoxyimine) titanium dichloride complex. Styrene homopolymerization, styrene-propene and styrene-ethene-propene copolymerizations have been carried out to this aim. A combination of 13C NMR analysis of the chain-end groups and of the microstructure of the homopolymers and copolymers reveals that styrene polymerization is highly regioselective and occurs prevalently through 2,1-monomer insertion. DFT calculations evidenced that steric interaction between the growing chain and the monomer in the transition state insertion stage is at the origin of this selectivity. The formation of isotactic polystyrene with a chain-end like microstructure is rationalized on the base of a mechanism similar to that proposed for the syndiospecific propene polymerization catalyzed by bis(phenoxyimine) titanium dichloride complexes. Finally, a general stereocontrol mechanism operative in olefin polymerization with this class of complexes is proposed. © 2012 American Chemical Society.

Mechanism of isotactic styrene polymerization with a C 6F 5-substituted bis(phenoxyimine) titanium system

KAUST Repository

Caporaso, Lucia

2012-11-13

We report a combined, experimental and theoretical, study of styrene polymerization to clarify the regio- and stereocontrol mechanism operating with a C 6F 5-substituted bis(phenoxyimine) titanium dichloride complex. Styrene homopolymerization, styrene-propene and styrene-ethene-propene copolymerizations have been carried out to this aim. A combination of 13C NMR analysis of the chain-end groups and of the microstructure of the homopolymers and copolymers reveals that styrene polymerization is highly regioselective and occurs prevalently through 2,1-monomer insertion. DFT calculations evidenced that steric interaction between the growing chain and the monomer in the transition state insertion stage is at the origin of this selectivity. The formation of isotactic polystyrene with a chain-end like microstructure is rationalized on the base of a mechanism similar to that proposed for the syndiospecific propene polymerization catalyzed by bis(phenoxyimine) titanium dichloride complexes. Finally, a general stereocontrol mechanism operative in olefin polymerization with this class of complexes is proposed. © 2012 American Chemical Society.

Contribution of galloylation and polymerization to the antioxidant activity of polyphenols in fish lipid systems.

Science.gov (United States)

Iglesias, Jacobo; Pazos, Manuel; Lois, Salomé; Medina, Isabel

2010-06-23

Polyphenolic fractions extracted from pine (Pinus pinaster) bark, grape (Vitis vinifera) pomace, and witch hazel (Hamamelis virginiana) bark were selected for investigating the influence of the number of phenolic units, polymerization, and the content of esterified galloyl residues (galloylation) on their efficacy for inhibiting lipid oxidation in fish lipid enriched foodstuffs. Experiments carried out with nongalloylated pine bark fractions with different polymerization degrees demonstrated that the number of catechin residues per molecule modulates their reducing and chelating properties in solution. In real food systems such as bulk fish oil and fish oil-in-water emulsions, the efficacy against lipid oxidation was highly dependent on the physical location of the antioxidant at the oxidative sensitive sites. The lowest polymerized fractions were the most efficient in bulk fish oil samples, whereas proanthocyanidins with an intermediate polymerization degree showed the highest activity in fish oil-in-water emulsions. Galloylation did not influence the antioxidant effectiveness of proanthocyanidins in bulk fish oils. The presence of galloyl groups favored the antioxidant activity of the polyphenols in emulsions, although results indicated that a high degree of galloylation did not improve significantly the activity found with medium galloylated proanthocyanidins. The results obtained in this research provide useful information about the relationship between structure and antioxidant activity in order to design antioxidant additives with application in fish oil-enriched functional foods.

Extracellular polymeric substances mediate bioleaching/biocorrosion via interfacial processes involving iron(III) ions and acidophilic bacteria.

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Sand, Wolfgang; Gehrke, Tilman

2006-01-01

Extracellular polymeric substances seem to play a pivotal role in biocorrosion of metals and bioleaching, biocorrosion of metal sulfides for the winning of precious metals as well as acid rock drainage. For better control of both processes, the structure and function of extracellular polymeric substances of corrosion-causing or leaching bacteria are of crucial importance. Our research focused on the extremophilic bacteria Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans, because of the "simplicity" and knowledge about the interactions of these bacteria with their substrate/substratum and their environment. For this purpose, the composition of the corresponding extracellular polymeric substances and their functions were analyzed. The extracellular polymeric substances of both species consist mainly of neutral sugars and lipids. The functions of the exopolymers seem to be: (i) to mediate attachment to a (metal) sulfide surface, and (ii) to concentrate iron(III) ions by complexation through uronic acids or other residues at the mineral surface, thus, allowing an oxidative attack on the sulfide. Consequently, dissolution of the metal sulfide is enhanced, which may result in an acceleration of 20- to 100-fold of the bioleaching process over chemical leaching. Experiments were performed to elucidate the importance of the iron(III) ions complexed by extracellular polymeric substances for strain-specific differences in oxidative activity for pyrite. Strains of A. ferrooxidans with a high amount of iron(III) ions in their extracellular polymeric substances possess greater oxidation activity than those with fewer iron(III) ions. These data provide insight into the function of and consequently the advantages that extracellular polymeric substances provide to bacteria. The role of extracellular polymeric substances for attachment under the conditions of a space station and resulting effects like biofouling, biocorrosion, malodorous gases, etc. will be discussed.

Microhardness of light- and dual-polymerizable luting resins polymerized through 7.5-mm-thick endocrowns.

Science.gov (United States)

Gregor, Ladislav; Bouillaguet, Serge; Onisor, Ioana; Ardu, Stefano; Krejci, Ivo; Rocca, Giovanni Tommaso

2014-10-01

The complete polymerization of luting resins through thick indirect restorations is still questioned. The purpose of this study was to evaluate the degree of polymerization of light- and dual-polymerizable luting resins under thick indirect composite resin and ceramic endocrowns by means of Vickers microhardness measurements. The Vickers microhardness measurements of a light-polymerizable microhybrid composite resin and a dual-polymerizable luting cement directly polymerized in a natural tooth mold for 40 seconds with a high-power light-emitting diode lamp (control) were compared with measurements after indirect irradiation through 7.5-mm-thick composite resin and ceramic endocrowns for 3 × 90 seconds. A test-to-control microhardness values ratio of 0.80 at a depth of 0.5 mm below the surface was assumed as the criterion for adequate conversion. For the Vickers microhardness measurements of a dual-polymerizable luting cement, no differences (P>.05) were found between Vickers microhardness control values and values reported after polymerization through composite resin and ceramic endocrowns. For The Vickers microhardness measurements (±SD) of a light-polymerizable microhybrid composite resin, control values were significantly (P.05). Under the conditions of this in vitro study, Vickers microhardness values of the dual-polymerizable resin cement and the light-polymerizable restorative composite resin irradiated for 3 × 90 seconds with a high irradiance light-emitting diode lamp through 7.5-mm-thick endocrowns reached at least 80% of the control Vickers microhardness values, which means that both materials can be adequately polymerized when they are used for luting thick indirect restorations. Copyright © 2014 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Gamma radiation-initiated polymerization of styrene at high pressure. II. Chain termination

International Nuclear Information System (INIS)

Moore, P.W.; Clouston, J.G.; Chaplin, R.P.

1981-01-01

The pressure dependence of the termination rate constant k/sub t/ for the free radical polymerization of monomers such as styrene is a function of polymer chain length, chain stiffness, and monomer viscosity, all of which influence the rate of segmental diffusion of an active radical chain end out of the coiled polymer chain to a position in which it can react with a proximate radical. Although k/sub t/ is not sensitive to changes in chain length, the large increase in molecular weight is responsible for a significant reduction in k/sub t/ at high pressures. For most of the common vinyl polymers, which exhibit some degree of chain stiffness, k/sub t/is inversely proportional to a fractional power of the monomer viscosity because it depends in part on the resistance of chain segments to movement and in part on the influence of viscosity in controlling diffusion of the chain ends. The fractional exponent appears to increase with pressure and this is interpreted as evidence that the polymer chains become more flexible in a more viscous solvent. Because the fractional exponent is higher for more flexible chains, the value of the activation volume for chain termination is an indication of the degree of flexibility of the polymer chains, provided that the monomer is a good solvent for the polymer and that chain transfer is negligible

Preparation of poly (alkylcyanoacrylate) nanoparticles by polymerization of water-free microemulsions

DEFF Research Database (Denmark)

Krauel, Karen; Graf, Anja; Hook, Sarah M

2006-01-01

designated as droplet, bicontinuous or solution type microemulsions using conductivity, viscosity and self-diffusion NMR. Nanoparticles were prepared by polymerization of selected microemulsions with ethyl-2-cyanoacrylate and the morphology of the particles was investigated. Addition of monomer to all types...... that polymerization is expected to occur at a water-oil interface by base-catalysed polymerization. It would appear that propylene glycol is sufficiently nucleophilic to initiate the polymerization. The use of water-free microemulsions as templates for the preparation of poly (alkylcyanoacrylate) nanoparticles opens...

Polymeric matrix materials for infrared metamaterials

Science.gov (United States)

Dirk, Shawn M; Rasberry, Roger D; Rahimian, Kamyar

2014-04-22

A polymeric matrix material exhibits low loss at optical frequencies and facilitates the fabrication of all-dielectric metamaterials. The low-loss polymeric matrix material can be synthesized by providing an unsaturated polymer, comprising double or triple bonds; partially hydrogenating the unsaturated polymer; depositing a film of the partially hydrogenated polymer and a crosslinker on a substrate; and photopatterning the film by exposing the film to ultraviolet light through a patterning mask, thereby cross-linking at least some of the remaining unsaturated groups of the partially hydrogenated polymer in the exposed portions.

Effects of water-absorption and thermal drift on a polymeric photonic crystal slab sensor

DEFF Research Database (Denmark)

Sørensen, Kristian Tølbøl; Ingvorsen, Charlotte Bonde; Nielsen, Line Hagner

2018-01-01

of resonant reflection during absorption, by monitoring the release of water using ellipsometry, and by rigorous coupled-wave analysis (RCWA). The approach presented here enables monitoring of water uptake and thermal fluctuations, for drift-free, high-performance operation of a polymeric PCS sensor....... with additional challenges, besides those relating to temperature-variations, which must be considered in any refractive index based method: The polymeric waveguide core was found to swell by ?0.3% as water absorbed into the waveguide core over ?1.5 h. This was investigated by monitoring the wavelength...

Polymeric micro/nanoparticles: Particle design and potential vaccine delivery applications.

Science.gov (United States)

Yue, Hua; Ma, Guanghui

2015-11-04

Particle based adjuvant showed promising signs on delivering antigen to immune cells and acting as stimulators to elicit preventive or therapeutic response. Nevertheless, the wide size distribution of available polymeric particles has so far obscured the immunostimulative effects of particle adjuvant, and compromised the progress in pharmacological researches. To conquer this hurdle, our research group has carried out a series of researches regarding the particulate vaccine, by taking advantage of the successful fabrication of polymeric particles with uniform size. In this review, we highlight the insight and practical progress focused on the effects of physiochemical property (e.g. particle size, charge, hydrophobicity, surface chemical group, and particle shape) and antigen loading mode on the resultant biological/immunological outcome. The underlying mechanisms of how the particles-based vaccine functioned in the immune system are also discussed. Based on the knowledge, particles with high antigen payload and optimized attributes could be designed for expected adjuvant purpose, leading to the development of high efficient vaccine candidates. Copyright © 2015 Elsevier Ltd. All rights reserved.

Fructanase and fructosyltransferase activity of non-Saccharomyces yeasts isolated from fermenting musts of Mezcal.

Science.gov (United States)

Arrizon, Javier; Morel, Sandrine; Gschaedler, Anne; Monsan, Pierre

2012-04-01

Fructanase and fructosyltransferase are interesting for the tequila process and prebiotics production (functional food industry). In this study, one hundred thirty non-Saccharomyces yeasts isolated from "Mezcal de Oaxaca" were screened for fructanase and fructosyltransferase activity. On solid medium, fifty isolates grew on Agave tequilana fructans (ATF), inulin or levan. In liquid media, inulin and ATF induced fructanase activities of between 0.02 and 0.27U/ml depending of yeast isolate. High fructanase activity on sucrose was observed for Kluyveromyces marxianus and Torulaspora delbrueckii, while the highest fructanase activity on inulin and ATF was observed for Issatchenkia orientalis, Cryptococcus albidus, and Candida apicola. Zygosaccharomyces bisporus and Candida boidinii had a high hydrolytic activity on levan. Sixteen yeasts belonging to K. marxianus, T. delbrueckii and C. apicola species were positive for fructosyltransferase activity. Mezcal microbiota proved to showed to be a source for new fructanase and fructosyltransferases with potential application in the tequila and food industry. Copyright © 2012 Elsevier Ltd. All rights reserved.

Characterization of polymeric microneedle arrays for transdermal drug delivery.

Directory of Open Access Journals (Sweden)

Yusuf K Demir

Full Text Available Microfabrication of dissolvable, swellable, and biodegradable polymeric microneedle arrays (MNs were extensively investigated based in a nano sensitive fabrication style known as micromilling that is then combined with conventional micromolding technique. The aim of this study was to describe the polymer selection, and optimize formulation compounding parameters for various polymeric MNs. Inverse replication of micromilled master MNs reproduced with polydimethylsiloxane (PDMS, where solid out of plane polymeric MNs were subsequently assembled, and physicochemically characterized. Dissolvable, swellable, and biodegradable MNs were constructed to depth of less than 1 mm with an aspect ratio of 3.6, and 1/2 mm of both inter needle tip and base spacing. Micromolding step also enabled to replicate the MNs very precisely and accurate. Polymeric microneedles (MN precision was ranging from ± 0.18 to ± 1.82% for microneedle height, ± 0.45 to ± 1.42% for base diameter, and ± 0.22 to ± 0.95% for interbase spacing. Although dissolvable sodium alginate MN showed less physical robustness than biodegradable polylactic-co-glycolic acid MN, their thermogravimetric analysis is of promise for constructing these polymeric types of matrix devices.

Neutral Polymeric Micelles for RNA Delivery

Science.gov (United States)

Lundy, Brittany B.; Convertine, Anthony; Miteva, Martina; Stayton, Patrick S.

2013-01-01

RNA interference (RNAi) drugs have significant therapeutic potential but delivery systems with appropriate efficacy and toxicity profiles are still needed. Here, we describe a neutral, ampholytic polymeric delivery system based on conjugatable diblock polymer micelles. The diblock copolymer contains a hydrophilic poly[N-(2-hydroxypropyl) methacrylamide-co-N-(2-(pyridin-2- yldisulfanyl)ethyl)methacrylamide) (poly[HPMA-co-PDSMA]) segment to promote aqueous stability and facilitate thiol-disulfide exchange reactions, and a second ampholytic block composed of propyl acrylic acid (PAA), dimethylaminoethyl methacrylate (DMAEMA), and butyl methacrylate (BMA). The poly[(HPMA-co-PDSMA)-b-(PAA-co-DMAEMA-co-BMA)] was synthesized using Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization with an overall molecular weight of 22,000 g/mol and a PDI of 1.88. Dynamic light scattering and fluorescence measurements indicated that the diblock copolymers self-assemble under aqueous conditions to form polymeric micelles with a hydrodynamic radius and critical micelle concentration of 25 nm and 25 μg/mL respectively. Red blood cell hemolysis experiments show that the neutral hydrophilic micelles have potent membrane destabilizing activity at endosomal pH values. Thiolated siRNA targeting glyceraldehyde 3-phosphate dehydrogenase (GAPDH) was directly conjugated to the polymeric micelles via thiol exchange reactions with the pyridal disulfide groups present in the micelle corona. Maximum silencing activity in HeLa cells was observed at a 1:10 molar ratio of siRNA to polymer following a 48 h incubation period. Under these conditions 90 % mRNA knockdown and 65 % and protein knockdown of at 48 h was achieved with negligible toxicity. In contrast the polymeric micelles lacking a pH-responsive endosomalytic segment demonstrated negligible mRNA and protein knockdown under these conditions. The potent mRNA knockdown and excellent biocompatibility of the neutral siRNA conjugates

Polymerization of Oriental Lacquer (Urushi with Epoxidized Linseed Oil as a New Reactive Diluent

Directory of Open Access Journals (Sweden)

Takahisa Ishimura

2015-01-01

Full Text Available A hybrid lacquer (HBL paint prepared by combining a natural kurome lacquer (KL paint and an amino silane reagent, for example, N-(2-aminoethyl-3-aminopropyl triethoxysilane (AATES, produced a polymerized film faster than the KL paint alone. However, the viscosity of the HBL paint was too viscous for easy handling. Addition of 10 wt% of an epoxidized linseed oil, ELO-6, with 6.4 mol% epoxidation as a reactive diluent to the HBL paint decreased the viscosity by 1/2 from 25476 mPa·s to 12841 mPa·s and improved the ease of coatability. The polymerization mechanism was elucidated by NMR measurements of extracts from the resulting polymerization films, suggesting that amino groups in the HBL paint reacted with epoxy groups of ELO-6 in the lacquer matrix, and then the complex reacted with double bonds of the urushiol side-chain by autooxidation and cross-linking reactions to give a hard polymerized film with a high quality of color and gloss. These results indicate that the addition of ELO-6 improved the polymerizability of both KL and HBL paints without decreasing the quality of the resulting films.

Metal-catalyzed living radical polymerization and radical polyaddition for precision polymer synthesis

Energy Technology Data Exchange (ETDEWEB)

Mizutani, M; Satoh, K [Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Kamigaito, M, E-mail: kamigait@apchem.nagoya-u.ac.j

2009-08-01

The metal-catalyzed radical addition reaction can be evolved into two different polymerization mechanisms, i.e.; chain- and step-growth polymerizations, while both the polymerizations are based on the same metal-catalyzed radical formation reaction. The former is a widely employed metal-catalyzed living radical polymerization or atom transfer radical polymerization of common vinyl monomers, and the latter is a novel metal-catalyzed radical polyaddition of designed monomer with an unconjugated C=C double bond and a reactive C-Cl bond in one molecule. The simultaneous ruthenium-catalyzed living radical polymerization of methyl acrylate and radical polyaddition of 3-butenyl 2-chloropropionate was achieved with Ru(Cp*)Cl(PPh{sub 3}){sub 2} to afford the controlled polymers, in which the homopolymer segments with the controlled chain length were connected by the ester linkage.

Polyaniline-coated halloysite nanotubes via in-situ chemical polymerization

Energy Technology Data Exchange (ETDEWEB)

Zhang Long [State Key Laboratory of Applied Organic Chemistry and Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Wang Tingmei [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Liu Peng [State Key Laboratory of Applied Organic Chemistry and Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China)], E-mail: pliu@lzu.edu.cn

2008-12-30

Polyaniline coated halloysite nanotubes (PANI/HNTs) were prepared by the in-situ soapless emulsion polymerization of the anilinium chloride adsorbed halloysite nanotubes (HNTs), obtained by the dispersion of HNTs in acidic aqueous solution of aniline with magnetic stirring and ultrasonic irradiation, by using ammonium persulfate (APS) as oxidant. The effect of the acidities of the polymerizing media on the crystal structure of the nanotubes was investigated with X-ray diffraction (XRD) technique. The surface conducting coatings of the hybrids were characterized with X-ray photoelectron spectroscopy (XPS). The morphological analyses showed that the polyaniline coated halloysite nanotubes via the in-situ chemical oxidation polymerization with ultrasonic irradiation had the better well-defined structures, by the transmission electron microscopy (TEM). The conductivities of the PANI/HNTs hybrids increased with the increasing of the amounts of HCl dopant added in the emulsion polymerization.

Polyaniline-coated halloysite nanotubes via in-situ chemical polymerization

International Nuclear Information System (INIS)