Reversible addition-fragmentation chain transfer polymerization of 2-chloro-1,3-butadiene

OpenAIRE

Pullan, Nikki; Liu, Max; Topham, Paul D.

2013-01-01

Controlled polymerization of 2-chloro-1,3-butadiene using reversible addition–fragmentation chain transfer (RAFT) polymerization has been demonstrated for the first time. 2-Chloro-1,3-butadiene, more commonly known as chloroprene, has significant industrial relevance as a crosslinked rubber, with uses ranging from adhesives to integral automotive components. However, problems surrounding the inherent toxicity of the lifecycle of the thiourea-vulcanized rubber have led to the need for control ...

Atom-transfer radical polymerization of methyl methacrylate (MMA) using CuSCN as the catalyst

NARCIS (Netherlands)

Singha, N.K.; Klumperman, B.

2000-01-01

The effect of CuSCN as a catalyst in atom-transfer radical polymerization (ATRP) was investigated. CuSCN can successfully be used for the ATRP of MMA. Substituted bipyridines as well as imines can be used to stabilize the copper complex in solution. CuSCN induces faster polymerization compared to

On Surface-Initiated Atom Transfer Radical Polymerization Using Diazonium Chemistry To Introduce the Initiator Layer

DEFF Research Database (Denmark)

Iruthayaraj, Joseph; Chernyy, Sergey; Lillethorup, Mie

2011-01-01

This work features the controllability of surface-initiated atom transfer radical polymerization (SI-ATRP) of methyl methacrylate, initiated by a multilayered 2-bromoisobutyryl moiety formed via diazonium chemistry. The thickness as a function of polymerization time has been studied by varying di...

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.

Hydrolysis of 4-Acetoxystyrene Polymers Prepared by Atom Transfer Radical Polymerization

DEFF Research Database (Denmark)

Chen, Xianyi; Jankova, Katja; Kops, Jørgen

1999-01-01

Hydrolysis of 4-acetoxystyrene polymers prepared by atom transfer radical polymerization was carried out under various reaction conditions. It was found that hydrazinolysis of 4-acetoxystyrene homopolymers, random and block copolymers with styrene in 1,4-dioxane, afforded the corresponding narrow...

Simultaneous Contact Sensing and Characterizing of Mechanical and Dynamic Heat Transfer Properties of Porous Polymeric Materials

Directory of Open Access Journals (Sweden)

Bao-guo Yao

2017-10-01

Full Text Available Porous polymeric materials, such as textile fabrics, are elastic and widely used in our daily life for garment and household products. The mechanical and dynamic heat transfer properties of porous polymeric materials, which describe the sensations during the contact process between porous polymeric materials and parts of the human body, such as the hand, primarily influence comfort sensations and aesthetic qualities of clothing. A multi-sensory measurement system and a new method were proposed to simultaneously sense the contact and characterize the mechanical and dynamic heat transfer properties of porous polymeric materials, such as textile fabrics in one instrument, with consideration of the interactions between different aspects of contact feels. The multi-sensory measurement system was developed for simulating the dynamic contact and psychological judgment processes during human hand contact with porous polymeric materials, and measuring the surface smoothness, compression resilience, bending and twisting, and dynamic heat transfer signals simultaneously. The contact sensing principle and the evaluation methods were presented. Twelve typical sample materials with different structural parameters were measured. The results of the experiments and the interpretation of the test results were described. An analysis of the variance and a capacity study were investigated to determine the significance of differences among the test materials and to assess the gage repeatability and reproducibility. A correlation analysis was conducted by comparing the test results of this measurement system with the results of Kawabata Evaluation System (KES in separate instruments. This multi-sensory measurement system provides a new method for simultaneous contact sensing and characterizing of mechanical and dynamic heat transfer properties of porous polymeric materials.

Novel fluorinated block copolymer architectures fuelled by atom transfer radical polymerization

DEFF Research Database (Denmark)

Jankova, Katja; Hvilsted, Søren

2005-01-01

Block copolymers based on poly(pentafluorostyrene), PFS, in various numbers and of different lengths, and polystyrene are prepared by atom transfer radical polymerization (ATRP). Di- and triblock copolymers with varying amounts of PFS were synthesized employing either I phenylethylbromide or 1,4-...

Surface modification of nanodiamond through metal free atom transfer radical polymerization

Science.gov (United States)

Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2016-12-01

Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by 1H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

A New Initiator Cholesteryl Chloroformate for Cupper-Based Atom Transfer Radical Polymerization of Methyl Methacrylate

Institute of Scientific and Technical Information of China (English)

曹健; 楚娟; 张可达

2004-01-01

The polymerization of metyl methacrylate (MMA) was studied in detail by use of CuCl/L as a catalyst and cholesteryl chloroformate (CC) as an initiator. It was found that the atom transfer radical polymerization of MMA could proceed when L equals to a multidentate aliphatic amine ligand, N,N,N',N",N"-penta(methyl acrylate)diethylenetriamine (MA5-DETA), and no polymerization was occurred while L=2,2'-bipyridine and 1,10-phenanthroline. The linear proportionality of the molecular weights to the conversions and straight lines observed in ln[M]0/[M] versus time plots indicated that the present polymerization system had the typical controlled polymerization characteristics.

Functionalization of lanthanum hydroxide nanowires by atom transfer radical polymerization

International Nuclear Information System (INIS)

Zhou Mi; Yuan Jinying; Yuan Weizhong; Yin Yingwu; Hong Xiaoyin

2007-01-01

Atom transfer radical polymerization (ATRP) has been used to prepare a core-shell hybrid nanostructure successfully: a hard core of single-crystalline lanthanum hydroxide nanowires and a soft shell of polystyrene (PS) brushes. Transmission electron microscopy (TEM) images indicated that the resulting products presented special structures and different thicknesses of polymer layers. The chemical components and grafted PS quantities of the samples were measured by Fourier transform infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA). The polymers showed narrow polydispersity, which proved that the lanthanum hydroxide nanowires initiated the 'living'/controlled polymerization of styrene. With the modifiability of lanthanum hydroxide nanowires, the solubility increased, which affords a new way to functionalize nanowires

Studies on atom transfer radical polymerization of acrylates and styrenes with controlled polymeric block structures

OpenAIRE

Ibrahim, Khalid

2006-01-01

Atom transfer radical polymerization (ATRP) was applied to homo and block copolymerization of vinyl monomers methacrylates, acrylates, and styrene with iron (FeCl2.4H2O) as the transition metal in most cases. As complexing ligand either a commercially available ligand (triphenyl phosphine) (PPh3) or synthetic aliphatic amines were used. As initiators, methyl 2-bromopropionate, ethyl 2-bromoisobutyrate, α,α-dichloroacetophenone, and poly(ethylene oxide) macroinitiator were employed. Block ...

Synthesis of poly(2-ethyl-2-oxazoline)-b-poly(styrene) copolymers via a dual initiator route combining cationic ring-opening polymerization and atom transfer radical polymerization

NARCIS (Netherlands)

Becer, C.R.; Paulus, R.M.; ppener, S.; Hoogenboom, R.; Fustin, C.A.; Gohy, J.M.W.; Schubert, U.S.

2008-01-01

Block copolymers of 2-ethyl-2-oxazoline (EtOx) and styrene were synthesized by a combination of cationic ring-opening polymerization (CROP) and atom transfer radical polymerization (ATRP). Initially, a detailed kinetic investigation for the ?-bromoisobutyrylbromide (BrEBBr) initiated CROP of EtOx

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.

Chemical vapor deposition graphene transfer process to a polymeric substrate assisted by a spin coater

International Nuclear Information System (INIS)

Kessler, Felipe; Da Rocha, Caique O C; Medeiros, Gabriela S; Fechine, Guilhermino J M

2016-01-01

A new method to transfer chemical vapor deposition graphene to polymeric substrates is demonstrated here, it is called direct dry transfer assisted by a spin coater (DDT-SC). Compared to the conventional method DDT, the improvement of the contact between graphene-polymer due to a very thin polymeric film deposited by spin coater before the transfer process prevented air bubbles and/or moisture and avoided molecular expansion on the graphene-polymer interface. An acrylonitrile-butadiene-styrene copolymer, a high impact polystyrene, polybutadiene adipate-co-terephthalate, polylactide acid, and a styrene-butadiene-styrene copolymer are the polymers used for the transfers since they did not work very well by using the DDT process. Raman spectroscopy and optical microscopy were used to identify, to quantify, and to qualify graphene transferred to the polymer substrates. The quantity of graphene transferred was substantially increased for all polymers by using the DDT-SC method when compared with the DDT standard method. After the transfer, the intensity of the D band remained low, indicating low defect density and good quality of the transfer. The DDT-SC transfer process expands the number of graphene applications since the polymer substrate candidates are increased. (paper)

Surface PEGylation of mesoporous silica materials via surface-initiated chain transfer free radical polymerization: Characterization and controlled drug release.

Science.gov (United States)

Huang, Long; Liu, Meiying; Mao, Liucheng; Huang, Qiang; Huang, Hongye; Wan, Qing; Tian, Jianwen; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

2017-12-01

As a new type of mesoporous silica materials with large pore diameter (pore size between 2 and 50nm) and high specific surface areas, SBA-15 has been widely explored for different applications especially in the biomedical fields. The surface modification of SBA-15 with functional polymers has demonstrated to be an effective way for improving its properties and performance. In this work, we reported the preparation of PEGylated SBA-15 polymer composites through surface-initiated chain transfer free radical polymerization for the first time. The thiol group was first introduced on SBA-15 via co-condensation with γ-mercaptopropyltrimethoxysilane (MPTS), that were utilized to initiate the chain transfer free radical polymerization using poly(ethylene glycol) methyl ether methacrylate (PEGMA) and itaconic acid (IA) as the monomers. The successful modification of SBA-15 with poly(PEGMA-co-IA) copolymers was evidenced by a series of characterization techniques, including 1 H NMR, FT-IR, TGA and XPS. The final SBA-15-SH- poly(PEGMA-co-IA) composites display well water dispersity and high loading capability towards cisplatin (CDDP) owing to the introduction of hydrophilic PEGMA and carboxyl groups. Furthermore, the CDDP could be released from SBA-15-SH-poly(PEGMA-co-IA)-CDDP complexes in a pH dependent behavior, suggesting the potential controlled drug delivery of SBA-15-SH-poly(PEGMA-co-IA). More importantly, the strategy should be also useful for fabrication of many other functional materials for biomedical applications owing to the advantages of SBA-15 and well monomer adoptability of chain transfer free radical polymerization. Copyright © 2017 Elsevier B.V. All rights reserved.

Activators generated by electron transfer for atom transfer radical polymerization of styrene in the presence of mesoporous silica nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Khezri, Khezrollah, E-mail: kh.khezri@ut.ac.ir [School of Chemistry, University College of Science, University of Tehran, PO Box 14155-6455, Tehran (Iran, Islamic Republic of); Roghani-Mamaqani, Hossein [Department of Polymer Engineering, Sahand University of Technology, PO Box 51335-1996, Tabriz (Iran, Islamic Republic of)

2014-11-15

Graphical abstract: Effect of mesoporous silica nanoparticles (MCM-41) on the activator generated by electron transfer for atom transfer radical polymerization (AGET ATRP) is investigated. Decrement of conversion and number average molecular weight and also increment of polydispersity index (PDI) values are three main results of addition of MCM-41 nanoparticles. Incorporation of MCM-41 nanoparticles in the polystyrene matrix can clearly increase thermal stability and decrease glass transition temperature of the nanocomposites. - Highlights: • Spherical morphology, hexagonal structure, and high surface area with regular pore diameters of the synthesized MCM-41 nanoparticles are examined. • AGET ATRP of styrene in the presence of MCM-41 nanoparticles is performed. • Effect of MCM-41 nanoparticles addition on the polymerization rate, conversion and molecular weights of the products are discussed. • Improvement in thermal stability of the nanocomposites and decreasing T{sub g} values was also observed by incorporation of MCM-41 nanoparticles. - Abstract: Activator generated by electron transfer for atom transfer radical polymerization was employed to synthesize well-defined mesoporous silica nanoparticles/polystyrene composites. Inherent features of spherical mesoporous silica nanoparticles were evaluated by nitrogen adsorption/desorption isotherm, X-ray diffraction and scanning electron microscopy analysis techniques. Conversion and molecular weight evaluations were carried out using gas and size exclusion chromatography respectively. By the addition of only 3 wt% mesoporous silica nanoparticles, conversion decreases from 81 to 58%. Similarly, number average molecular weight decreases from 17,116 to 12,798 g mol{sup −1}. However, polydispersity index (PDI) values increases from 1.24 to 1.58. A peak around 4.1–4.2 ppm at proton nuclear magnetic resonance spectroscopy results clearly confirms the living nature of the polymerization. Thermogravimetric

Extraction or adsorption? Voltammetric assessment of protamine transfer at ionophore-based polymeric membranes.

Science.gov (United States)

Garada, Mohammed B; Kabagambe, Benjamin; Amemiya, Shigeru

2015-01-01

Cation-exchange extraction of polypeptide protamine from water into an ionophore-based polymeric membrane has been hypothesized as the origin of a potentiometric sensor response to this important heparin antidote. Here, we apply ion-transfer voltammetry not only to confirm protamine extraction into ionophore-doped polymeric membranes but also to reveal protamine adsorption at the membrane/water interface. Protamine adsorption is thermodynamically more favorable than protamine extraction as shown by cyclic voltammetry at plasticized poly(vinyl chloride) membranes containing dinonylnaphthalenesulfonate as a protamine-selective ionophore. Reversible adsorption of protamine at low concentrations down to 0.038 μg/mL is demonstrated by stripping voltammetry. Adsorptive preconcentration of protamine at the membrane/water interface is quantitatively modeled by using the Frumkin adsorption isotherm. We apply this model to ensure that stripping voltammograms are based on desorption of all protamine molecules that are transferred across the interface during a preconcentration step. In comparison to adsorption, voltammetric extraction of protamine requires ∼0.2 V more negative potentials, where a potentiometric super-Nernstian response to protamine is also observed. This agreement confirms that the potentiometric protamine response is based on protamine extraction. The voltammetrically reversible protamine extraction results in an apparently irreversible potentiometric response to protamine because back-extraction of protamine from the membrane extremely slows down at the mixed potential based on cation-exchange extraction of protamine. Significantly, this study demonstrates the advantages of ion-transfer voltammetry over potentiometry to quantitatively and mechanistically assess protamine transfer at ionophore-based polymeric membranes as foundation for reversible, selective, and sensitive detection of protamine.

Improved performance and stability of field-effect transistors with polymeric residue-free graphene channel transferred by gold layer.

Science.gov (United States)

Jang, Mi; Trung, Tran Quang; Jung, Jin-Heak; Kim, Bo-Yeong; Lee, Nae-Eung

2014-03-07

One of the most significant issues that occurs when applying chemical-vapor deposited (CVD) graphene (Gr) to various high-performance device applications is the result of polymeric residues. Polymeric residues remain on the Gr surface during Gr polymer support transfer to an arbitrary substrate, and these residues degrade CVD Gr electrical properties. In this paper, we propose that a thin layer of gold be used as a CVD Gr transfer layer, instead of a polymer support layer, to enable a polymer residue-free transfer. Comparative investigation of the surface morphological and qualitative analysis of residues on Gr surfaces and Gr field-effect transistors (GFETs) using two transfer methods demonstrates that gold-transferred Gr, with uniform, smooth, and clean surfaces, enable GFETs to perform better than Gr transferred by the polymer, polymethylmethacrylate (PMMA). In GFETs fabricated by the gold transfer method, field-effect carrier mobility was greatly enhanced and the position of the Dirac point was significantly reduced compared to GFETs fabricated by the PMMA transfer method. In addition, compared to the PMMA-transferred GFETs, the gold-transferred GFETs showed greatly increased stability with smaller hysteresis and higher resistance to gate bias stress effects. These results suggest that the gold transfer method for Gr provides significant improvements in GFET performance and reliability by minimizing the polymeric residues and defects on Gr.

ATOM TRANSFER RADICAL POLYMERIZATION OF N-BUTYL METHACRYLATE IN AQUEOUS DISPERSED SYSTEMS: A MINIEMULSION APPROACH. (R826735)

Science.gov (United States)

Ultrasonication was applied in combination with a hydrophobe for the copper-mediated atom transfer radical polymerization of n-butyl methacrylate in an aqueous dispersed system. A controlled polymerization was successfully achieved, as demonstrated by a linear correlation between...

Surface-initiated Atom Transfer Radical Polymerization - a Technique to Develop Biofunctional Coatings

DEFF Research Database (Denmark)

Fristrup, Charlotte Juel; Jankova Atanasova, Katja; Hvilsted, Søren

2009-01-01

The initial formation of initiating sites for atom transfer radical polymerization (ATRP) on various polymer surfaces and numerous inorganic and metallic surfaces is elaborated. The subsequent ATRP grafting of a multitude of monomers from such surfaces to generate thin covalently linked polymer...

Surface modification of carbon nanotubes via combination of mussel inspired chemistry and chain transfer free radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Wan, Qing; Tian, Jianwen; Liu, Meiying; Zeng, Guangjian; Huang, Qiang [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Wang, Ke; Zhang, Qingsong [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of 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)

2015-08-15

Graphical abstract: A novel strategy combination of mussel inspired chemistry and chain transfer free radical polymerization has been developed for surface modification of carbon nanotubes with polymers for the first time. - Highlights: • Surface modification of CNTs via mussel inspired chemistry. • Preparation of aminated polymers through free radical polymerization. • Functionalized CNTs with aminated polymers via Michael addition reaction. • Highly dispersed CNTs in organic and aqueous solution. - Abstract: In this work, a novel strategy for surface modification of carbon nanotubes (CNTs) was developed via combination of mussel inspired chemistry and chain transfer free radical polymerization. First, pristine CNTs were functionalized with polydopamine (PDA), which is formed via self-polymerization of dopamine in alkaline conditions. These PDA functionalized CNTs can be further reacted with amino-terminated polymers (named as PDMC), which was synthesized through chain transfer free radical polymerization using cysteamine hydrochloride as chain transfer agent and methacryloxyethyltrimethyl ammonium chloride as the monomer. PDMC perfectly conjugated with CNT-PDA was ascertained by a series of characterization techniques including transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The dispersibility of obtained CNT nanocomposites (named as CNT-PDA-PDMC) was further examined. Results showed that the dispersibility of CNT-PDA-PDMC in aqueous and organic solutions was obviously enhanced. Apart from PDMC, many other amino-terminated polymers can also be used to functionalization of CNTs via similar strategy. Therefore, the method described in this work should be a general strategy for fabrication various polymer nanocomposites.

Synthesis of triblock and random copolymers of 4- acetoxystyrene and styrene by living atom transfer radical polymerization

DEFF Research Database (Denmark)

Gao, Bo; Chen, Xianyi; Ivan, Bela

1997-01-01

Triblock copolymers containing polystyrene (PSt) and poly(4-acetoxystyrene) (PAcOSt) segments have been prepared by atom transfer radical polymerization (ATRP). In the first step one of the two monomers was polymerized in bulk using the initiating system alpha,alpha'-dibromo-p-xylene/CuBr/2,2'-bi...

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.

In situ AFM investigation of electrochemically induced surface-initiated atom-transfer radical polymerization.

Science.gov (United States)

Li, Bin; Yu, Bo; Zhou, Feng

2013-02-12

Electrochemically induced surface-initiated atom-transfer radical polymerization is traced by in situ AFM technology for the first time, which allows visualization of the polymer growth process. It affords a fundamental insight into the surface morphology and growth mechanism simultaneously. Using this technique, the polymerization kinetics of two model monomers were studied, namely the anionic 3-sulfopropyl methacrylate potassium salt (SPMA) and the cationic 2-(metharyloyloxy)ethyltrimethylammonium chloride (METAC). The growth of METAC is significantly improved by screening the ammonium cations by the addition of ionic liquid electrolyte in aqueous solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of Robust and Antifouling Superhydrophobic Surfaces via Surface-Initiated Atom Transfer Radical Polymerization.

Science.gov (United States)

Xue, Chao-Hua; Guo, Xiao-Jing; Ma, Jian-Zhong; Jia, Shun-Tian

2015-04-22

Superhydrophobic surfaces were fabricated via surface-initiated atom transfer radical polymerization of fluorinated methacrylates on poly(ethylene terephthalate) (PET) fabrics. The hydrophobicity of the PET fabric was systematically tunable by controlling the polymerization time. The obtained superhydrophobic fabrics showed excellent chemical robustness even after exposure to different chemicals, such as acid, base, salt, acetone, and toluene. Importantly, the fabrics maintained superhydrophobicity after 2500 abrasion cycles, 100 laundering cycles, and long time exposure to UV irradiation. Also, the surface of the superhydrophobic fabrics showed excellent antifouling properties.

Synthesis and characterization of TiO2/Ag/polymer ternary nanoparticles via surface-initiated atom transfer radical polymerization

International Nuclear Information System (INIS)

Park, Jung Tae; Koh, Joo Hwan; Seo, Jin Ah; Cho, Yong Soo; Kim, Jong Hak

2011-01-01

We report on the novel ternary hybrid materials consisting of semiconductor (TiO 2 ), metal (Ag) and polymer (poly(oxyethylene methacrylate) (POEM)). First, a hydrophilic polymer, i.e. POEM, was grafted from TiO 2 nanoparticles via the surface-initiated atom transfer radical polymerization (ATRP) technique. These TiO 2 -POEM brush nanoparticles were used to template the formation of Ag nanoparticles by introduction of a AgCF 3 SO 3 precursor and a NaBH 4 aqueous solution for reduction process. Successful grafting of polymeric chains from the surface of TiO 2 nanoparticles and the in situ formation of Ag nanoparticles within the polymeric chains were confirmed using transmission electron microscopy (TEM), UV-vis spectroscopy, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). FT-IR spectroscopy also revealed the specific interaction of Ag nanoparticles with the C=O groups of POEM brushes. This study presents a simple route for the in situ synthesis of both metal and polymer confined within the semiconductor, producing ternary hybrid inorganic-organic nanomaterials.

Proton-Conducting Sulfonated Ionomers by Chemical Modification and Atom Transfer Radical Polymerization

DEFF Research Database (Denmark)

Nielsen, Mads Møller

The cornerstone in this dissertation is made up by three individual assessments of the diversity in the macromolecular landscape that can be obtained by applying relatively few efficient chemical tools. The intention is to gain deeper knowledge on the chemical tuning of proton exchange membranes...... of hydrocarbon macromolecular architectures, PSU with postsulfonated polystyrene (PS) grafts are investigated. Here, IEC is controlled through the degree of substitution, the graft length and DS. The grafting is performed with atom transfer radical polymerization (ATRP). The third assessment is dedicated...... of control by ATRP and click chemistry enables a wide selection of polymer structures with the handles: degree of substitution (DS), polymerization and sulfonation, and blending....

Simple preparation of thiol-ene particles in glycerol and surface functionalization by thiol-ene chemistry (TEC) and surface chain transfer free radical polymerization (SCT-FRP)

DEFF Research Database (Denmark)

Hoffmann, Christian; Chiaula, Valeria; Yu, Liyun

2018-01-01

functionalization of excess thiol groups via photochemical thiol-ene chemistry (TEC) resulting in a functional monolayer. In addition, surface chain transfer free radical polymerization (SCT-FRP) was used for the first time to introduce a thicker polymer layer on the particle surface. The application potential...

Study of energy transfer to solvent in radiation graft polymerization of styrene onto polyethylene

International Nuclear Information System (INIS)

Rabie, A.; Odian, G.

1977-01-01

The radiation-initiated graft polymerization of styrene onto polyethylene was studied to determine whether energy transfer to diluent was responsible for the previously observed high orders of dependence of the grafting rate on monomer concentration. n-Octane was used as the diluent instead of benzene. If energy transfer from excited polyethylene to benzene were present, it should not be with n-octane. The percent swelling of polyethylene by various n-octane--styrene mixtures was determined. The compositions of various n-octane--styrene mixtures absorbed inside polyethylene were determined by ultraviolet and refractive index measurements and found to be richer in styrene than the corresponding mixtures in which the polyethylene had been placed. The graft polymerization rates were determined at 0.000761, 0.0371, and 0.213 Mrad/hr and plotted against the inside styrene concentrations on a log-log scale to yield the kinetic orders of dependence of rate on monomer as 2, 3, and 3, respectively. It was concluded that energy transfer to diluent was not responsible for the high-order dependence observed

Preparation of polystyrene brush film by radical chain-transfer polymerization and micromechanical properties

Energy Technology Data Exchange (ETDEWEB)

Zhao Jing [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Chen Miao [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China)], E-mail: miaochen99@yahoo.com; An Yanqing [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Liu Jianxi [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Yan Fengyuan [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China)], E-mail: fyyan@lzb.ac.cn

2008-12-30

A radical chain-transfer polymerization technique has been applied to graft-polymerize brushes of polystyrene (PSt) on single-crystal silicon substrates. 3-Mercapto-propyltrimethoxysilane (MPTMS), as a chain-transfer agent for grafting, was immobilized on the silicon surface by a self-assembling process. The structure and morphology of the graft-functionalized silicon surfaces were characterized by the means of contact-angle measurement, ellipsometric thickness measurement, Fourier transformation infrared (FTIR) spectroscopy, and atomic force microscopy (AFM). The nanotribological and micromechanical properties of the as-prepared polymer brush films were investigated by frictional force microscopy (FFM), force-volume analysis and scratch test. The results indicate that the friction properties of the grafted polymer films can be improved significantly by the treatment of toluene, and the chemically bonded polystyrene film exhibits superior scratch resistance behavior compared with the spin-coated polystyrene film. The resultant polystyrene brush film is expected to develop as a potential lubrication coating for microelectromechanical systems (MEMS)

Surface modification of nanodiamond through metal free atom transfer radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of 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)

2016-12-30

Highlights: • Surface modification of ND with water soluble and biocompatible polymers. • Functionalized ND through metal free surface initiated ATRP. • The metal free surface initiated ATRP is rather simple and effective. • The ND-poly(MPC) showed high dispersibility and desirable biocompatibility. - Abstract: Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by {sup 1}H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

Surface modification of nanodiamond through metal free atom transfer radical polymerization

International Nuclear Information System (INIS)

Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2016-01-01

Highlights: • Surface modification of ND with water soluble and biocompatible polymers. • Functionalized ND through metal free surface initiated ATRP. • The metal free surface initiated ATRP is rather simple and effective. • The ND-poly(MPC) showed high dispersibility and desirable biocompatibility. - Abstract: Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by 1 H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

Diastereoisomeric diversity dictates reactivity of epoxy groups in limonene dioxide polymerization

Directory of Open Access Journals (Sweden)

M. Soto

2018-06-01

Full Text Available Limonene dioxide (LDO has the potential to find a wide application as a bio-based epoxy resin. Its polymerizations by catalyzed ring-opening, and by polyaddition with diamines were compared with the polymerizations of the commercial epoxy resins bisphenol-A diglycidyl ether (BADGE, and 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate (ECC. Differential scanning calorimetry (DSC studies showed that LDO polymerizations suffer in all cases studied from incomplete conversions. Nuclear magnetic resonance (NMR studies revealed that in cis-isomers of LDO the internal epoxide rings were not reacting. The low reactivity of this epoxide group was explained by mechanistic considerations making use of the Fürst-Plattner rule, or trans-diaxial effect. Due to diastereomeric diversity approximately one-fourth of epoxide groups present in LDO could not react. Therefore, a diastereoselective epoxidation of limonene could provide a fully reactive bio-based epoxy resin.

The Effect of Allylic Sulfide-Mediated IrreversibleAddition-Fragment Chain Transfer on the EmulsionPolymerization Kinetics of Styrene

Directory of Open Access Journals (Sweden)

Li An

2015-09-01

Full Text Available The effect of the irreversible addition-fragment chain transfer agent, butyl(2-phenylallylsulfane (BPAS, on the course of the emulsion polymerization of styrene and on the product molecular weight was investigated. The emulsion polymerizations were performed using various amounts of sodium dodecyl sulfate (SDS as the surfactant and potassium peroxodisulfate (KPS as the initiator. The relationships between the rates of polymerization (\\(R_{p} \\ and the number of particles per volume (\\(N_{c} \\ with respect to the concentrations of KPS, SDS, and BPAS were found to be \\(R_{p} \\propto \\left\\lbrack KPS \\right\\rbrack^{0.29} \\, \\(N_{c} \\propto \\left\\lbrack KPS \\right\\rbrack^{0.26} \\,\\(R_{p} \\propto \\left\\lbrack SDS \\right\\rbrack^{0.68} \\, \\(N_{c} \\propto \\left\\lbrack SDS \\right\\rbrack^{0.72} \\, and \\(R_{p} \\propto \\left\\lbrack BPAS \\right\\rbrack^{- 0.73} \\ . The obtained relationships can be attributed to the exit of the leaving group radicals on BPAS from the polymer particles. The experimental values of the average number of radicals per particle (\\(\\overset{\\_}{n} \\ were strongly dependent on the BPAS concentration and were in good agreement with the theoretical values (\\({\\overset{\\_}{n}}_{theo} \\ from model calculations. The number-average molecular weight (\\(\\overset{\\_}{M_{n}} \\ can be controlled by BPAS over nearly the entire conversion range, which is also in agreement with the mathematical model. In addition, the transfer rate coefficient (\\(k_{tr} \\ of BPAS can be estimated as 326 L/mol/s at 70 \\(^\\circ\\C. Moreover, similar good results were found for the tested redox reactions at 30 \\(^\\circ\\C.

Direct dry transfer of CVD graphene to an optical substrate by in situ photo-polymerization

Science.gov (United States)

Kessler, Felipe; Muñoz, Pablo A. R.; Phelan, Ciaran; Romani, Eric C.; Larrudé, Dunieskys R. G.; Freire, Fernando L.; Thoroh de Souza, Eunézio A.; de Matos, Christiano J. S.; Fechine, Guilhermino J. M.

2018-05-01

Here, we report on a method that allows graphene produced by chemical vapor deposition (CVD) to be directly transferred to an optically transparent photo resin, by in situ photo-polymerization of the latter, with high efficiency and low contamination. Two photocurable resins, A and B, with different viscosities but essentially the same chemical structure, were used. Raman spectroscopy and surface energy results show that large continuous areas of graphene were transferred with minimal defects to the lower viscosity resin (B), due to the better contact between the resin and graphene. As a proof-of-principle optical experiment, graphene on the polymeric substrate was subjected to high-intensity femtosecond infrared pulses and third-harmonic generation was observed with no noticeable degradation of the sample. A sheet third-order susceptibility χ (3) = 0.71 ×10-28m3V-2 was obtained, matching that of graphene on a glass substrate. These results indicate the suitability of the proposed transfer method, and of the photo resin, for the production of nonlinear photonic components and devices.

Influence of substituents in vinyl groups on reactivity of parylene during polymerization process

International Nuclear Information System (INIS)

Freza, Sylwia; Skurski, Piotr; Bobrowski, Maciej

2010-01-01

The MCSCF calculations indicate that both triplet and singlet state of biradical di-para-xylylene can exist during polymerization of parylene in gas phase and both can potentially react with vinyl molecules. The singlet-state open-shell dimer turned out to exhibit multiconfigurational character. In the case of triplet state of the dimer two mechanisms of the reactions with various species containing vinyl groups have been examined at the B3LYP/6-31G level. The kinetic and thermodynamical barriers have been estimated for the reaction path involving the π-bond cleavage as well as for the route describing the hydrogen atom transfer. It was found that the overall reactions are thermodynamically favorable, whereas appropriate kinetic barriers for certain derivatives are very small (close to 0 kcal/mol) which in turn makes allowances for easy reactivity under accessible conditions. The calculated mechanisms indicate the influence of substituents in vinyl groups for reactivity of parylene during LPCVD process.

Preparation of nanocomposites by reversible addition-fragmentation chain transfer polymerization from the surface of quantum dots in miniemulsion

NARCIS (Netherlands)

Carvalho Esteves, de A.C.; Hodge, P.; Trindade, T.; Barros-Timmons, A.M.M.V.

2009-01-01

Herein, we report the synthesis of quantum dots (QDs)/polymer nanocomposites by reversible addition-fragmentation chain transfer (RAFT) polymerization in miniemulsions using a grafting from approach. First, the surfaces of CdS and CdSe QDs were functionalized using a chain transfer agent, a

Organic thin film transistors with polymer brush gate dielectrics synthesized by atom transfer radical polymerization

DEFF Research Database (Denmark)

Pinto, J.C.; Whiting, G.L.; Khodabakhsh, S.

2008-01-01

, synthesized by atom transfer radical polymerization (ATRP), were used to fabricate low voltage OFETs with both evaporated pentacene and solution deposited poly(3-hexylthiophene). The semiconductor-dielectric interfaces in these systems were studied with a variety of methods including scanning force microscopy...

Evaluation of shrinkage polymerization and temperature of different acrylic resins used to splinting transfer copings in indirect impression technique

Science.gov (United States)

Franco, Ana Paula G. O.; Karam, Leandro Z.; Galvão, José R.; Kalinowski, Hypolito J.

2015-09-01

The aim of the present study was evaluate the shrinkage polymerization and temperature of different acrylic resins used to splinting transfer copings in indirect impression technique. Two implants were placed in an artificial bone, with the two transfer copings joined with dental floss and acrylic resins; two dental resins are used. Measurements of deformation and temperature were performed with Fiber Braggs grating sensor for 17 minutes. The results revealed that one type of resin shows greater values of polymerization shrinkage than the other. Pattern resins did not present lower values of shrinkage, as usually reported by the manufacturer.

Polymer coating comprising 2-methoxyethyl acrylate units synthesized by surface-initiated atom transfer radical polymerization

DEFF Research Database (Denmark)

2011-01-01

Source: US2012184029A The present invention relates to preparation of a polymer coating comprising or consisting of polymer chains comprising or consisting of units of 2-methoxyethyl acrylate synthesized by Surface-Initiated Atom Transfer Radical Polymerization (SI ATRP) such as ARGET SI ATRP...

Modification of Jute Fibers with Polystyrene via Atom Transfer Radical Polymerization

DEFF Research Database (Denmark)

Plackett, David; Jankova, Katja Atanassova; Egsgaard, Helge

2005-01-01

Atom transfer radical polymerization (ATRP) was investigated as a method of covalently bonding polystyrene to jute (Corchorus capsularis) and as a possible approach to fiber composites with enhanced properties. Jute fibers were modified with a brominated initiator and subsequently ATRP modified...... to attach polystyrene and then examined using SEM, DSC, TGA, FTIR, XPS, elemental analysis, and Py-GC-MS. These techniques confirmed that polystyrene had been covalently bound to the fibers and consequently ATRP-modified jute fiber mats were used to prepare hot-pressed polystyrene composites. Composite...

Carprofen-imprinted monolith prepared by reversible addition-fragmentation chain transfer polymerization in room temperature ionic liquids.

Science.gov (United States)

Ban, Lu; Han, Xu; Wang, Xian-Hua; Huang, Yan-Ping; Liu, Zhao-Sheng

2013-10-01

To obtain fast separation, ionic liquids were used as porogens first in combination with reversible addition-fragmentation chain transfer (RAFT) polymerization to prepare a new type of molecularly imprinted polymer (MIP) monolith. The imprinted monolithic column was synthesized using a mixture of carprofen (template), 4-vinylpyridine, ethylene glycol dimethacrylate, [BMIM]BF4, and chain transfer agent (CTA). Some polymerization factors, such as template-monomer molar ratio, the degree of crosslinking, the composition of the porogen, and the content of CTA, on the column efficiency and imprinting effect of the resulting MIP monolith were systematically investigated. Affinity screening of structurally similar compounds with the template can be achieved in 200 s on the MIP monolith due to high column efficiency (up to 12,070 plates/m) and good column permeability. Recognition mechanism of the imprinted monolith was also investigated.

Scale-up of the Reversible Addition-Fragmentation Chain Transfer (RAFT Polymerization Using Continuous Flow Processing

Directory of Open Access Journals (Sweden)

Nenad Micic

2014-01-01

Full Text Available A controlled radical polymerization process using the Reversible Addition-Fragmentation Chain Transfer (RAFT approach was scaled up by a factor of 100 from a small laboratory scale of 5 mL to a preparative scale of 500 mL, using batch and continuous flow processing. The batch polymerizations were carried out in a series of different glass vessels, using either magnetic or overhead stirring, and different modes of heating: Microwave irradiation or conductive heating in an oil bath. The continuous process was conducted in a prototype tubular flow reactor, consisting of 6 mm ID stainless steel tubing, fitted with static mixers. Both reactor types were tested for polymerizations of the acid functional monomers acrylic acid and 2-acrylamido-2-methylpropane-1-sulfonic acid in water at 80 °C with reaction times of 30 to 40 min. By monitoring the temperature during the exothermic polymerization process, it was observed that the type and size of reactor had a significant influence on the temperature profile of the reaction.

Visible Light-Induced Metal Free Surface Initiated Atom Transfer Radical Polymerization of Methyl Methacrylate on SBA-15

Directory of Open Access Journals (Sweden)

Liang Ma

2017-02-01

Full Text Available Surface-initiated atom transfer radical polymerization (SI-ATRP is one of the most versatile techniques to modify the surface properties of materials. Recent developed metal-free SI-ATRP makes such techniques more widely applicable. Herein photo-induced metal-free SI-ATRP of methacrylates, such as methyl methacrylate, N-isopropanyl acrylamide, and N,N-dimethylaminoethyl methacrylate, on the surface of SBA-15 was reported to fabricate organic-inorganic hybrid materials. A SBA-15-based polymeric composite with an adjustable graft ratio was obtained. The structure evolution during the SI-ATRP modification of SBA-15 was monitored and verified by FT-IR, XPS, TGA, BET, and TEM. The obtained polymeric composite showed enhanced adsorption ability for the model compound toluene in aqueous conditions. This procedure provides a low-cost, readily available, and easy modification method to synthesize polymeric composites without the contamination of metal.

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

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.

3D scaffolds from vertically aligned carbon nanotubes/poly(methyl methacrylate) composites via atom transfer radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Tebikachew, Behabtu; Magina, Sandra [CICECO, Department of Chemistry, University of Aveiro (Portugal); Mata, Diogo; Oliveira, Filipe J.; Silva, Rui F. [CICECO, Department of Materials and Ceramic Engineering, University of Aveiro (Portugal); Barros-Timmons, Ana, E-mail: anabarros@ua.pt [CICECO, Department of Chemistry, University of Aveiro (Portugal)

2015-01-15

Vertically aligned carbon nanotubes (VACNTs) synthesized by Thermal Chemical Vapour Deposition (TCVD) were modified using an Ar:O{sub 2} (97:3) plasma to generate oxygen-containing functional groups on the surface for subsequent modification. X-ray photo-emission spectroscopy (XPS) and micro-Raman analyses confirmed the grafting of those functional groups onto the surface of the nanotubes as well as the removal of amorphous carbon produced and deposited on the VACNT forests during the CVD process. The plasma treated VACNT forests were further modified with 2-bromo-2-methylpropionyl bromide, an atom transfer radical polymerization (ATRP) initiator, to grow poly(methyl methacrylate) (PMMA) chains from the forests via ATRP. Scanning transmission electron microscopy (STEM) of the ensuing VACNT/PMMA composites confirmed the coating of the nanotube forests with the PMMA polymer. 3D scaffolds of polymeric composites with honeycomb like structure were then obtained. Compressive tests have shown that the VACNT/PMMA composite has higher compressive strength than the pristine forest. - Highlights: • Vertically aligned carbon nanotubes (VACNTs) were synthesized and plasma modified. • X-ray photo-emission and Raman spectroscopies confirmed the VACNTs modification. • Poly(methyl methacrylate) chains were grown via ATRP from the VACNTs. • STEM of the VACNT/PMMA composites confirmed that PMMA surrounds the nanotubes. • VACNT/PMMA composite has higher compressive strength compared to the pristine forest.

3D scaffolds from vertically aligned carbon nanotubes/poly(methyl methacrylate) composites via atom transfer radical polymerization

International Nuclear Information System (INIS)

Tebikachew, Behabtu; Magina, Sandra; Mata, Diogo; Oliveira, Filipe J.; Silva, Rui F.; Barros-Timmons, Ana

2015-01-01

Vertically aligned carbon nanotubes (VACNTs) synthesized by Thermal Chemical Vapour Deposition (TCVD) were modified using an Ar:O 2 (97:3) plasma to generate oxygen-containing functional groups on the surface for subsequent modification. X-ray photo-emission spectroscopy (XPS) and micro-Raman analyses confirmed the grafting of those functional groups onto the surface of the nanotubes as well as the removal of amorphous carbon produced and deposited on the VACNT forests during the CVD process. The plasma treated VACNT forests were further modified with 2-bromo-2-methylpropionyl bromide, an atom transfer radical polymerization (ATRP) initiator, to grow poly(methyl methacrylate) (PMMA) chains from the forests via ATRP. Scanning transmission electron microscopy (STEM) of the ensuing VACNT/PMMA composites confirmed the coating of the nanotube forests with the PMMA polymer. 3D scaffolds of polymeric composites with honeycomb like structure were then obtained. Compressive tests have shown that the VACNT/PMMA composite has higher compressive strength than the pristine forest. - Highlights: • Vertically aligned carbon nanotubes (VACNTs) were synthesized and plasma modified. • X-ray photo-emission and Raman spectroscopies confirmed the VACNTs modification. • Poly(methyl methacrylate) chains were grown via ATRP from the VACNTs. • STEM of the VACNT/PMMA composites confirmed that PMMA surrounds the nanotubes. • VACNT/PMMA composite has higher compressive strength compared to the pristine forest

Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

OpenAIRE

Shahabuddin, Syed; Hamime Ismail, Fatem; Mohamad, Sharifah; Muhamad Sarih, Norazilawati

2015-01-01

Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydro...

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.

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.

Synthesis of Environmentally Responsive Polymers by Atom Transfer Radical Polymerization: Generation of Reversible Hydrophilic and Hydrophobic Surfaces

Directory of Open Access Journals (Sweden)

Vikas Mittal

2010-05-01

Full Text Available Environmentally responsive poly(N-isopropylacrylamide brushes were grafted from the surface of polymer particles or flat surfaces in order to generate reversible hydrophilic and hydrophobic surfaces. The use of atom transfer radical polymerization was demonstrated for the grafting of polymer brushes as it allows efficient control on the amount of grafted polymer. The polymer particles were generated with or without surfactant in the emulsion polymerization and their surface could be modified with the atom transfer radical polymerization (ATRP initiator. The uniform functionalization of the surface with ATRP initiator was responsible for the uniform grafting of polymer brushes. The grafted brushes responded reversibly with changes in temperature indicating that the reversible responsive behavior could be translated to the particle surfaces. The particles were observed to adsorb and desorb protein and virus molecules by changing the temperatures below or higher than 32 °C. The initiator functionalized particles could also be adsorbed on the flat surfaces. The adsorption process also required optimization of the heat treatment conditions to form a uniform layer of the particles on the substrate. The grafted polymer brushes also responded to the changes in temperatures similar to the spherical particles studied through water droplets placed on the flat substrates.

Metallophilic interactions in polymeric group 11 thiols

Science.gov (United States)

Kolari, Kalle; Sahamies, Joona; Kalenius, Elina; Novikov, Alexander S.; Kukushkin, Vadim Yu.; Haukka, Matti

2016-10-01

Three polymeric group 11 transition metal polymers featuring metallophilic interactions were obtained directly via self-assembly of metal ions and 4-pyridinethiol ligands. In the cationic [Cu2(S-pyH)4]n2+ with [ZnCl4]n2- counterion (1) and in the neutral [Ag(S-py) (S-pyH)]n (2) 4-pyridinethiol (S-pyH) and its deprotonated form (S-py) are coordinated through the sulfur atom. Both ligands are acting as bridging ligands linking the metal centers together. In the solid state, the gold(I) polymer [Au(S-pyH)2]Cl (3) consists of the repeating cationic [Au(S-pyH)2]+ units held together by aurophilic interactions. Compound 1 is a zig-zag chain, whereas the metal chains in the structures of 2 and 3 are linear. The protonation level of the thiol ligand had an impact on the crystallization of polymers. Both nature of the metal center and reaction conditions affected the polymerization. QTAIM analysis confirmed direct metal-metal contacts only in polymers 1 and 3. In polymer 2, no theoretical evidence of argentophilic contacts was obtained even though the AgṡṡṡAg distance was found to be less than sum of the Bondi's van der Waals radius of silver.

Poly(vinyl acetate-Based Block Copolymer/Clay Nanocomposites Prepared by In Situ Atom Transfer Radical Polymerization

Directory of Open Access Journals (Sweden)

M.A. Semsarzadeh

2009-12-01

Full Text Available Atom transfer radical polymerization of styrene (St and methyl methacrylate (MMA was performed at 90oC in the absence and presence of nanoclay (Cloisite 30B. Trichloromethyl-terminated poly(vinyl acetate telomerand CuCl/ PMDETA were used as a macroinitiator and catalyst system, respectively. The experimental results showed that the atom transfer radical polymerization of St and MMA in the absence or presence of nanoclay proceeds via a controlled/living mode. It was observed that nanoclay significantly enhances the homopolymerization rate of MMA, which was attributed to the activated conjugated C=C bond of MMA monomer via interaction between the carbonyl group of MMA monomer and the hydroxyl moiety (Al-O-H of nanoclay as well as the effect of nanoclay on the dynamic equilibrium between the active (macro radicals and dormant species.Homopolymerization rate of St (a non-coordinative monomer with nanoclay decreased slightly in the presence of nanoclay. This could be explained by insertion of a portion of macroinitiator into the clay galleries, where no sufficient St monomer exists due to the low compatibility or interaction of St monomer with nanoclay to react with the macroinitiator. The results obtained from XRD, TEM and TGA analyses were fully in agreement with the kinetic data. Structure of the poly(vinyl acetate-bpolystyrene nanocomposite was found to be a combination of stacking layers and exfoliated structures while poly(vinyl acetate-b-poly(methyl methacryale nanocomposite had an exfoliated structure. This difference in the structure of nanocomposites was attributed to the different capability of the monomers (styrene and methyl methacrylate to react with the hydroxyl moiety (Al-O-H of nanoclay.

Complexity in modeling of residual stresses and strains during polymerization of bone cement: effects of conversion, constraint, heat transfer, and viscoelastic property changes.

Science.gov (United States)

Gilbert, Jeremy L

2006-12-15

Aseptic loosening of cemented joint prostheses remains a significant concern in orthopedic biomaterials. One possible contributor to cement loosening is the development of porosity, residual stresses, and local fracture of the cement that may arise from the in-situ polymerization of the cement. In-situ polymerization of acrylic bone cement is a complex set of interacting processes that involve polymerization reactions, heat generation and transfer, full or partial mechanical constraint, evolution of conversion- and temperature-dependent viscoelastic material properties, and thermal and conversion-driven changes in the density of the cement. Interactions between heat transfer and polymerization can lead to polymerization fronts moving through the material. Density changes during polymerization can, in the presence of mechanical constraint, lead to the development of locally high residual strain energy and residual stresses. This study models the interactions during bone cement polymerization and determines how residual stresses develop in cement and incorporates temperature and conversion-dependent viscoelastic behavior. The results show that the presence of polymerization fronts in bone cement result in locally high residual strain energies. A novel heredity integral approach is presented to track residual stresses incorporating conversion and temperature dependent material property changes. Finally, the relative contribution of thermal- and conversion-dependent strains to residual stresses is evaluated and it is found that the conversion-based strains are the major contributor to the overall behavior. This framework provides the basis for understanding the complex development of residual stresses and can be used as the basis for developing more complex models of cement behavior.

Introduction of various amine groups onto polyethylene bead prepared by radiation-induced polymerization

International Nuclear Information System (INIS)

Kim, M.S.; Choi, S.H.; Lee, K.P.

2002-01-01

Complete text of publication follows. Radiation-induced graft polymerization is a good method for modification of chemical and physical properties of polymeric materials because it can endow properties such as membrane quality, ion exchange, blood compatibility, dyeability, protein adsorption, and immobilization of bioactive materials. Polyethylene microbead is very useful material due to the following advantages; low price, simple purchase, high sensitivity, and simple analysis. On the other hand, the epoxy group of the glycidyl methacrylate (GMA) can easily be converted to the various functional groups such as amines, alcohols, phosphoric acid, sulfonic acid, and amino acid, etc. Cyclodextrin have been applied universally in various industries such as foods, cosmetics, pharmaceutical industry, analytical chemistry, and chemical industry. In order to obtain cyclodextrins, polyethylene microbead with the epoxy group were prepared by radiation-induced graft polymerization of GMA onto polyethylene microbead. The physical and chemical properties of the GMA-induced polyethylene microbeads were investigated by IR, thermal analysis (TGA/DSC), and SEM, respectively. Subsequently, the various amine groups such as diethylamine. diethylenetriamine, triethylamine, triethylenetetramine, and 1,6-hexanediamine were induced onto the epoxy group in polyethylene microbead. Finally, cyclodextrin glucanotransferase were immobilized onto polyethylene microbead with various amines under the various experimental conditions, such as pH, amin content, immobilization time, and etc. The activity of CGTase-immobilized polyethylene microbead was determined by Phenolphthein method. The production of the cyclodextrins from starch is in progress

Ion conducting solid polymer electrolytes based on polypentafluorostyrene-b-polyether-b-polypentafluorostyrene prepared by atom transfer radical polymerization

DEFF Research Database (Denmark)

Jankova, Katja; Jannasch, P.; Hvilsted, Søren

2004-01-01

Novel triblock copolymers based on central poly( ethylene glycol) ( PEG) or poly( ethylene glycol-co-propylene glycol) (PEGPG) blocks with poly( pentafluorostyrene) (PFS) outer blocks were prepared by Atom Transfer Radical Polymerization (ATRP) with polydispersities on the order of 1.2 - 1...

Design and synthesis of structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization chemistry

Institute of Scientific and Technical Information of China (English)

Dong Jinyong

2006-01-01

Functionalization of polyolefins is an industrially important yet scientifically challenging research subject.This paper summarizes our recent effort to access structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization.In one approach,polypropylenes containing side chain functional groups of controlled concentrations were obtained by Ziegler-Natta-catalyzed copolymerization of propylene in combination with either living anionic or controlled radical polymerization of polar monomers.The copolymerization of propylene with 1,4-divinylbenzene using an isospecific MgC12-supported TIC14 catalyst yielded potypropylenes containing pendant styrene moieties.Both metalation reaction with n-butyllithium and hydrochlorination reaction with dry hydrogen chloride selectively and quantitatively occurred at the pendant reactive sites,generating polymeric benzyllithium and 1-chloroethylbenzene species.These species initiated living anionic polymerization of styrene(S)and atom transfer radical polymerization(in the presence of CuC1 and pentamethyldiethylenetriamine) of methyl methacrylate(MMA),respectively,resulting in functional polypropylene graft copolymers(PP-g-PS and PP-g-PMMA)with controllable graft lengths.In another approach,chain end-functionalized polypropylenes containing a terminal OH-group with controlled molecular weights were directly prepared by propylene polymerization with a metaUocene catalyst through a selective aluminum chain transfer reaction.Both approaches proved to be desirable polyolefin functionalization routes in terms of efficiency and polymer structure controllability.

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.

The pentafluorostyrene endeavours with atom transfer radical polymerization - quo vadis?

DEFF Research Database (Denmark)

Hvilsted, Søren

2014-01-01

The versatility of the atom transfer radical polymerization (ATRP) of pentafluorostyrene (FS) is comprehensively evaluated. The ATRP of a wide range of monomers derived from FS is likewise discussed with emphasis on the potential polymer applications. A large number of block and star copolymers...... centred around polypentafluorostyrene (PFS) and prepared primarily using the bromomacroinitiator concept is surveyed. Here the main emphasis is on the feasibility of the polymer design, but also the very many different applications are highlighted. The potential grafting onto PFS and PFS block copolymers...... by exploitation of the very labile para-fluorine demonstrates new material architecture possibilities through very mild reaction conditions. Finally the utility of PFS in various conducting materials is elaborated. The amphiphilic nature of PFS in triblock copolymers with polyethers has been exploited for Li+ ion...

Poly(n-isopropylacrylamide)-based hydrogel coatings on magnetite nanoparticles via atom transfer radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Frimpong, Reynolds A; Hilt, J Zach [Department of Chemical and Materials Engineering, University of Kentucky, Lexington, KY 40506 (United States)], E-mail: hilt@engr.uky.edu

2008-04-30

Core magnetite (Fe{sub 3}O{sub 4}) nanoparticles have been functionalized with a model intelligent hydrogel system based on the temperature responsive polymer poly(n-isopropyl acrylamide) (PNIPAAm) to obtain magnetically responsive core-shell nanocomposites. Fe{sub 3}O{sub 4} nanoparticles were obtained from a one-pot co-precipitation method which provided either oleic acid (hydrophobic) or citric acid (hydrophilic) coated nanoparticles. Subsequent ligand exchange of these coatings with various bromine alkyl halides and a bromo silane provided initiating sites for functionalization with NIPAAm using atom transfer radical polymerization (ATRP). The bromine alkyl halides that were used were 2-bromo-2-methyl propionic acid (BMPA) and 2-bromopropionyl bromide (BPB). The bromo silane that was used was 3-bromopropyl trimethoxysilane (BPTS). The intelligent polymeric shell consists of NIPAAm crosslinked with poly(ethylene glycol) 400 dimethacrylate (PEG400DMA). Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were used to confirm the presence of the polymeric shell. Dynamic light scattering (DLS) was used to characterize the nanocomposites for particle size changes with temperature. Their magnetic and temperature responsiveness show great promise for further biomedical applications. This platform for functionalizing magnetic nanoparticles with intelligent hydrogels promises to impact a wide range of medical and biological applications of magnetic nanoparticles.

Poly(n-isopropylacrylamide)-based hydrogel coatings on magnetite nanoparticles via atom transfer radical polymerization

International Nuclear Information System (INIS)

Frimpong, Reynolds A; Hilt, J Zach

2008-01-01

Core magnetite (Fe 3 O 4 ) nanoparticles have been functionalized with a model intelligent hydrogel system based on the temperature responsive polymer poly(n-isopropyl acrylamide) (PNIPAAm) to obtain magnetically responsive core-shell nanocomposites. Fe 3 O 4 nanoparticles were obtained from a one-pot co-precipitation method which provided either oleic acid (hydrophobic) or citric acid (hydrophilic) coated nanoparticles. Subsequent ligand exchange of these coatings with various bromine alkyl halides and a bromo silane provided initiating sites for functionalization with NIPAAm using atom transfer radical polymerization (ATRP). The bromine alkyl halides that were used were 2-bromo-2-methyl propionic acid (BMPA) and 2-bromopropionyl bromide (BPB). The bromo silane that was used was 3-bromopropyl trimethoxysilane (BPTS). The intelligent polymeric shell consists of NIPAAm crosslinked with poly(ethylene glycol) 400 dimethacrylate (PEG400DMA). Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were used to confirm the presence of the polymeric shell. Dynamic light scattering (DLS) was used to characterize the nanocomposites for particle size changes with temperature. Their magnetic and temperature responsiveness show great promise for further biomedical applications. This platform for functionalizing magnetic nanoparticles with intelligent hydrogels promises to impact a wide range of medical and biological applications of magnetic nanoparticles

Crystalline TiO2 grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

International Nuclear Information System (INIS)

Zhao Yuancong; Tu Qiufen; Wang Jin; Huang Qiongjian; Huang Nan

2010-01-01

Crystalline TiO 2 films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO 2 films by self-assembling, and the HUPA on TiO 2 films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO 2 films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

Crystalline TiO 2 grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

Science.gov (United States)

Zhao, Yuancong; Tu, Qiufen; Wang, Jin; Huang, Qiongjian; Huang, Nan

2010-12-01

Crystalline TiO 2 films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO 2 films by self-assembling, and the HUPA on TiO 2 films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO 2 films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

Directory of Open Access Journals (Sweden)

Syed Shahabuddin

2015-01-01

Full Text Available Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydroxyphenylethane, a trifunctional core molecule, to give well-defined triple-arm star-branched polystyrene.

Preparation of magnetic latexes functionalized with chloromethyl groups via emulsifier-free miniemulsion polymerization

International Nuclear Information System (INIS)

Faridi-Majidi, Reza; Sharifi-Sanjani, Naser

2007-01-01

Functionalized crosslinked polystyrene-co-divinylbenzene-co-chloromethylstyrene magnetic latex particles were prepared via emulsifier-free miniemulsion polymerization using 2, 2' azobis (2-amidinopropane) dihydrochloride (V-50) as an initiator and in the presence of magnetite nanoparticles in the monomers. Transmission electron microscopy (TEM) proved the presence of magnetite nanoparticles in polymer particles. Differential scanning calorimetery (DSC) analysis of the product showed an exothermic signal due to crosslinking of chains through electrophilic aromatic substitution of phenyl groups with chloromethyl groups in the presence of the dispersed Fe 3 O 4 as Lewis acid. This was proven by thermogravimetric analysis (TGA) via the loss of gaseous HCl. The results were also compared with those of magnetite-free miniemulsion polymerization using V-50

Preparation of magnetic latexes functionalized with chloromethyl groups via emulsifier-free miniemulsion polymerization

Energy Technology Data Exchange (ETDEWEB)

Faridi-Majidi, Reza [School of Chemistry, University College of Science, Tehran University, Tehran (Iran, Islamic Republic of)]. E-mail: refaridi@khayam.ut.ac.ir; Sharifi-Sanjani, Naser [School of Chemistry, University College of Science, Tehran University, Tehran (Iran, Islamic Republic of)

2007-04-15

Functionalized crosslinked polystyrene-co-divinylbenzene-co-chloromethylstyrene magnetic latex particles were prepared via emulsifier-free miniemulsion polymerization using 2, 2' azobis (2-amidinopropane) dihydrochloride (V-50) as an initiator and in the presence of magnetite nanoparticles in the monomers. Transmission electron microscopy (TEM) proved the presence of magnetite nanoparticles in polymer particles. Differential scanning calorimetery (DSC) analysis of the product showed an exothermic signal due to crosslinking of chains through electrophilic aromatic substitution of phenyl groups with chloromethyl groups in the presence of the dispersed Fe{sub 3}O{sub 4} as Lewis acid. This was proven by thermogravimetric analysis (TGA) via the loss of gaseous HCl. The results were also compared with those of magnetite-free miniemulsion polymerization using V-50.

Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions.

Science.gov (United States)

Zheng, Haiyan; Li, Kuo; Cody, George D; Tulk, Christopher A; Dong, Xiao; Gao, Guoying; Molaison, Jamie J; Liu, Zhenxian; Feygenson, Mikhail; Yang, Wenge; Ivanov, Ilia N; Basile, Leonardo; Idrobo, Juan-Carlos; Guthrie, Malcolm; Mao, Ho-Kwang

2016-09-19

Acetonitrile (CH3 CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH⋅⋅⋅N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp(2) and sp(3) bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Antifouling coatings via plasma polymerization and atom transfer radical polymerization on thin film composite membranes for reverse osmosis

Science.gov (United States)

Hirsch, Ulrike; Ruehl, Marco; Teuscher, Nico; Heilmann, Andreas

2018-04-01

A major drawback to otherwise highly efficient membrane-based desalination techniques like reverse osmosis (RO) is the susceptibility of the membranes to biofouling. In this work, a combination of plasma activation, plasma bromination and surface-initiated atom transfer radical polymerization (si-ATRP) of hydrophilic and zwitterionic monomers, namely hydroxyethyl methacrylate (HEMA), 2-methacryloyloxyethyl phosphorylcholine (MPC) and [2-(methacryloyloxy)ethyl]-dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA), was applied to generate non-specific, anti-adhesive coatings on thin film composite (TFC) membranes. The antifouling effect of the coatings was shown by short-time batch as well as long-time steady state cultivation experiments with the microorganism Pseudomonas fluorescens. It could be shown that plasma functionalization and polymerization is possible on delicate thin film composite membranes without restricting their filtration performance. All modified membranes showed an increased resistance towards the adhesion of Pseudomonas fluorescens. On average, the biofilm coverage was reduced by 51.4-12.6% (for HEMA, SBMA, and MPC), the highest reduction was monitored for MPC with a biofilm reduction by 85.4%. The hydrophilic coatings applied did not only suppress the adhesion of Pseudomonas fluorescens, but also significantly increase the permeate flux of the membranes relative to uncoated membranes. The stability of the coatings was however not ideal and will have to be improved for future commercial use.

Synthesis of Amphiphilic Copolymwers by Atom Transfer Radical Polymerization

DEFF Research Database (Denmark)

Hansen, Natanya Majbritt Louie

2007-01-01

Fluorerede polymerer besidder en række enestående egenskaber såsom god biokom-patibilitet og lav overfladeenergi såvel som god kemisk og termisk stabilitet. Målsæt-ningen for denne afhandling var at fremstille fluorerede polymerer og copolymerer, der potentielt kunne finde anvendelse som...... egenskaber der genfindes i homopolymerer af den dominerende monomer i copolymeren. Som indikation af de nye materialers mulige vekselvirkning med omgivelserne udførtes omfattende studier af kontaktvinkler. Film fremstillet af de fluorerede copolymerer og polymerer udviste øget hydrofobicitet (vandafvisning...

Iron halide mediated atom transfer radical polymerization of methyl methacrylate with N-Alkyl-2-pyridylmethanimine as the ligand

NARCIS (Netherlands)

Zhang, H.; Schubert, U.S.

2004-01-01

The controlled atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) catalyzed by iron halide/N-(n-hexyl)-2-pyridylmethanimine (NHPMI) is described. The ethyl 2-bromoisobutyrate (EBIB)-initiated ATRP with [MMA]0/[EBIB]0/[iron halide]0/[NHPMI]0 = 150/1/1/2 was better controlled in

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...

Crystalline TiO{sub 2} grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Zhao Yuancong; Tu Qiufen; Wang Jin; Huang Qiongjian [Key Lab. of Advanced Technology for Materials, Education Ministry, School of Material Science and Technology of Southwest Jiaotong University, Chengdu, Sichuan (China); Huang Nan, E-mail: zhaoyc7320@163.com [Key Lab. of Advanced Technology for Materials, Education Ministry, School of Material Science and Technology of Southwest Jiaotong University, Chengdu, Sichuan (China)

2010-12-15

Crystalline TiO{sub 2} films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO{sub 2} films by self-assembling, and the HUPA on TiO{sub 2} films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO{sub 2} films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

Conditional Monte Carlo sampling to find branching architectures of polymers from radical polymerizations with transfer to polymer and recombination termination

NARCIS (Netherlands)

Iedema, P.D.; Wulkow, M.; Hoefsloot, H.C.J.

2007-01-01

A model is developed that predicts branching architectures of polymers from radical polymerization with transfer to polymer and termination by disproportionation and recombination, in a continuously stirred tank reactor (CSTR). It is a so-called conditional Monte Carlo (MC) method generating

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

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.

Self-Assembled Colloidal Particle Clusters from In Situ Pickering-Like Emulsion Polymerization via Single Electron Transfer Mechanism.

Science.gov (United States)

Yuan, Jinfeng; Zhao, Weiting; Pan, Mingwang; Zhu, Lei

2016-08-01

A simple route is reported to synthesize colloidal particle clusters (CPCs) from self-assembly of in situ poly(vinylidene fluoride)/poly(styrene-co-tert-butyl acrylate) [PVDF/P(St-co-tBA)] Janus particles through one-pot seeded emulsion single electron transfer radical polymerization. In the in situ Pickering-like emulsion polymerization, the tBA/St/PVDF feed ratio and polymerization temperature are important for the formation of well-defined CPCs. When the tBA/St/PVDF feed ratio is 0.75 g/2.5 g/0.5 g and the reaction temperature is 35 °C, relatively uniform raspberry-like CPCs are obtained. The hydrophobicity of the P(St-co-tBA) domains and the affinity of PVDF to the aqueous environment are considered to be the driving force for the self-assembly of the in situ formed PVDF/P(St-co-tBA) Janus particles. The resultant raspberry-like CPCs with PVDF particles protruding outward may be promising for superhydrophobic smart coatings. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Antibacterial inorganic-organic hybrid coatings on stainless steel via consecutive surface-initiated atom transfer radical polymerization for biocorrosion prevention.

Science.gov (United States)

Yuan, S J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

2010-05-04

To enhance the corrosion resistance of stainless steel (SS) and to impart its surface with antibacterial functionality for inhibiting biofilm formation and biocorrosion, well-defined inorganic-organic hybrid coatings, consisting of a polysilsesquioxane inner layer and quaternized poly(2-(dimethyamino)ethyl methacrylate) (P(DMAEMA)) outer blocks, were prepared via successive surface-initiated atom transfer radical polymerization (ATRP) of 3-(trimethoxysilyl)propyl methacrylate (TMSPMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA). The cross-linked P(TMASPMA), or polysilsesquioxane, inner layer provided a durable and resistant coating to electrolytes. The pendant tertiary amino groups of the P(DMAEMA) outer block were quaternized with alkyl halide to produce a high concentration of quaternary ammonium groups with biocidal functionality. The so-synthesized inorganic-organic hybrid coatings on the SS substrates exhibited good anticorrosion and antibacterial effects and inhibited biocorrosion induced by sulfate-reducing bacteria (SRB) in seawater media, as revealed by antibacterial assay and electrochemical analyses, and they are potentially useful to steel-based equipment under harsh industrial and marine environments.

Vinylimidazole-Based Asymmetric Ion Pair Comonomers: Synthesis, Polymerization Studies and Formation of Ionically Crosslinked PMMA

NARCIS (Netherlands)

Jana, S.; Vasantha, V.A.; Stubbs, L.P.; Parthiban, A.; Vancso, Gyula J.

2013-01-01

Vinylimidazole-based asymmetric ion pair comonomers (IPCs) which are free from nonpolymerizable counter ions have been synthesized, characterized and polymerized by free radical polymerization (FRP), atom transfer radical polymerization (ATRP), and reversible addition-fragmentation chain transfer

Protein adsorption resistance of PVP-modified polyurethane film prepared by surface-initiated atom transfer radical polymerization

International Nuclear Information System (INIS)

Yuan, Huihui; Qian, Bin; Zhang, Wei; Lan, Minbo

2016-01-01

Highlights: • Antifouling PVP brushes were successfully grafted on PU films by SI-ATRP. • The effect of polymerization time on surface property and topography was studied. • Hydrophilicity and protein fouling resistance of PVP–PU films were greatly promoted. • Competitive adsorption of three proteins on PVP–PU films was evaluated. - Abstract: An anti-fouling surface of polyurethane (PU) film grafted with Poly(N-vinylpyrrolidone) (PVP) was prepared through surface-initiated atom transfer radical polymerization (SI-ATRP). And the polymerization time was investigated to obtain PU films with PVP brushes of different lengths. The surface properties and protein adsorption of modified PU films were evaluated. The results showed that the hydrophilicity of PU–PVP films were improved with the increase of polymerization time, which was not positive correlation with the surface roughness due to the brush structure. Additionally, the protein resistance performance was promoted when prolonging the polymerization time. The best antifouling PU–PVP (6.0 h) film reduced the adsoption level of bovine serum albumin (BSA), lysozyme (LYS), and brovin serum fibrinogen (BFG) by 93.4%, 68.3%, 85.6%, respectively, compared to the unmodified PU film. The competitive adsorption of three proteins indicated that LYS preferentially adsorbed on the modified PU film, while BFG had the lowest adsorption selectivity. And the amount of BFG on PU–PVP (6.0 h) film reduced greatly to 0.08 μg/cm"2, which was almost one-tenth of its adsorption from the single-protein system. Presented results suggested that both hydrophilicity and surface roughness might be the important factors in all cases of protein adsorption, and the competitive or selective adsorption might be related to the size of the proteins, especially on the non-charged films.

Protein adsorption resistance of PVP-modified polyurethane film prepared by surface-initiated atom transfer radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Yuan, Huihui; Qian, Bin; Zhang, Wei [Shanghai Key Laboratory of Functional Materials Chemistry and Research Center of Analysis and Test, East China University of Science and Technology, Shanghai 200237 (China); Lan, Minbo, E-mail: minbolan@ecust.edu.cn [Shanghai Key Laboratory of Functional Materials Chemistry and Research Center of Analysis and Test, East China University of Science and Technology, Shanghai 200237 (China); State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, Shanghai 200237 (China)

2016-02-15

Highlights: • Antifouling PVP brushes were successfully grafted on PU films by SI-ATRP. • The effect of polymerization time on surface property and topography was studied. • Hydrophilicity and protein fouling resistance of PVP–PU films were greatly promoted. • Competitive adsorption of three proteins on PVP–PU films was evaluated. - Abstract: An anti-fouling surface of polyurethane (PU) film grafted with Poly(N-vinylpyrrolidone) (PVP) was prepared through surface-initiated atom transfer radical polymerization (SI-ATRP). And the polymerization time was investigated to obtain PU films with PVP brushes of different lengths. The surface properties and protein adsorption of modified PU films were evaluated. The results showed that the hydrophilicity of PU–PVP films were improved with the increase of polymerization time, which was not positive correlation with the surface roughness due to the brush structure. Additionally, the protein resistance performance was promoted when prolonging the polymerization time. The best antifouling PU–PVP (6.0 h) film reduced the adsoption level of bovine serum albumin (BSA), lysozyme (LYS), and brovin serum fibrinogen (BFG) by 93.4%, 68.3%, 85.6%, respectively, compared to the unmodified PU film. The competitive adsorption of three proteins indicated that LYS preferentially adsorbed on the modified PU film, while BFG had the lowest adsorption selectivity. And the amount of BFG on PU–PVP (6.0 h) film reduced greatly to 0.08 μg/cm{sup 2}, which was almost one-tenth of its adsorption from the single-protein system. Presented results suggested that both hydrophilicity and surface roughness might be the important factors in all cases of protein adsorption, and the competitive or selective adsorption might be related to the size of the proteins, especially on the non-charged films.

In Situ Monitoring of RAFT Polymerization by Tetraphenylethylene-Containing Agents with Aggregation-Induced Emission Characteristics.

Science.gov (United States)

Liu, Shunjie; Cheng, Yanhua; Zhang, Haoke; Qiu, Zijie; Kwok, Ryan T K; Lam, Jacky W Y; Tang, Ben Zhong

2018-05-22

A facile and efficient approach is demonstrated to visualize the polymerization in situ. A group of tetraphenylethylene (TPE)-containing dithiocarbamates were synthesized and screened as agents for reversible addition fragmentation chain transfer (RAFT) polymerizations. The spatial-temporal control characteristics of photochemistry enabled the RAFT polymerizations to be ON and OFF on demand under alternating visible light irradiation. The emission of TPE is sensitive to the local viscosity change owing to its aggregation-induced emission characteristic. Quantitative information could be easily acquired by the naked eye without destroying the reaction system. Furthermore, the versatility of such a technique was well demonstrated by 12 different polymerization systems. The present approach thus demonstrated a powerful platform for understanding the controlled living radical polymerization process. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface-Initiated Atom Transfer Radical Polymerization and Electrografting Technique as a Means For Attaining Tailor-Made Polymer Coatings

DEFF Research Database (Denmark)

Chernyy, Sergey

2012-01-01

strategies for initiator grafting, physicochemical properties of polymer brushes and basic principles of quartz crystal microbalance technique (QCM) are discussed. In Chapter 2 various ATRP conditions are probed. The effects of solvent polarity, monomer concentration, initiator surface density, ligand nature......Atom transfer radical polymerization initiated from a surface of various substrates (SI-ATRP) has become a progressively popular technique for obtaining thin polymer films with predetermined properties. The present work addresses the main features of SI-ATRP with respect to the controllability...... and temperature on the kinetics of methyl methacrylate polymerization are elucidated. The strategy was based on the observation of dry polymer thickness versus time evolution by means of ellipsometry, profilometry and IR spectroscopy. An alternative approach, constituting Chapter 3, was based on optimization...

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

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.

Atom Transfer Radical Polymerization of Styrene in Presence of Mesoporous Silica Nanoparticles: Application of Reverse, Simultaneous Reverse and Normal Initiation Techniques

Directory of Open Access Journals (Sweden)

Khezrollah Khezri

2014-04-01

Full Text Available Atom transfer radical polymerization (ATRP of styrene in presence of mesoporous silica nanoparticles was carried out at 110 °C. Reverse atom transfer radical polymerization (RATRP and simultaneous reverse and normal initiation for atom transfer radical polymerization (SR&NI ATRP techniques were used as two appropriate introduced techniques for circumventing oxidation problems. Usage of metal catalyst in its higher oxidation state was the main feature of these initiation techniques in which deficiencies of normal ATRP were circumvented. Structure, surface area and pore diameter of synthesized mesoporous silica nanoparticles were evaluated using X–ray diffraction and nitrogen adsorption/desorption isotherm analysis. Average particle size was estimated around 600 nm by electron microscopy images. In addition, according to these images, nanoparticles revealed an appropriate size distribution. Particles size and their distribution were examined using scanning. Final monomer conversion was determined by using gas chromatography. The number and weight average molecular weights (Mn and Mw and polydispersity indexes (PDI were also evaluated by gel permeation chromatography. According to the results obtained, addition of mesoporous silica nanoparticles in both RATRP and SR&NI ATRP systems revealed similar effects: decrement of conversion and Mn and also increment of PDI values observed by increasing of mesoporous silica nanoparticles content. Improvement in thermal stability of the nanocomposites in comparison with neat polystyrene was demonstrated by thermogravimetric analysis (TGA. Moreover, in case of nanocomposites, thermal stability was obtained by higher loading of nanoparticles. A decrease in glass transition temperature by higher content of mesoporous silica nanoparticles has been demonstrated by differential scanning calorimetry analysis.

Mechanistic Studies of Hafnium-Pyridyl Amido-Catalyzed 1-Octene Polymerization and Chain Transfer Using Quench-Labeling Methods.

Science.gov (United States)

Cueny, Eric S; Johnson, Heather C; Anding, Bernie J; Landis, Clark R

2017-08-30

Chromophore quench-labeling applied to 1-octene polymerization as catalyzed by hafnium-pyridyl amido precursors enables quantification of the amount of active catalyst and observation of the molecular weight distribution (MWD) of Hf-bound polymers via UV-GPC analysis. Comparison of the UV-detected MWD with the MWD of the "bulk" (all polymers, from RI-GPC analysis) provides important mechanistic information. The time evolution of the dual-detection GPC data, concentration of active catalyst, and monomer consumption suggests optimal activation conditions for the Hf pre-catalyst in the presence of the activator [Ph 3 C][B(C 6 F 5 ) 4 ]. The chromophore quench-labeling agents do not react with the chain-transfer agent ZnEt 2 under the reaction conditions. Thus, Hf-bound polymeryls are selectively labeled in the presence of zinc-polymeryls. Quench-labeling studies in the presence of ZnEt 2 reveal that ZnEt 2 does not influence the rate of propagation at the Hf center, and chain transfer of Hf-bound polymers to ZnEt 2 is fast and quasi-irreversible. The quench-label techniques represent a means to study commercial polymerization catalysts that operate with high efficiency at low catalyst concentrations without the need for specialized equipment.

Buried Volume Analysis for Propene Polymerization Catalysis Promoted by Group 4 Metals: a Tool for Molecular Mass Prediction

KAUST Repository

Falivene, Laura; Cavallo, Luigi; Talarico, Giovanni

2015-01-01

A comparison of the steric properties of homogeneous single site catalysts for propene polymerization using the percentage of buried volume (%VBur) as molecular descriptor is reported. The %VBur calculated on the neutral precursors of the active species seems to be a reliable tool to explain several experimental data related to the propene insertion and to the monomer chain transfer. Interestingly, a linear correlation between the buried volume calculated for a large set of neutral precursors and the energetic difference between propagation and termination steps calculated by DFT methods is found for Group 4 metal catalysts. The “master curves” derived for Ti, Zr and Hf confirm not only that the %VBur is an appropriate molecular descriptor for the systems considered but also that it could be used as tool for a large computational screening of new ligands.

Buried Volume Analysis for Propene Polymerization Catalysis Promoted by Group 4 Metals: a Tool for Molecular Mass Prediction

KAUST Repository

Falivene, Laura

2015-10-02

A comparison of the steric properties of homogeneous single site catalysts for propene polymerization using the percentage of buried volume (%VBur) as molecular descriptor is reported. The %VBur calculated on the neutral precursors of the active species seems to be a reliable tool to explain several experimental data related to the propene insertion and to the monomer chain transfer. Interestingly, a linear correlation between the buried volume calculated for a large set of neutral precursors and the energetic difference between propagation and termination steps calculated by DFT methods is found for Group 4 metal catalysts. The “master curves” derived for Ti, Zr and Hf confirm not only that the %VBur is an appropriate molecular descriptor for the systems considered but also that it could be used as tool for a large computational screening of new ligands.

Construction of Hierarchical Polymer Brushes on Upconversion Nanoparticles via NIR-Light-Initiated RAFT Polymerization.

Science.gov (United States)

Xie, Zhongxi; Deng, Xiaoran; Liu, Bei; Huang, Shanshan; Ma, Pingan; Hou, Zhiyao; Cheng, Ziyong; Lin, Jun; Luan, Shifang

2017-09-13

Photoinduced reversible addition-fragmentation chain transfer (RAFT) polymerization generally adopts high-energy ultraviolet (UV) or blue light. In combination with photoredox catalyst, the excitation light wavelength was extended to the visible and even near-infrared (NIR) region for photoinduced electron transfer RAFT polymerization. In this report, we introduce for the first time a surface NIR-light-initiated RAFT polymerization on upconversion nanoparticles (UCNPs) without adding any photocatalyst and construct a functional inorganic core/polymer shell nanohybrid for application in cancer theranostics. The multilayer core-shell UCNPs (NaYF 4 :Yb/Tm@NaYbF 4 :Gd@NaNdF 4 :Yb@NaYF 4 ), with surface anchorings of chain transfer agents, can serve as efficient NIR-to-UV light transducers for initiating the RAFT polymerization. A hierarchical double block copolymer brush, consisting of poly(acrylic acid) (PAA) and poly(oligo(ethylene oxide)methacrylate-co-2-(2-methoxy-ethoxy)ethyl methacrylate) (PEG for short), was grafted from the surface in sequence. The targeting arginine-glycine-aspartic (RGD) peptide was modified at the end of the copolymer through the trithiolcarbonate end group. After loading of doxorubicin, the UCNPs@PAA-b-PEG-RGD exhibited an enhanced U87MG cancer cell uptake efficiency and cytotoxicity. Besides, the unique upconversion luminescence of the nanohybrids was used for the autofluoresence-free cell imaging and labeling. Therefore, our strategy verified that UCNPs could efficiently activate RAFT polymerization by NIR photoirradiation and construct the complex nanohybrids, exhibiting prospective biomedical applications due to the low phototoxicity and deep penetration of NIR light.

Efficient Functionalization of Polyethylene Fibers for the Uranium Extraction from Seawater through Atom Transfer Radical Polymerization

Energy Technology Data Exchange (ETDEWEB)

Neti, Venkata S. [Chemical; Das, Sadananda [Chemical; Brown, Suree [Department; Janke, Christopher J. [Materials; Kuo, Li-Jung [Marine; Gill, Gary A. [Marine; Dai, Sheng [Chemical; Department; Mayes, Richard T. [Chemical

2017-09-14

Brush-on-brush structures are proposed as one method to overcome support effects in grafted polymers. Utilizing glycidyl methacrylate (GMA) grafted on polyethylene (PE) fibers using radiation-induced graft polymerization (RIGP) provides a hydrophilic surface on the hydrophobic PE. When integrated with atom transfer radical polymerization (ATRP), the grafting of acrylonitrile (AN) and hydroxyethyl acrylate (HEA) can be controlled and manipulated more easily than with RIGP. Poly(acrylonitrile)-co-poly(hydroxyethyl acrylate) chains were grown via ATRP on PE-GMA fibers to generate an adsorbent for the extraction of uranium from seawater. The prepared adsorbents in this study demonstrated promise (159.9 g- U/kg of adsorbent) in laboratory screening tests using a high uranium concentration brine and 1.24 g-U/Kg of adsorbent in the filtered natural seawater in 21-days. The modest capacity in 21- days exceeds previous efforts to generate brush-on-brush adsorbents by ATRP while manipulating the apparent surface hydrophilicity of the trunk material (PE).

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.

Multiblock Copolymers of Styrene and Butyl Acrylate via Polytrithiocarbonate-Mediated RAFT Polymerization

Directory of Open Access Journals (Sweden)

Bastian Ebeling

2011-03-01

Full Text Available When linear polytrithiocarbonates as Reversible Addition-Fragmentation chain Transfer (RAFT agents are employed in a radical polymerization, the resulting macromolecules consist of several homogeneous polymer blocks, interconnected by the functional groups of the respective RAFT agent. Via a second polymerization with another monomer, multiblock copolymers—polymers with alternating segments of both monomers—can be prepared. This strategy was examined mechanistically in detail based on subsequent RAFT polymerizations of styrene and butyl acrylate. Size-exclusion chromatography (SEC of these polymers showed that the examined method yields low-disperse products. In some cases, resolved peaks for molecules with different numbers of blocks (polymer chains separated by the trithiocarbonate groups could be observed. Cleavage of the polymers at the trithiocarbonate groups and SEC analysis of the products showed that the blocks in the middle of the polymers are longer than those at the ends and that the number of blocks corresponds to the number of functional groups in the initial RAFT agent. Furthermore, the produced multiblock copolymers were analyzed via differential scanning calorimetry (DSC. This work underlines that the examined methodology is very well suited for the synthesis of well-defined multiblock copolymers.

Effect of homopolymer in polymerization-induced microphase separation process

Energy Technology Data Exchange (ETDEWEB)

Park, Jongmin; Saba, Stacey A.; Hillmyer, Marc A.; Kang, Dong-Chang; Seo, Myungeun (IBS-Korea); (KAIST); (UMMN)

2017-09-01

We report on the phase separation behaviors of polymerization mixtures containing a polylactide macro-chain transfer agent (PLA-CTA), styrene, divinylbenzene, hydroxyl-terminated PLA (PLA-OH), and a molecular chain transfer agent which enable the ability to tune the pore size of a cross-linked polymer monolith in a facile manner. Cross-linked monoliths were produced from the mixtures via reversible addition-fragmentation chain transfer (RAFT) polymerization and converted into cross-linked porous polymers by selective removal of PLA while retaining the parent morphology. We demonstrate that pore sizes are tunable over a wide range of length scales from the meso- to macroporous regimes by adjusting the ratio of PLA-CTA to PLA-OH in the reaction mixture which causes the phase separation mechanism to change from polymerization-induced microphase separation to polymerization-induced phase separation. The possibility of increasing porosity and inducing simultaneous micro- and macrophase separation was also realized by adjustments in the molar mass of PLA which enabled the synthesis of hierarchically meso- and macroporous polymers.

PREPARATION AND PROPERTIES OF MMA/1-PROPYLMETHACRYLATE-POSS COPOLYMER WITH ATOM TRANSFER RADICAL POLYMERIZATION

Institute of Scientific and Technical Information of China (English)

He-xin Zhang; Ho-young Lee; Young-jun Shin; Dong-ho Lee; Seok Kyun Noh

2008-01-01

The methyl methacrylate(MMA)/1-propylmethacrylate-polyhedral oligomeric silsesquioxane(PM-POSS) copolymers were synthesized via atom transfer radical polymerization with CuBr as catalyst.The unreacted PM-POSS monomer could be removed completely by washing the copolymerization product with n-hexane.The copolymers were characterized with 1H-NMR,X-ray diffraction,difierential scanning calorimetry,thermogravimetric analysis and gel permeatlon chromatography.With increasing PM-POSS feed ratio.the total conversion increased while the glass transition temperatures of copolymer decreased.The thermogravimetric analysis demonstrated that the thermal stability of copolymer improved slightly with PM-POSS addition.The molecular weight of copolymers increased with incorporation of PM-POSS.

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.

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

In Situ Investigation of Electrochemically Mediated Surface-Initiated Atom Transfer Radical Polymerization by Electrochemical Surface Plasmon Resonance.

Science.gov (United States)

Chen, Daqun; Hu, Weihua

2017-04-18

Electrochemically mediated atom transfer radical polymerization (eATRP) initiates/controls the controlled/living ATRP chain propagation process by electrochemically generating (regenerating) the activator (lower-oxidation-state metal complex) from deactivator (higher-oxidation-state metal complex). Despite successful demonstrations in both of the homogeneous polymerization and heterogeneous systems (namely, surface-initiated ATRP, SI-ATRP), the eATRP process itself has never been in situ investigated, and important information regarding this process remains unrevealed. In this work, we report the first investigation of the electrochemically mediated SI-ATRP (eSI-ATRP) by rationally combining the electrochemical technique with real-time surface plasmon resonance (SPR). In the experiment, the potential of a SPR gold chip modified by the self-assembled monolayer of the ATRP initiator was controlled to electrochemically reduce the deactivator to activator to initiate the SI-ATRP, and the whole process was simultaneously monitored by SPR with a high time resolution of 0.1 s. It is found that it is feasible to electrochemically trigger/control the SI-ATRP and the polymerization rate is correlated to the potential applied to the gold chip. This work reveals important kinetic information for eSI-ATRP and offers a powerful platform for in situ investigation of such complicated processes.

Characterization of inclusion complexes of organic ions with hydrophilic hosts by ion transfer voltammetry with solvent polymeric membranes.

Science.gov (United States)

Olmos, José Manuel; Laborda, Eduardo; Ortuño, Joaquín Ángel; Molina, Ángela

2017-03-01

The quantitative characterization of inclusion complexes formed in aqueous phase between organic ions and hydrophilic hosts by ion-transfer voltammetry with solvent polymeric membrane ion sensors is studied, both in a theoretical and experimental way. Simple analytical solutions are presented for the determination of the binding constant of the complex from the variation with the host concentration of the electrochemical signal. These solutions are valid for any voltammetric technique and for solvent polymeric membrane ion sensors comprising one polarisable interface (1PI) and also, for the first time, two polarisable interfaces (2PIs). Suitable experimental conditions and data analysis procedures are discussed and applied to the study of the interactions of a common ionic liquid cation (1-octyl-3-metyl-imidazolium) and an ionisable drug (clomipramine) with two hydrophilic cyclodextrins: α-cyclodextrin and 2-hydroxypropyl-β-cyclodextrin. The experimental study is performed via square wave voltammetry with 2PIs and 1PI solvent polymeric membranes and in both cases the electrochemical experiments enable the detection of inclusion complexes and the determination of the corresponding binding constant. Copyright © 2016 Elsevier B.V. All rights reserved.

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

The potential of Cu(I)Cl/2,2'-bipyridine catalysis in a triblock copolymer preparation by atom transfer radical polymerization

Czech Academy of Sciences Publication Activity Database

Masař, Bohumil; Vlček, Petr; Kříž, Jaroslav

2001-01-01

Roč. 81, č. 14 (2001), s. 3514-3522 ISSN 0021-8995 R&D Projects: GA MŠk OC P1.10; GA AV ČR KSK2050602 Institutional research plan: CEZ:AV0Z4050913 Keywords : atom transfer radical polymerization * triblock copolymers * sequential synthesis Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.992, year: 2001

Functionalization of vertically aligned carbon nanotubes with polystyrene via surface initiated reversible addition fragmentation chain transfer polymerization

Energy Technology Data Exchange (ETDEWEB)

Macdonald, Thomas; Gibson, Christopher T.; Constantopoulos, Kristina; Shapter, Joseph G. [Flinders Centre for Nanoscale Science and Technology, School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, SA, 5001 (Australia); Ellis, Amanda V., E-mail: amanda.ellis@flinders.edu.au [Flinders Centre for Nanoscale Science and Technology, School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, SA, 5001 (Australia)

2012-01-15

Here we demonstrate the covalent attachment of vertically aligned (VA) acid treated single-walled carbon nanotubes (SWCNTs) onto a silicon substrate via dicyclohexylcarbodiimide (DCC) coupling chemistry. Subsequently, the pendant carboxyl moieties on the sidewalls of the VA-SWCNTs were derivatized to acyl chlorides, and then finally to bis(dithioester) moieties using a magnesium chloride dithiobenzoate salt. The bis(dithioester) moieties were then successfully shown to act as a chain transfer agent (CTA) in the reversible addition fragmentation chain transfer (RAFT) polymerization of styrene in a surface initiated 'grafting-from' process from the VA-SWCNT surface. Atomic force microscopy (AFM) verified vertical alignment of the SWCNTs and the maintenance thereof throughout the synthesis process. Finally, Raman scattering spectroscopy and AFM confirmed polystyrene functionalization.

Functionalization of vertically aligned carbon nanotubes with polystyrene via surface initiated reversible addition fragmentation chain transfer polymerization

International Nuclear Information System (INIS)

Macdonald, Thomas; Gibson, Christopher T.; Constantopoulos, Kristina; Shapter, Joseph G.; Ellis, Amanda V.

2012-01-01

Here we demonstrate the covalent attachment of vertically aligned (VA) acid treated single-walled carbon nanotubes (SWCNTs) onto a silicon substrate via dicyclohexylcarbodiimide (DCC) coupling chemistry. Subsequently, the pendant carboxyl moieties on the sidewalls of the VA-SWCNTs were derivatized to acyl chlorides, and then finally to bis(dithioester) moieties using a magnesium chloride dithiobenzoate salt. The bis(dithioester) moieties were then successfully shown to act as a chain transfer agent (CTA) in the reversible addition fragmentation chain transfer (RAFT) polymerization of styrene in a surface initiated “grafting-from” process from the VA-SWCNT surface. Atomic force microscopy (AFM) verified vertical alignment of the SWCNTs and the maintenance thereof throughout the synthesis process. Finally, Raman scattering spectroscopy and AFM confirmed polystyrene functionalization.

PREPARATION OF BLOCK COPOLYMERS OF POLY(STYRENE) AND POLY(T-BUTYL ACRYLATE) OF VARIOUS MOLECULAR WEIGHTS AND ARCHITECTURES BY ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

Science.gov (United States)

Block copolymers of polystyrene and poly(t-butyl acrylate) were prepared using atom transfer radical polymerization techniques. These polymers were synthesized with a CuBr/N,N,N,NA DFT Study of R-X Bond Dissociation Enthalpies of Relevance to the Initiation Process of Atom Transfer Radical Polymerization

DEFF Research Database (Denmark)

Gillies, Malcolm Bjørn; Matyjaszewski, Krzysztof; Norrby, Per-Ola

2003-01-01

DFT calculations at the B3P86/6-31G** level have been carried out to derive the bond dissociation energies (BDE) and free energies for a number of R-X systems (X ) Cl, Br, I, N3, and S2-CNMe2) that have been or can potentially be used as initiators for atom transfer radical polymerization (ATRP...

Grafting of antibacterial polymers on stainless steel via surface-initiated atom transfer radical polymerization for inhibiting biocorrosion by Desulfovibrio desulfuricans.

Science.gov (United States)

Yuan, S J; Xu, F J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

2009-06-01

To enhance the biocorrosion resistance of stainless steel (SS) and to impart its surface with bactericidal function for inhibiting bacterial adhesion and biofilm formation, well-defined functional polymer brushes were grafted via surface-initiated atom transfer radical polymerization (ATRP) from SS substrates. The trichlorosilane coupling agent, containing the alkyl halide ATRP initiator, was first immobilized on the hydroxylated SS (SS-OH) substrates for surface-initiated ATRP of (2-dimethylamino)ethyl methacrylate (DMAEMA). The tertiary amino groups of covalently immobilized DMAEMA polymer or P(DMAEMA), brushes on the SS substrates were quaternized with benzyl halide to produce the biocidal functionality. Alternatively, covalent coupling of viologen moieties to the tertiary amino groups of P(DMAEMA) brushes on the SS surface resulted in an increase in surface concentration of quaternary ammonium groups, accompanied by substantially enhanced antibacterial and anticorrosion capabilities against Desulfovibrio desulfuricans in anaerobic seawater, as revealed by antibacterial assay and electrochemical studies. With the inherent advantages of high corrosion resistance of SS, and the good antibacterial and anticorrosion capabilities of the viologen-quaternized P(DMAEMA) brushes, the functionalized SS is potentially useful in harsh seawater environments and for desalination plants. Copyright 2009 Wiley Periodicals, Inc.

Polymer@gold Nanoparticles Prepared via RAFT Polymerization for Opto-Biodetection

Directory of Open Access Journals (Sweden)

Sónia O. Pereira

2018-02-01

Full Text Available Colloidal gold nanoparticles (Au NPs have been used in several biological applications, which include the exploitation of size- and shape-dependent Localized Surface Plasmon Resonance (LSPR in biosensing devices. In order to obtain functional and stable Au NPs in a physiological medium, surface modification and functionalization are crucial steps in these endeavors. Reversible addition-fragmentation chain transfer (RAFT polymerization meets this need offering the possibility of control over the composition and architecture of polymeric shells coating Au NPs. Furthermore, playing with a careful choice of monomers, RAFT polymerization allows the possibility to design a polymer shell with the desired functional groups aiming at Au based nanocomposites suitable for biorecognition and biotargeting. This review provides important aspects concerning the synthesis and optical properties of Au NPs as well as concepts of RAFT polymerization. Understanding these concepts is crucial to appreciate the chemical strategies available towards RAFT-polymer coated Au core-shell nanostructures, which are here reviewed. Finally, examples of applications in opto-biodetection devices are provided and the potential of responsive “smart” nanomaterials based on such structures can be applied to other biological applications.

Polymerization-Driven Immobilization of dc-APGD Synthesized Gold Nanoparticles into a Quaternary Ammonium-Based Hydrogel Resulting in a Polymeric Nanocomposite with Heat-Transfer Applications

Directory of Open Access Journals (Sweden)

Piotr Cyganowski

2018-03-01

Full Text Available A new method for the production of nanocomposites, composed of gold nanoparticles (AuNPs and (vinylbenzyltrimethylammonium chloride-co-N,N-methylene bisacrylamide (VBTAC-co-MBA hydrogel, is described. Raw-AuNPs of defined optical and granulometric properties were synthesized using direct current atmospheric pressure glow discharge (dc-APGD generated in contact with a solution of HAuCl4. Different approaches to the polymerization-driven synthesis of Au/VBTAC-co-MBA nanocomposites were tested. It was established that homogenous dispersion of AuNPs in this new nanomaterial with was achieved in the presence of NaOH in the reaction mixture. The new nanocomposite was found to have excellent heat-transfer properties.

Proton-Transfer Polymerization by N-Heterocyclic Carbenes: Monomer and Catalyst Scopes and Mechanism for Converting Dimethacrylates into Unsaturated Polyesters

KAUST Repository

Hong, Miao

2016-01-18

This contribution presents a full account of experimental and theoretical/computational investigations into the N-heterocyclic carbene (NHC)-catalyzed proton-transfer polymerization (HTP) that converts common dimethacrylates (DMAs) containing no protic groups into unsaturated polyesters. This new HTP proceeds through the step-growth propagation cycles via enamine intermediates, consisting of the proposed conjugate addition–proton transfer–NHC release fundamental steps. This study examines the monomer and catalyst scopes as well as the fundamental steps involved in the overall HTP mechanism. DMAs having six different types of linkages connecting the two methacrylates have been polymerized into the corresponding unsaturated polyesters. The most intriguing unsaturated polyester of the series is that based on the biomass-derived furfuryl dimethacrylate, which showed a unique self-curing ability Four MeO– and Cl–substituted TPT (1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene) derivatives as methanol insertion products, RxTPT(MeO/H) (R = MeO, Cl; x = 2, 3), and two free carbenes (catalysts), OMe2TPT and OMe3TPT, have been synthesized, while OMe2TPT(MeO/H) and OMe2TPT have also been structurally characterized. The structure/reactivity relationship study revealed that OMe2TPT, being both a strong nucleophile and a good leaving group, exhibits the highest HTP activity and also produced the polyester with the highest Mn, while the Cl–substituted TPT derivatives are least active and efficient. Computational studies have provided mechanistic insights into the tail-to-tail dimerization coupling step as a suitable model for the propagation cycle of the HTP. The extensive energy profile was mapped out and the experimentally observed unicity of the TPT-based catalysts was satisfactorily explained with the thermodynamic formation of key spirocyclic species.

On the mechanism of activation of copper-catalyzed atom transfer radical polymerization

International Nuclear Information System (INIS)

Isse, Abdirisak Ahmed; Bortolamei, Nicola; De Paoli, Patrizia; Gennaro, Armando

2013-01-01

The mechanism of activation of atom transfer radical polymerization (ATRP) has been analyzed by investigating the kinetics of dissociative electron transfer (ET) to alkyl halides (RX) in acetonitrile. Using a series of alkyl halides, including both bromides and chlorides, the rate constants of ET (k ET ) to RX by electrogenerated aromatic radical anions (A· − ) acting as outer-sphere donors have been measured and analyzed according to the current theories of dissociative ET. This has shown that the kinetic data fit very well the “sticky” dissociative ET model with the formation of a weak adduct held together by electrostatic interactions. The rate constants of activation, k act , of some alkyl halides, namely chloroacetonitrile, methyl 2-bromopropionate and ethyl chloroacetate, by [Cu I L] + (L = tris(2-dimethylaminoethyl)amine, tris(2-pyridylmethyl)amine, 1,1,4,7,7-pentamethyldiethylenetriamine) have also been measured in the same experimental conditions. Comparisons of the measured k act values with those predicted assuming an outer-sphere ET for the complexes have shown that activation by Cu(I) is 7–10 orders of magnitude faster than required by outer-sphere ET. Therefore, the mechanism of RX activation by Cu(I) complexes used as catalysts in ATRP occurs by an inner-sphere ET or more appropriately by a halogen atom abstraction

Three Arm Star Homo- And Co-Polymers Via Atom Transfer Radical Polymerization

International Nuclear Information System (INIS)

Amin, A.; Sobh, R.A.; Ayoub, M.M.H.

2005-01-01

Star homo and co-polymers of some vinyl monomers such as methylmethacrylate, butylmethacrylate and styrene (MMA, BMA, St.) were prepared using N, N, N', N' tetramethylethylenediamine ligand/ CuBr catalytic system via atom transfer radical polymerization (ATRP). Three armed benzene based core was successfully used as initiator. Low polydispersities and regular molecular weight values were obtained in most cases especially at low conversions. MMA and BuMA showed comparable behavior where controlled and true ATRP was observed even at the high conversions. However, styrene monomer recorded irregular high polydispersities at high conversions in spite of the relatively low molecular weight values. 1HNMR confirmed the structures of the resulting polymers. Transmission Electron microscope (TEM) proved the nano-structure of the star polymers. The thermal behavior of the MMA star homo and copolymers was studied. The effect of the star shape on the thermal behavior was very clear with respect to the linear ones

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�

Fabrication of ultrahydrophobic poly(lauryl acrylate) brushes on silicon wafer via surface-initiated atom transfer radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Oztuerk, Esra; Turan, Eylem [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey); Caykara, Tuncer, E-mail: caykara@gazi.edu.tr [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey)

2010-11-15

In this report, ultrahydrophobic poly(lauryl acrylate) [poly(LA)] brushes were synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP) of lauryl acrylate (LA) in N,N-dimethylformamide (DMF) at 90 deg. C. The formation of ultrahydrophobic poly(LA) films, whose thickness can be turned by changing polymerization time, is evidenced by using the combination of ellipsometry, X-ray photoelectron spectroscopy (XPS), grazing angle attenuated total reflectance-Fourier transform infrared spectroscopy (GATR-FTIR), atomic force microscopy (AFM), gel permeation chromatography (GPC), and water contact angle measurements. The SI-ATRP can be conducted in a well-controlled manner, as revealed by the linear kinetic plot, linear evolution of number-average molecular weights (M-bar{sub n}) versus monomer conversions, and the relatively narrow PDI (<1.28) of the grafted poly(LA) chains. The calculation of grafting parameters from experimental measurements indicated the synthesis of densely grafted poly(LA) films and allowed us to predict a 'brushlike' conformation for the chains in good solvent. The poly(LA) brushes exhibited high water contact angle of 163.3 {+-} 2.8{sup o}.

Analysis of transference in Gestalt group psychotherapy.

Science.gov (United States)

Frew, J E

1990-04-01

In Gestalt therapy, transference is viewed as a contact boundary disturbance which impairs the patient's ability to accurately perceive the present therapy situation. The boundary disturbances in Gestalt therapy most closely related to the analytic notion of transference are projection, introjection, and confluence. In Gestalt group psychotherapy, group members interfere with the process of need identification and satisfaction by distorting their contact with each other through projecting, introjecting, and being confluent. The Gestalt group therapist uses interventions directed to individuals and to the group to increase participants' awareness of these boundary disturbances and of the present contact opportunities available to them when these disturbances are resolved. In formulating interventions, the leader is mindful of the function of boundary disturbances to the group-as-a-whole as well as to individuals.

Polymethylene-based copolymers by polyhomologation or by its combination with controlled/living and living polymerizations

KAUST Repository

Zhang, Hefeng

2014-01-20

Polyhomologation, recently developed by Shea, is a borane-initiated living polymerization of ylides leading to linear polymethylenes (C1 polymerization) with controlled molecular weight, low polydispersity, and well-defined structures. In this Review, the copolyhomologation of different ylides as well as the combination of polyhomologation with controlled/living (nitroxide-mediated, atom transfer radical, reversible addition-fragmentation chain-transfer) and living (ring opening, anionic) polymerizations is discussed. Polyhomologation of ylides, in combination with living and controlled/living polymerizations, leads to a plethora novel well-defined polymethylene (polyethylene)-based polymeric materials, which are very important for understanding/improving the behavior of industrial polyethylenes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface modification of thermoplastic poly(vinyl alcohol)/saponite nanocomposites via surface-initiated atom transfer radical polymerization enhanced by air dielectric discharges barrier plasma treatment

International Nuclear Information System (INIS)

Zhen Weijun; Lu Canhui

2012-01-01

To improve the water resistance of thermoplastic poly(vinyl alcohol)/saponite nanocomposites (TPVA), a simple two-step method was developed for the covalent immobilization of atom transfer radical polymerization (ATRP) initiators on the TPVA surfaces enhanced by air dielectric barrier discharges (DBD) plasma treatment, and hydrophobic poly(methyl methacrylate) (PMMA) brushes were then grafted onto the surface of TPVA via surface-initiated atom transfer radical polymerization (SI-ATRP). The chemical composition, morphology and hydrophobicity of the modified TPVA surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), respectively. The water resistance of the surface-functionalized PMMA was evaluated by the contact angle and water adsorption method. It was shown that air DBD plasma treatment activated the TPVA surface and accelerated the immobilization of ATRP initiator on the TPVA surface. Compared with TPVA control, TPVA modified by SI-ATRP can be grafted well-defined and covalently tethered network PMMA brushes onto the surface and the hydrophobicity of TPVA were significantly enhanced.

Surface modification of silk fibroin fibers with poly(methyl methacrylate) and poly(tributylsilyl methacrylate) via RAFT polymerization for marine antifouling applications

Energy Technology Data Exchange (ETDEWEB)

Buga, Mihaela-Ramona [National Research and Development Institute for Cryogenics and Isotopic Technologies, ICIT Rm. Valcea, 240050 Rm. Valcea, Uzinei 4, CP7, Raureni, Valcea (Romania); Zaharia, Cătălin, E-mail: zaharia.catalin@gmail.com [Advanced Polymer Materials Group, University Politehnica of Bucharest, 1-7, Gh. Polizu Street, Sector 1, 011061 Bucharest (Romania); Bălan, Mihai [National Research and Development Institute for Cryogenics and Isotopic Technologies, ICIT Rm. Valcea, 240050 Rm. Valcea, Uzinei 4, CP7, Raureni, Valcea (Romania); Bressy, Christine [Université de Toulon, MAPIEM, EA 4323, 83957 La Garde (France); Ziarelli, Fabio [Fédération des Sciences Chimiques de Marseille, CNRS-FR1739, Spectropole, 13397 Marseille (France); Margaillan, André [Université de Toulon, MAPIEM, EA 4323, 83957 La Garde (France)

2015-06-01

In this study, silk fibroin surface containing hydroxyl and aminogroups was firstly modified using a polymerizable coupling agent 3-(trimethoxysilyl) propyl methacrylate (MPS), in order to induce vinyl groups onto the fiber surface. The reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization of methyl methacrylate (MMA) and tributylsilyl methacrylate (TBSiMA) through the immobilized vinyl bond on the silk fibroin surface in the presence of 2-cyanoprop-2-yl dithiobenzoate (CPDB) as chain-transfer agent and 2,2′-azobis(isobutyronitrile) (AIBN) as initiator was conducted in toluene solution at 70 °C for 24 h. The structure and properties of the modified fiber were characterized by Fourier Transform Infrared Spectroscopy, {sup 13}C, {sup 29}Si Nuclear Magnetic Resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), confirming the presence of the coupling molecule and the methacrylate groups onto the silk fibroin fiber surface. Molecular weight distributions were assessed by triple detection size exclusion chromatography (TD-SEC) in order to verify the livingness of the polymerization. - Highlights: • SF surface containing hydroxyl and amino groups was firstly modified with MPS. • RAFT polymerizations of MMA and TBSiMA were studied. • TD-SEC was used to verify the livingness of the RAFT polymerization. • The grafted polymer chains enhance the thermal stability of the SF fibers. • The grafted fibers could be potentially promising candidates as antifouling agents.

Surface modification of silk fibroin fibers with poly(methyl methacrylate) and poly(tributylsilyl methacrylate) via RAFT polymerization for marine antifouling applications

International Nuclear Information System (INIS)

Buga, Mihaela-Ramona; Zaharia, Cătălin; Bălan, Mihai; Bressy, Christine; Ziarelli, Fabio; Margaillan, André

2015-01-01

In this study, silk fibroin surface containing hydroxyl and aminogroups was firstly modified using a polymerizable coupling agent 3-(trimethoxysilyl) propyl methacrylate (MPS), in order to induce vinyl groups onto the fiber surface. The reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization of methyl methacrylate (MMA) and tributylsilyl methacrylate (TBSiMA) through the immobilized vinyl bond on the silk fibroin surface in the presence of 2-cyanoprop-2-yl dithiobenzoate (CPDB) as chain-transfer agent and 2,2′-azobis(isobutyronitrile) (AIBN) as initiator was conducted in toluene solution at 70 °C for 24 h. The structure and properties of the modified fiber were characterized by Fourier Transform Infrared Spectroscopy, 13 C, 29 Si Nuclear Magnetic Resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), confirming the presence of the coupling molecule and the methacrylate groups onto the silk fibroin fiber surface. Molecular weight distributions were assessed by triple detection size exclusion chromatography (TD-SEC) in order to verify the livingness of the polymerization. - Highlights: • SF surface containing hydroxyl and amino groups was firstly modified with MPS. • RAFT polymerizations of MMA and TBSiMA were studied. • TD-SEC was used to verify the livingness of the RAFT polymerization. • The grafted polymer chains enhance the thermal stability of the SF fibers. • The grafted fibers could be potentially promising candidates as antifouling agents

Investigations in the field of solid-state polymerization Pt. 37

International Nuclear Information System (INIS)

Mahr, L.; Cser, F.; Kovacs, G.; Hardy, Gy.

1978-01-01

Chloranil (CA) and bromanil (BA) which have otherwise similar radiation-chemical properties affect the solid state polymerization of acenaphthylene (ACN) in different manner. CA decreases the rate of polymerization proportionally to its concentration and besides, it also decreases the conversion limit and the molecular weight of the product. BA does not influence the reaction up to a conversion of 20%, but soon afterwards the conversion limit of the polymerization is reached. This limit, above 8M% BA content, is independent of the BA concentration. The reason for the different behaviour is that while BA forms an ideal eutectics with ACN, CA forms a solid solution of limited miscibility at the temperature of the experiments. Both pairs of compounds give charge transfer complex in solid state. The charge transfer complex of BA exists merely at the boundary layer of the crystals, but that of CA is within the crystal lattice of ACN as in a solid solvent. In none of the studied cases could be detected the charge transfer complex with its own specific crystal structure. The effect of CA on the solid state polymerization of ACN is discussed on the basis of the results obtained by PPP and CNDO/2 calculations on ACN and CA. (author)

Acrylamide-b-N-isopropylacrylamide block copolymers : Synthesis by atomic transfer radical polymerization in water and the effect of the hydrophilic-hydrophobic ratio on the solution properties

NARCIS (Netherlands)

Wever, Diego Armando Z.; Ramalho, Graham; Picchioni, Francesco; Broekhuis, Antonius Augustinus

2014-01-01

A series of block copolymers of acrylamide and N-isopropylacrylamide (NIPAM) characterized by different ratios between the length of the two blocks have been prepared through atomic transfer radical polymerization in water at room temperature. The solution properties of the block copolymers were

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 �

Preparation of Transparent Bulk TiO2/PMMA Hybrids with Improved Refractive Indices via an in Situ Polymerization Process Using TiO2 Nanoparticles Bearing PMMA Chains Grown by Surface-Initiated Atom Transfer Radical Polymerization.

Science.gov (United States)

Maeda, Satoshi; Fujita, Masato; Idota, Naokazu; Matsukawa, Kimihiro; Sugahara, Yoshiyuki

2016-12-21

Transparent TiO 2 /PMMA hybrids with a thickness of 5 mm and improved refractive indices were prepared by in situ polymerization of methyl methacrylate (MMA) in the presence of TiO 2 nanoparticles bearing poly(methyl methacrylate) (PMMA) chains grown using surface-initiated atom transfer radical polymerization (SI-ATRP), and the effect of the chain length of modified PMMA on the dispersibility of modified TiO 2 nanoparticles in the bulk hybrids was investigated. The surfaces of TiO 2 nanoparticles were modified with both m-(chloromethyl)phenylmethanoyloxymethylphosphonic acid bearing a terminal ATRP initiator and isodecyl phosphate with a high affinity for common organic solvents, leading to sufficient dispersibility of the surface-modified particles in toluene. Subsequently, SI-ATRP of MMA was achieved from the modified surfaces of the TiO 2 nanoparticles without aggregation of the nanoparticles in toluene. The molecular weights of the PMMA chains cleaved from the modified TiO 2 nanoparticles increased with increases in the prolonging of the polymerization period, and these exhibited a narrow distribution, indicating chain growth controlled by SI-ATRP. The nanoparticles bearing PMMA chains were well-dispersed in MMA regardless of the polymerization period. Bulk PMMA hybrids containing modified TiO 2 nanoparticles with a thickness of 5 mm were prepared by in situ polymerization of the MMA dispersion. The transparency of the hybrids depended significantly on the chain length of the modified PMMA on the nanoparticles, because the modified PMMA of low molecular weight induced aggregation of the TiO 2 nanoparticles during the in situ polymerization process. The refractive indices of the bulk hybrids could be controlled by adjusting the TiO 2 content and could be increased up to 1.566 for 6.3 vol % TiO 2 content (1.492 for pristine PMMA).

The influence of polymeric membrane gas spargers on hydrodynamics and mass transfer in bubble column bioreactors.

Science.gov (United States)

Tirunehe, Gossaye; Norddahl, B

2016-04-01

Gas sparging performances of a flat sheet and tubular polymeric membranes were investigated in 3.1 m bubble column bioreactor operated in a semi batch mode. Air-water and air-CMC (Carboxymethyl cellulose) solutions of 0.5, 0.75 and 1.0 % w/w were used as interacting gas-liquid mediums. CMC solutions were employed in the study to simulate rheological properties of bioreactor broth. Gas holdup, bubble size distribution, interfacial area and gas-liquid mass transfer were studied in the homogeneous bubbly flow hydrodynamic regime with superficial gas velocity (U(G)) range of 0.0004-0.0025 m/s. The study indicated that the tubular membrane sparger produced the highest gas holdup and densely populated fine bubbles with narrow size distribution. An increase in liquid viscosity promoted a shift in bubble size distribution to large stable bubbles and smaller specific interfacial area. The tubular membrane sparger achieved greater interfacial area and an enhanced overall mass transfer coefficient (K(L)a) by a factor of 1.2-1.9 compared to the flat sheet membrane.

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

Proton-transfer lasers based on solid copolymers of modified 2-(2'-hydroxyphenyl)benzimidazoles with methacrylate monomers

Science.gov (United States)

Costela, A.; García-Moreno, I.; Mallavia, Ricardo; Amat-Guerri, F.; Barroso, J.; Sastre, R.

1998-06-01

We report on the lasing action of two newly synthesized 2-(2'-hydroxyphenyl) benzimidazole derivatives copolymerized with methyl methacrylate. The laser samples were transversely pumped with a N 2 laser at 337 nm. The influence on the proton-transfer laser performance of the distance between the chromophore group and the polymeric main chain and of the rigidity of the polymeric host matrix, were studied. Significant increases in lasing efficiency and photostability are demonstrated for some of the new materials, as compared to those previously obtained with related proton-transfer dyes also covalently bound to methacrylic monomers.

Surface modification of polypropylene membrane by polyethylene glycol graft polymerization

Energy Technology Data Exchange (ETDEWEB)

Abednejad, Atiye Sadat, E-mail: atiyeabednejad@gmail.com [Department of Biomedical Engineering, Faculty of New Sciences and Technologies, University of Tehran, P.O. Box 14395-1561, Tehran (Iran, Islamic Republic of); Amoabediny, Ghasem [Department of Life Science Engineering, Faculty of New Sciences and Technologies, University of Tehran, P.O. Box 14395-1561, Tehran (Iran, Islamic Republic of); Research Center for New Technologies in Life Science Engineering, University of Tehran, P.O. Box 63894-14179, Tehran (Iran, Islamic Republic of); Ghaee, Azadeh [Department of Biomedical Engineering, Faculty of New Sciences and Technologies, University of Tehran, P.O. Box 14395-1561, Tehran (Iran, Islamic Republic of)

2014-09-01

Polypropylene hollow fiber microporous membranes have been used in a wide range of applications, including blood oxygenator. The hydrophobic feature of the polypropylene surface causes membrane fouling. To minimize fouling, a modification consisting of three steps: surface activation in H{sub 2} and O{sub 2} plasma, membrane immersion in polyethylene glycol (PEG) and plasma graft polymerization was performed. The membranes were characterized by contact angle measurement, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), tensile test, scanning electron microscopy (SEM) and atomic force microscopy (AFM). Oxygen transfer of modified membranes was also tested. The stability of grafted PEG was measured in water and in phosphate buffer saline (PBS) at 37 °C. Blood compatibility of modified surfaces was evaluated by the platelet adhesion method. Water contact angel reduction from 110° to 72° demonstrates the enhanced hydrophilicity, and XPS results verify the presence of oxygenated functional groups due to the peak existence in 286 eV as a result of PEG grafting. The results clearly indicate that plasma graft-polymerization of PEG is an effective way for antifouling improvement of polypropylene membranes. Also, the results show that oxygen transfer changes in PEG grafted membranes are not significant. - Highlights: • H{sub 2} and O{sub 2} plasma graft polymerization of PEG on polypropylene membrane was carried out. • Changes in surface properties were investigated by FTIR, XPS, SEM, and AFM. • Surface wettability enhanced as a result of poly ethylene glycol grafting. • PEG grafting degree increase causes reduction of fouling and adhesion.

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

Effect of organoelemental compounds of group 3 elements on radical polymerization of vinyl monomers

International Nuclear Information System (INIS)

Grishin, D.F.; Mojkin, A.A.

1996-01-01

When alkyl, alkyl alkoxy, and alkyl halide derivatives of boron and aluminium are introduced into the system in amounts that are comparable to the concentration of initiator, they coordinate to the growing macroradicals, thus changing their reactivity, and exert regulating effect on the rate of polymerization of vinyl monomers and the molecular mass of the resulting polymers. The said organoelemental compounds accelerate the polymerization of butyl acrylate, methyl methacrylate, acrylonitrile, vinyl acetate, and vinylidene chloride, reduce the molecular mass of acrylic polymers, and virtually do not affect the polymerization of styrene. The specific features of vinyl polymerization are associated with participation of organoelemental additives at the stages of chain growth and chain termination and can be explained within the framework of the mechanism of radical-coordination polymerization. 32 refs., 3 tabs

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.

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.

Modeling and sensitivity analysis of mass transfer in active multilayer polymeric film for food applications

Science.gov (United States)

Bedane, T.; Di Maio, L.; Scarfato, P.; Incarnato, L.; Marra, F.

2015-12-01

The barrier performance of multilayer polymeric films for food applications has been significantly improved by incorporating oxygen scavenging materials. The scavenging activity depends on parameters such as diffusion coefficient, solubility, concentration of scavenger loaded and the number of available reactive sites. These parameters influence the barrier performance of the film in different ways. Virtualization of the process is useful to characterize, design and optimize the barrier performance based on physical configuration of the films. Also, the knowledge of values of parameters is important to predict the performances. Inverse modeling and sensitivity analysis are sole way to find reasonable values of poorly defined, unmeasured parameters and to analyze the most influencing parameters. Thus, the objective of this work was to develop a model to predict barrier properties of multilayer film incorporated with reactive layers and to analyze and characterize their performances. Polymeric film based on three layers of Polyethylene terephthalate (PET), with a core reactive layer, at different thickness configurations was considered in the model. A one dimensional diffusion equation with reaction was solved numerically to predict the concentration of oxygen diffused into the polymer taking into account the reactive ability of the core layer. The model was solved using commercial software for different film layer configurations and sensitivity analysis based on inverse modeling was carried out to understand the effect of physical parameters. The results have shown that the use of sensitivity analysis can provide physical understanding of the parameters which highly affect the gas permeation into the film. Solubility and the number of available reactive sites were the factors mainly influencing the barrier performance of three layered polymeric film. Multilayer films slightly modified the steady transport properties in comparison to net PET, giving a small reduction

The influence of polymeric membrane gas spargers on hydrodynamics and mass transfer in bubble column bioreactors

DEFF Research Database (Denmark)

Tirunehe, Gossay; Norddahl, B.

2016-01-01

Gas sparging performances of a flat sheet and tubular polymeric membranes were investigated in 3.1 m bubble column bioreactor operated in a semi batch mode. Air–water and air–CMC (Carboxymethyl cellulose) solutions of 0.5, 0.75 and 1.0 % w/w were used as interacting gas–liquid mediums. CMC....../s. The study indicated that the tubular membrane sparger produced the highest gas holdup and densely populated fine bubbles with narrow size distribution. An increase in liquid viscosity promoted a shift in bubble size distribution to large stable bubbles and smaller specific interfacial area. The tubular...... membrane sparger achieved greater interfacial area and an enhanced overall mass transfer coefficient (KLa) by a factor of 1.2–1.9 compared to the flat sheet membrane....

Tuning the Solubility of Copper Complex in Atom Transfer Radical Self-Condensing Vinyl Polymerizations to Control Polymer Topology via One-Pot to the Synthesis of Hyperbranched Core Star Polymers

Directory of Open Access Journals (Sweden)

Zong-Cheng Chen

2014-09-01

Full Text Available In this paper, we propose a simple one-pot methodology for proceeding from atom transfer reaction-induced conventional free radical polymerization (AT-FRP to atom transfer self-condensing vinyl polymerization (AT-SCVP through manipulation of the catalyst phase homogeneity (i.e., CuBr/2,2'-bipyridine (CuBr/Bpy in a mixture of styrene (St, 4-vinyl benzyl chloride (VBC, and ethyl 2-bromoisobutyrate. Tests of the solubilities of CuBr/Bpy and CuBr2/Bpy under various conditions revealed that both temperature and solvent polarity were factors affecting the solubility of these copper complexes. Accordingly, we obtained different polymer topologies when performing AT-SCVP in different single solvents. We investigated two different strategies to control the polymer topology in one-pot: varying temperature and varying solvent polarity. In both cases, different fractions of branching revealed the efficacy of varying the polymer topology. To diversify the functionality of the peripheral space, we performed chain extensions of the resulting hyperbranched poly(St-co-VBC macroinitiator (name as: hbPSt MI with either St or tBA (tert-butyl acrylate. The resulting hyperbranched core star polymer had high molecular weights (hbPSt-g-PSt: Mn = 25,000, Đ = 1.77; hbPSt-g-PtBA: Mn = 27,000, Đ = 1.98; hydrolysis of the tert-butyl groups of the later provided a hyperbranched core star polymer featuring hydrophilic poly(acrylic acid segments.

Modeling intraparticle transports during propylene polymerizations using supported metallocene and dual function metallocene as catalysts: Single particle model

Directory of Open Access Journals (Sweden)

Li Hua-Rong

2014-01-01

Full Text Available Two improved multigrain models (MGMs for preparing homopolypropylene and long chain branched polypropylene via propylene polymerization using silica-supported metallocene or dual function metallocene as catalysts are presented in this paper. The presented models are used to predict the intraparticle flow fields involved in the polymerizations. The simulation results show that the flow field distributions involve dare basically identical. The results also show that both the two polymerization processes have an initiation stage and the controlling step for them is reaction-diffusion-reaction with the polymerization proceeding. Furthermore, the simulation results show that the intra particle mass transfer resistance has significant effect on the polymerization but the heat transfer resistance can be ignored.

Fabrication of luminescent hydroxyapatite nanorods through surface-initiated RAFT polymerization: Characterization, biological imaging and drug delivery applications

Energy Technology Data Exchange (ETDEWEB)

Heng, Chunning [Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an, 710069 (China); Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zheng, Xiaoyan [Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an, 710069 (China); Liu, Meiying; Xu, Dazhuang; Huang, Hongye; Deng, Fengjie [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Hui, Junfeng, E-mail: huijunfeng@126.com [Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an, 710069 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of 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)

2016-11-15

Highlights: • Hydrophobic hydroxyapatite nanorods were obtained from hydrothermal synthesis. • Surface initiated RAFT polymerization was adopted to surface modification of hydroxyapatite nanorods. • These modified hydroxyapatite nanorods showed high water dispersibility and biocompatibility. • These modified hydroxyapatite nanorods can be used for controlled drug delivery. - Abstract: Hydroxyapatite nanomaterials as an important class of nanomaterials, have been widely applied for different biomedical applications for their excellent biocompatibility, biodegradation potential and low cost. In this work, hydroxyapatite nanorods with uniform size and morphology were prepared through hydrothermal synthesis. The surfaces of these hydroxyapatite nanorods are covered with hydrophobic oleic acid, making them poor dispersibility in aqueous solution and difficult for biomedical applications. To overcome this issue, a simple surface initiated polymerization strategy has been developed via combination of the surface ligand exchange and reversible addition fragmentation chain transfer (RAFT) polymerization. Hydroxyapatite nanorods were first modified with Riboflavin-5-phosphate sodium (RPSSD) via ligand exchange reaction between the phosphate group of RPSSD and oleic acid. Then hydroxyl group of nHAp-RPSSD was used to immobilize chain transfer agent, which was used as the initiator for surface-initiated RAFT polymerization. The nHAp-RPSSD-poly(IA-PEGMA) nanocomposites were characterized by means of {sup 1}H nuclear magnetic resonance, Fourier transform infrared spectroscopy, fluorescence spectroscopy and thermal gravimetric analysis in detailed. The biocompatibility, biological imaging and drug delivery of nHAp-RPSSD-poly(IA-PEGMA) were also investigated. Results showed that nHAp-RPSSD-poly(IA-PEGMA) exhibited excellent water dispersibility, desirable optical properties, good biocompatibility and high drug loading capability, making them promising candidates for

Fabrication of luminescent hydroxyapatite nanorods through surface-initiated RAFT polymerization: Characterization, biological imaging and drug delivery applications

International Nuclear Information System (INIS)

Heng, Chunning; Zheng, Xiaoyan; Liu, Meiying; Xu, Dazhuang; Huang, Hongye; Deng, Fengjie; Hui, Junfeng; Zhang, Xiaoyong; Wei, Yen

2016-01-01

Highlights: • Hydrophobic hydroxyapatite nanorods were obtained from hydrothermal synthesis. • Surface initiated RAFT polymerization was adopted to surface modification of hydroxyapatite nanorods. • These modified hydroxyapatite nanorods showed high water dispersibility and biocompatibility. • These modified hydroxyapatite nanorods can be used for controlled drug delivery. - Abstract: Hydroxyapatite nanomaterials as an important class of nanomaterials, have been widely applied for different biomedical applications for their excellent biocompatibility, biodegradation potential and low cost. In this work, hydroxyapatite nanorods with uniform size and morphology were prepared through hydrothermal synthesis. The surfaces of these hydroxyapatite nanorods are covered with hydrophobic oleic acid, making them poor dispersibility in aqueous solution and difficult for biomedical applications. To overcome this issue, a simple surface initiated polymerization strategy has been developed via combination of the surface ligand exchange and reversible addition fragmentation chain transfer (RAFT) polymerization. Hydroxyapatite nanorods were first modified with Riboflavin-5-phosphate sodium (RPSSD) via ligand exchange reaction between the phosphate group of RPSSD and oleic acid. Then hydroxyl group of nHAp-RPSSD was used to immobilize chain transfer agent, which was used as the initiator for surface-initiated RAFT polymerization. The nHAp-RPSSD-poly(IA-PEGMA) nanocomposites were characterized by means of "1H nuclear magnetic resonance, Fourier transform infrared spectroscopy, fluorescence spectroscopy and thermal gravimetric analysis in detailed. The biocompatibility, biological imaging and drug delivery of nHAp-RPSSD-poly(IA-PEGMA) were also investigated. Results showed that nHAp-RPSSD-poly(IA-PEGMA) exhibited excellent water dispersibility, desirable optical properties, good biocompatibility and high drug loading capability, making them promising candidates for biological

Surface-Initiated Graft Atom Transfer Radical Polymerization of Methyl Methacrylate from Chitin Nanofiber Macroinitiator under Dispersion Conditions

Directory of Open Access Journals (Sweden)

Ryo Endo

2015-08-01

Full Text Available Surface-initiated graft atom transfer radical polymerization (ATRP of methyl methacrylate (MMA from self-assembled chitin nanofibers (CNFs was performed under dispersion conditions. Self-assembled CNFs were initially prepared by regeneration from a chitin ion gel with 1-allyl-3-methylimidazolium bromide using methanol; the product was then converted into the chitin nanofiber macroinitiator by reaction with α-bromoisobutyryl bromide in a dispersion containing N,N-dimethylformamide. Surface-initiated graft ATRP of MMA from the initiating sites on the CNFs was subsequently carried out under dispersion conditions, followed by filtration to obtain the CNF-graft-polyMMA film. Analysis of the product confirmed the occurrence of the graft ATRP on the surface of the CNFs.

Collaborative Research: Polymeric Multiferroics

Energy Technology Data Exchange (ETDEWEB)

Ren, Shenqiang [Temple Univ., Philadelphia, PA (United States). College of Engineering

2017-04-20

The goal of this project is to investigate room temperature magnetism and magnetoelectric coupling of polymeric multiferroics. A new family of molecular charge-transfer crystals has been emerged as a fascinating opportunity for the development of all-organic electrics and spintronics due to its weak hyperfine interaction and low spin-orbit coupling; nevertheless, direct observations of room temperature magnetic spin ordering have yet to be accomplished in organic charge-transfer solids. Furthermore, room temperature magnetoelectric coupling effect hitherto known multiferroics, is anticipated in organic donor-acceptor complexes because of magnetic field effects on charge-transfer dipoles, yet this is also unexplored. The PI seeks to fundamental understanding of the control of organic crystals to demonstrate and explore room temperature multiferroicity. The experimental results have been verified through the theoretical modeling.

Colorful Polyelectrolytes: An Atom Transfer Radical Polymerization Route to Fluorescent Polystyrene Sulfonate.

Science.gov (United States)

Huberty, Wayne; Tong, Xiaowei; Balamurugan, Sreelatha; Deville, Kyle; Russo, Paul S; Zhang, Donghui

2016-03-01

A labeled green fluorescent polystyrene sulfonate (LNaPSS) has been synthesized using atom transfer radical polymerization of a styrene sulfonate monomer with a fluorescent co-monomer, fluorescein thiocyanate-vinyl aniline. As a result this 100 % sulfonated polymer contains no hydrophobic patches along the chain backbone besides the fluorescent marker itself. The concentration of the fluorescent monomer was kept low to maintain the characteristic properties of the anionic polyelectrolyte, LNaPSS. ATRP conditions facilitated the production of polymers spanning a range of molecular weights from 35,000 to 175,000 in gram-scale batches with polydispersity indices of 1.01-1.24. Molecular weight increased with the monomer to initiator ratio. Gel permeation chromatography results show a unimodal distribution, and the polymer structure was also confirmed by (1)H NMR and FT-IR spectroscopy. Fluorescence spectroscopy confirmed covalent bonding of fluorescein isothiocyanate to the polymer, indicating that the polymer is suitable as a probe in fluorescence microscopy. To demonstrate this ability, the polymer was used to locate structural features in salt crystals formed during drying, as in the evaporation of sea mist. A second application to probe diffusion studies is also demonstrated.

Poly(glycidyl methacrylate) grafted CdSe quantum dots by surface-initiated atom transfer radical polymerization: Novel synthesis, characterization, properties, and cytotoxicity studies

Energy Technology Data Exchange (ETDEWEB)

Bach, Long Giang; Islam, Md. Rafiqul [Department of Imaging System Engineering, Pukyong National University, Busan 608-737 (Korea, Republic of); Lee, Doh Chang [Department of Chemical and Biomolecular Engineering, KAIST Institute for the Nanocentury (KINC), Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701 (Korea, Republic of); Lim, Kwon Taek, E-mail: ktlim@pknu.ac.kr [Department of Imaging System Engineering, Pukyong National University, Busan 608-737 (Korea, Republic of)

2013-10-15

A novel approach for the synthesis of poly(glycidyl methacrylate) grafted CdSe quantum dot (QDs) (PGMA-g-CdSe) was developed. The PGMA-g-CdSe nanohybrids were synthesized by the surface-initiated atom transfer radical polymerization of glycidyl methacrylate from the surface of the strategic initiator, CdSe-BrIB QDs prepared by the interaction of 2-bromoisobutyryl bromide (BrIB) and CdSe-OH QDs. The structure, morphology, and optical property of the PGMA-g-CdSe nanohybrids were analyzed by FT-IR, XPS, TGA, XRD, TEM, and PL. The as-synthesized PGMA-g-CdSe nanohybrids having multi-epoxide groups were employed for the direct coupling of biotin via ring-opening reaction of the epoxide groups to afford the Biotin-f-PGMA-g-CdSe nanobioconjugate. The covalent immobilization of biotin onto PGMA-g-CdSe was confirmed by FT-IR, XPS, and EDX. Biocompatibility and imaging properties of the Biotin-f-PGMA-g-CdSe were investigated by MTT bioassay and PL analysis, respectively. The cell viability study suggested that the biocompatibility was significantly enhanced by the functionalization of CdSe QDs by biotin and PGMA.

Poly(glycidyl methacrylate) grafted CdSe quantum dots by surface-initiated atom transfer radical polymerization: Novel synthesis, characterization, properties, and cytotoxicity studies

International Nuclear Information System (INIS)

Bach, Long Giang; Islam, Md. Rafiqul; Lee, Doh Chang; Lim, Kwon Taek

2013-01-01

A novel approach for the synthesis of poly(glycidyl methacrylate) grafted CdSe quantum dot (QDs) (PGMA-g-CdSe) was developed. The PGMA-g-CdSe nanohybrids were synthesized by the surface-initiated atom transfer radical polymerization of glycidyl methacrylate from the surface of the strategic initiator, CdSe-BrIB QDs prepared by the interaction of 2-bromoisobutyryl bromide (BrIB) and CdSe-OH QDs. The structure, morphology, and optical property of the PGMA-g-CdSe nanohybrids were analyzed by FT-IR, XPS, TGA, XRD, TEM, and PL. The as-synthesized PGMA-g-CdSe nanohybrids having multi-epoxide groups were employed for the direct coupling of biotin via ring-opening reaction of the epoxide groups to afford the Biotin-f-PGMA-g-CdSe nanobioconjugate. The covalent immobilization of biotin onto PGMA-g-CdSe was confirmed by FT-IR, XPS, and EDX. Biocompatibility and imaging properties of the Biotin-f-PGMA-g-CdSe were investigated by MTT bioassay and PL analysis, respectively. The cell viability study suggested that the biocompatibility was significantly enhanced by the functionalization of CdSe QDs by biotin and PGMA.

Polymeric hollow fiber heat exchanger as an automotive radiator

International Nuclear Information System (INIS)

Krásný, Ivo; Astrouski, Ilya; Raudenský, Miroslav

2016-01-01

Highlights: • Polymeric hollow fiber heat exchanger as an automotive radiator is proposed. • The mechanism of heat transfer (HT) relies on diameter of polymeric hollow fiber. • Grimson equation is sufficient for approximate prediction of the heat transfers. - Abstract: Nowadays, different automotive parts (tubing, covers, manifolds, etc.) are made of plastics because of their superior characteristics, low weight, chemical resistance, reasonable price and several other aspects. Manufacturing technologies are already well-established and the application of plastics is proven. Following this trend, the production of compact and light all-plastic radiators seems reasonable. Two plastic heat exchangers were manufactured based on polypropylene tubes of diameter 0.6 and 0.8 mm (so-called fibers) and tested. The heat transfer performance and pressure drops were studied with hot (60 °C) ethyleneglycol-water brine flowing inside the fibers and air (20 °C) outside because these conditions are conventional for car radiator operation. It was observed that heat transfer rates (up to 10.2 kW), overall heat transfer coefficients (up to 335 W/m"2 K), and pressure drops are competitive to conventional aluminium finned-tube radiators. Moreover, influence of fiber diameter was studied. It was observed that air-side convective coefficients rise with a decrease of fiber diameter. Air-side pressure drops of plastic prototypes were slightly higher than of aluminium radiator but it is expected that additional optimization will eliminate this drawback. Experimentally obtained air-side heat transfer coefficients were compared with the theoretical prediction using the Grimson equation and the Churchill and Bernstein approach. It was found that the Grimson equation is sufficient for approximate prediction of the outer HTCs and can be used for engineering calculations. Further work will concentrate on optimizing and developing a polymeric hollow fiber heat exchanger with reduced size

Fabrication of an SPR Sensor Surface with Antifouling Properties for Highly Sensitive Detection of 2,4,6-Trinitrotoluene Using Surface-Initiated Atom Transfer Polymerization

Directory of Open Access Journals (Sweden)

Kiyoshi Toko

2013-07-01

Full Text Available In this study, we modified a surface plasmon resonance immunosensor chip with a polymer using surface-initiated atom transfer polymerization (SI-ATRP for the highly sensitive detection of 2,4,6-trinitrotoluene (TNT. To immobilize a TNT analogue on the polymer, mono-2-(methacryloyloxyethylsuccinate (MES, which has a carboxyl group, was used in this study. However, the anti-TNT antibody may adsorb non-specifically on the polymer surface by an electrostatic interaction because MES is negatively charged. Therefore, a mixed monomer with MES and diethylaminoethylmethacrylate (DEAEM, which has a tertiary amino group and is positively charged, was prepared to obtain electroneutrality for suppressing the nonspecific adsorption. The detection of TNT was performed by inhibition assay using the polymer surface. To ensure high sensitivity to TNT, the affinity between the surface and the antibody was optimized by controlling the density of the initiator for ATRP by mixing two types of self-assembled monolayer reagents. As a result, a limit of detection of 5.7 pg/mL (ppt for TNT was achieved using the optimized surface.

Controlled Grafting of Poly(methyl methacrylate) Brushes on Poly(vinylidene fluoride) Powders by Surface-initiated Atom Transfer Radical Polymerization

Institute of Scientific and Technical Information of China (English)

TANG Zhaoqi; LI Wei; LIU Lanqin; HUANG Lei; ZHOU Jin; YU Haiyin

2009-01-01

Controlled grafting of well-defined polymer brushes of methyl methacrylate (MMA) on the poly(vinylidene fluoride) (PVDF) powders was carded out by the surface-initiated atom transfer radical polymerization (ATRP). The ATRP initiator was anchored on the PVDF surface by alkaline treatment, followed by UV-induced bromination; then methyl methacrylate (MMA) was grafted onto the brominated PVDF by the ATRP technique. The chemical composition changes of PVDF were characterized by Fourier transform-infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). FT-IR and XPS results clearly indicated the successful graft of poly(methyl methacrylate) onto the PVDF surface.

Uranium Adsorbent Fibers Prepared by Atom-Transfer Radical Polymerization (ATRP) from Poly(vinyl chloride)- co -chlorinated Poly(vinyl chloride) (PVC- co -CPVC) Fiber

Energy Technology Data Exchange (ETDEWEB)

Brown, Suree; Yue, Yanfeng; Kuo, Li-Jung; Mehio, Nada; Li, Meijun; Gill, Gary; Tsouris, Costas; Mayes, Richard T.; Saito, Tomonori; Dai, Sheng

2016-04-20

The need to secure future supplies of energy attracts researchers in several countries to a vast resource of nuclear energy fuel: uranium in seawater (estimated at 4.5 billion tons in seawater). In this study, we developed effective adsorbent fibers for the recovery of uranium from seawater via atom-transfer radical polymerization (ATRP) from a poly- (vinyl chloride)-co-chlorinated poly(vinyl chloride) (PVC-co-CPVC) fiber. ATRP was employed in the surface graft polymerization of acrylonitrile (AN) and tert-butyl acrylate (tBA), precursors for uranium-interacting functional groups, from PVC-co-CPVC fiber. The [tBA]/[AN] was systematically varied to identify the optimal ratio between hydrophilic groups (from tBA) and uranyl-binding ligands (from AN). The best performing adsorbent fiber, the one with the optimal [tBA]/[AN] ratio and a high degree of grafting (1390%), demonstrated uranium adsorption capacities that are significantly greater than those of the Japan Atomic Energy Agency (JAEA) reference fiber in natural seawater tests (2.42-3.24 g/kg in 42 days of seawater exposure and 5.22 g/kg in 49 days of seawater exposure, versus 1.66 g/kg in 42 days of seawater exposure and 1.71 g/kg in 49 days of seawater exposure for JAEA). Adsorption of other metal ions from seawater and their corresponding kinetics were also studied. The grafting of alternative monomers for the recovery of uranium from seawater is now under development by this versatile technique of ATRP.

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.

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.

Preparation of poly(methyl methacrylate) grafted titanate nanotubes by in situ atom transfer radical polymerization

International Nuclear Information System (INIS)

Gao Yuan; Zhou Yongfeng; Yan Deyue; Gao Xueping

2008-01-01

This paper reports the successful preparation of core-shell hybrid nanocomposites by a 'grafting from' approach based on in situ atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) from titanate nanotubes (TNTs). Transmission electron microscope (TEM) images of the products provide direct evidence for the formation of a core-shell structure, possessing a hard core of TNTs and a soft shell of poly-MMA (PMMA). Fourier-transform infrared spectroscopy (FT-IR), hydrogen nuclear magnetic resonance ( 1 H NMR), scanning electron microscopy (SEM), and thermal gravimetric analysis (TGA) were used to determine the chemical structure, morphology, and the grafted PMMA quantities of the resulting products. The grafted PMMA content was well controlled and increased with increasing monomer/initiator ratio. Further copolymerization of hydroxyethyl methacrylate (HEMA) with PMMA-coated TNTs as initiators was realized, illustrating the 'living' characteristics of the ATRP method used in this paper.

Improving the drug delivery characteristics of graphene oxide based polymer nanocomposites through the “one-pot” synthetic approach of single-electron-transfer living radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Gao, Peng; Liu, Meiying; Tian, Jianwen; Deng, Fengjie [Department of 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); Xu, Dazhuang [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Liu, Liangji [Affiliated Hospital of Jiangxi University of Traditional Chinese Medicine, Nanchang 330006 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of 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)

2016-08-15

Graphical abstract: The PEGylated graphene oxides with high water dispersibility, good biocompatibility as well as high drug loading capability were fabricated via “one-pot” SET-LRP. - Highlights: • Surface modification of graphene oxide with polymers. • One-pot single-electron-transfer living radical polymerization. • Improving drug delivery characteristics. • The synthetic approach is rather simple, universal and effective. - Abstract: Graphene oxide (GO) based polymer nanocomposites have attracted extensive research interest recently for their outstanding physicochemical properties and potential applications. However, surface modification of GO with synthetic polymers has demonstrated to be trouble for most polymerization procedures are occurred under non-aqueous solution, which will in turn lead to the restacking of GO. In this work, a facile and efficient “one-pot” strategy has been developed for surface modification of GO with synthetic polymers through single-electron-transfer living radical polymerization (SET-LRP). The GO based polymer nanocomposites were obtained via SET-LRP in aqueous solution using poly(ethylene glycol) methyl ether methacrylate (PEGMA) as the monomer and 11-bromoundecanoic acid as the initiator, which could be effectively adsorbed on GO through hydrophobic interaction. The successful preparation of GO based polymer nanocomposites was confirmed by a series of characterization techniques such as {sup 1}H nuclear magnetic resonance, Fourier transform infrared spectroscopy, thermogravimetric analysis, transmission electron microscopy and X-ray photoelectron spectroscopy. The resultant products exhibit high water disperisibility, excellent biocompatibility and high efficient drug loading capability, making these PEGylated GO nanocomposites promising candidates for biomedical applications.

Self-assembly of block copolymer micelles: synthesis via reversible addition-fragmentation chain transfer polymerization and aqueous solution properties.

Science.gov (United States)

Mya, Khine Y; Lin, Esther M J; Gudipati, Chakravarthy S; Gose, Halima B A S; He, Chaobin

2010-07-22

Poly(hexafluorobutyl methacrylate) (PHFBMA) homopolymer was synthesized by reversible addition-fragmentation chain transfer (RAFT)-mediated living radical polymerization in the presence of cyano-2-propyl dithiobenzoate (CPDB) RAFT agent. A block copolymer of PHFBMA-poly(propylene glycol acrylate) (PHFBMA-b-PPGA) with dangling poly(propylene glycol) (PPG) side chains was then synthesized by using CPDB-terminated PHFBMA as a macro-RAFT agent. The amphiphilic properties and self-assembly of PHFBMA-b-PPGA block copolymer in aqueous solution were investigated by dynamic and static light scattering (DLS and SLS) studies, in combination with fluorescence spectroscopy and transmission electron microscopy (TEM). Although PPG shows moderately hydrophilic character, the formation of nanosize polymeric micelles was confirmed by fluorescence and TEM studies. The low value of the critical aggregation concentration exhibited that the tendency for the formation of copolymer aggregates in aqueous solution was very high due to the strong hydrophobicity of the PHFBMA(145)-b-PPGA(33) block copolymer. The combination of DLS and SLS measurements revealed the existence of micellar aggregates in aqueous solution with an association number of approximately 40 +/- 7 for block copolymer micelles. It was also found in TEM observation that there are 40-50 micelles accumulated into one aggregate and these micelles are loosely packed inside the aggregate.

Selective polymerization catalysis: controlling the metal chain end group to prepare block copolyesters.

Science.gov (United States)

Zhu, Yunqing; Romain, Charles; Williams, Charlotte K

2015-09-30

Selective catalysis is used to prepare block copolyesters by combining ring-opening polymerization of lactones and ring-opening copolymerization of epoxides/anhydrides. By using a dizinc complex with mixtures of up to three different monomers and controlling the chemistry of the Zn-O(polymer chain) it is possible to select for a particular polymerization route and thereby control the composition of block copolyesters.

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

The effect of ethanol on the γ radiation induced polymerization of styrene

International Nuclear Information System (INIS)

Zhang Xujia; Ha Hongfei; Wu Jilan

1990-01-01

The γ radiation induced polymerization of styrene in the presence of ethanol was studied at dose rate of 5 x 10 17 eV/ml min. The result showed that the radiation induced polymerization of styrene was sensitized by ethanol. The experimental results were in agreement with the theoretical calculation of WAS equation. The mechanism of sensitization was proposed as proton transfer reaction

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)

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.

Some regularities of separate and simultaneous radiation polymerization of vinyl acetate and acrylonitrile in adsorption layer on aerosil surface

International Nuclear Information System (INIS)

Mund, S.L.; Bruk, M.A.; Abkin, A.D.

1976-01-01

The kinetics has been studied of initial stage radiation copolymerization and separate radiation polymerization of aerosil adsorbed vinylacetate (VA) and acrylonitrile (AN). The monomers were irradiated using a Co 60 gamma source or a RUP-400 X-ray unit. Infrared spectroscopy, nuclear magnetic resonance and gravimetry were used in the study. It has been found that in the dose rate interval studied (over 60-450 rad./sec) the break of kinetic chains during the polymerization of VA and its mixtures with AN is due to the reaction of degenerate transfer of the chains to the surface hydroxyl groups. When AN is polymerized, biomolecular break of chains prevails. The effective activation energy of polymerization is 1.5 kcal/mol for VA and 2.5 kcal/mol for AN. The order of polymerization rates by the concentration of adsorbed monomers at 50 deg, as well as by the irradiation dose rate is equal to 1 and 1 for VA and 3/2 and 0.7 for AN, respectively. The calculated values of copolymerization constants coincide with those characteristic of their radical polymerization in liquid phase. Isotherms for adsorption of VA and AN on aerosil at 30, 50 and 70 deg have been studied [ru

Preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization for the selective recognition of tetracycline from aqueous medium

International Nuclear Information System (INIS)

Dai, Jiangdong; Pan, Jianming; Xu, Longcheng; Li, Xiuxiu; Zhou, Zhiping; Zhang, Rongxian; Yan, Yongsheng

2012-01-01

Highlights: ► Atom transfer radical emulsion polymerization is a “living” and green technique. ► Nanoparticles can overcome mass transfer limitations and improve accessibility. ► Molecular imprinted nanoparticles with magnetic property for fast separation. ► The performance of imprinted nanoparticles was investigated in detail. ► Nanoparticles were used to selective recognize Tetracycline from water medium. - Abstract: In the work, we reported an effective method for the preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization (ATREP), and then as-prepared magnetic molecularly imprinted nanoparticles (MMINs) were evaluated as adsorbents for selective recognition of tetracycline (TC) molecules from aqueous medium. The resulting nanoparticles were characterized by FT-IR, TGA, VSM, SEM and TEM. The results demonstrated MMINs with a narrow diameter distribution were cross-linked with modified Fe 3 O 4 particles, composed of imprinted layer and exhibited good magnetic sensitivity, magnetic and thermal stability. Batch rebinding studies were carried out to determine the specific adsorption equilibrium, kinetics, and selective recognition. The estimated adsorption capacity of MMINs towards TC by the Langmuir isotherm model was 12.10 mg g −1 at 298 K, which was 6.33 times higher than that of magnetic non-molecularly imprinted nanoparticles (MNINs). The kinetic property of MMINs was well-described by the pseudo-second-order rate equation. The results of selective recognition experiments demonstrated outstanding affinity and selectivity towards TC over competitive antibiotics. The reusability of MMINs showed no obviously deterioration at least five repeated cycles in performance. In addition, the MMINs prepared were successfully applied to the extraction of TC from the spiked pork sample.

Unique effects of microwave heating on polymerization kinetics of poly(methyl methacrylate) composites

Energy Technology Data Exchange (ETDEWEB)

Spasojević, Pavle [Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120 Belgrade (Serbia); Jovanović, Jelena, E-mail: jelenaj@ffh.bg.ac.rs [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11001 Belgrade (Serbia); Adnadjevic, Borivoj [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11001 Belgrade (Serbia)

2013-09-16

The effects of heating mode (conventional and microwave) on the kinetics of isothermal polymerization of MMA composite materials were investigated. Isothermal kinetics curves at temperature range from 343 K to 363 K for both conventional (CH) and microwave heating (MWH) were determined. It was found that the polymerization of MMA composite materials was kinetically elementary reaction for both CH and MWH. The kinetics of CH polymerization can be described by the model of phase-boundary controlled process (contracting volume), whereas the kinetics of MWH polymerization can be described by the model of first-order chemical reaction. The kinetics parameters (E{sub a} and ln A) of the polymerization under microwave heating are lower than for conventional heating. The established decreases in the activation energy and pre-exponential factor under the MWH compared to the CH is explained with the increase in the energy of ground vibrational level of the C–O valence vibrations (ν = 987 cm{sup −1}) in methyl methacrylate molecule and with the decrease in its anharmonicity factor which is caused with the selective resonant transfer of energy from the energetic reservoir to the oscillators in methyl methacrylate molecules. - Graphical abstract: Display Omitted - Highlights: • The MWH speeds the MMA material polymerization and changes the kinetics model. • A novel concept of MWH action based on activation complexes formation is presented. • The Selective Energy Transfer model is used to explain the effects of MWH. • The kinetics parameters under MWH are lower than for CH. • The activation energy for both MWH and CH polymerization is quantized.

THE KINETICS OF METHYL METHACRYLATE POLYMERIZATION INITIATED BY THE VOLATILE PRODUCTS OF A METHYL METHACRYLATE PLASMA

Institute of Scientific and Technical Information of China (English)

杨梅林; 马於光; 郑莹光; 沈家骢

1990-01-01

It is found that the volatile products of methyl methacrylate plasma can very actively initiate the polymerization of the monomer to produce ultrahigh molecular weight polymers. This polymerization of MMA occurs by a livlng free radical mechanism with instantaneous initiation and monomer transfer.

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.

A KIND OF FLUORESCENCE PROBE TO STUDY THE KINETICS OF POLYMERIZATION PROCESS

Institute of Scientific and Technical Information of China (English)

YANG Guoqiang; WU Shikang

1994-01-01

Fluorescence properties of 1-phenyl-3-(4'-nitrophenyl) pyrazoline (PNP) were studied in bulk polymerization process of methylmethacrylate (MMA). The fluorescence intensity of PNP was enhanced and the emission maximum was blue shifted with the polymerization progress. In the period of auto-acceleration of the polymerization the enhancement of fluorescence intensity and blue shift of peak wavelength in spectra could be observed evidently. This means that the solvatochromic properties of PNP are influenced not only by the solvent polarity but also by the viscosity of the medium(especially by the phase transition). In solid state PNP emits from the charge transfer excited state without solvent relaxation. The transient emission spectra and the results from Bakhshiev model of solvent relaxation coincide with that from the polymerization experiment.

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)

Facile Synthesis of Well-Defined MDMO-PPV Containing (TriBlock—Copolymers via Controlled Radical Polymerization and CuAAC Conjugation

Directory of Open Access Journals (Sweden)

Neomy Zaquen

2015-02-01

Full Text Available A systematic investigation into the chain transfer polymerization of the so-called radical precursor polymerization of poly(p-phenylene vinylene (PPV materials is presented. Polymerizations are characterized by systematic variation of chain transfer agent (CTA concentration and reaction temperature. For the chain transfer constant, a negative activation energy of −12.8 kJ·mol−1 was deduced. Good control over molecular weight is achieved for both the sulfinyl and the dithiocarbamate route (DTC. PPVs with molecular weights ranging from thousands to ten thousands g·mol−1 were obtained. To allow for a meaningful analysis of the CTA influence, Mark–Houwink–Kuhn–Sakurada (MHKS parameters were determined for conjugated MDMO-PPV ([2-methoxy-5-(3',7'-dimethyloctyloxy]-1,4-phenylenevinylene to α = 0.809 and k = 0.00002 mL·g−1. Further, high-endgroup fidelity of the CBr4-derived PPVs was proven via chain extension experiments. MDMO-PPV-Br was successfully used as macroinitiator in atom transfer radical polymerization (ATRP with acrylates and styrene. A more polar PPV counterpart was chain extended by an acrylate in single-electron transfer living radical polymerization (SET-LRP. In a last step, copper-catalyzed azide alkyne cycloaddition (CuAAC was used to synthesize block copolymer structures. Direct azidation followed by macromolecular conjugation showed only partial success, while the successive chain extension via ATRP followed by CuAAC afforded triblock copolymers of the poly(p-phenylene vinylene-block-poly(tert-butyl acrylate-block-poly(ethylene glycol (PPV-b-PtBuA-b-PEG.

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.

Radiation-induced controlled polymerization of acrylic acid by RAFT and RAFT-MADIX methods in protic solvents

Science.gov (United States)

Sütekin, S. Duygu; Güven, Olgun

2018-01-01

The kinetic investigation of one-pot synthesis of poly(acrylic acid) (PAA) prepared via gamma radiation induced controlled polymerization was reported. PAA homopolymers were prepared by Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization in the presence of trithiocarbonate-based chain transfer agent (CTA) 2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) and also by Reversible Addition-Fragmentation/Macromolecular Design by Inter-change of Xanthates (RAFT/MADIX) polymerization in the presence of a xanthate based CTA O-ethyl-S-(1-methoxycarbonyl) ethyl dithiocarbonate (RA1). The polymerizations were performed at room temperature by the virtue of ionizing radiation. Protic solvents were used for the RAFT polymerization of AA considering environmental profits. The linear first-order kinetic plot, close control of molecular weight by the monomer/CTA molar ratio supported that the polymerization proceeds in a living fashion. The linear increase in molecular weight with conversion monitored by Size Exclusion Chromatography (SEC) is another proof of controlling of polymerization. [Monomer]/[RAFT] ratio and conversion was controlled to obtain PAA in the molecular weight range of 6900-35,800 with narrow molecular weight distributions. Reaction kinetics and effect of the amount of RAFT agent were investigated in detail. Between two different types of CTA, trithiocarbonate based DDMAT was found to be more efficient in terms of low dispersity (Đ) and linear first-order kinetic behavior for the radiation induced controlled synthesis of PAA homopolymers.

Preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization for the selective recognition of tetracycline from aqueous medium

Energy Technology Data Exchange (ETDEWEB)

Dai, Jiangdong; Pan, Jianming; Xu, Longcheng; Li, Xiuxiu [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); Zhou, Zhiping [School of Material Science and Engineering, Jiangsu University, Zhenjiang 212013 (China); Zhang, Rongxian [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); Yan, Yongsheng, E-mail: djdxxx123@163.com [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Beijing, 100191 (China)

2012-02-29

Highlights: Black-Right-Pointing-Pointer Atom transfer radical emulsion polymerization is a 'living' and green technique. Black-Right-Pointing-Pointer Nanoparticles can overcome mass transfer limitations and improve accessibility. Black-Right-Pointing-Pointer Molecular imprinted nanoparticles with magnetic property for fast separation. Black-Right-Pointing-Pointer The performance of imprinted nanoparticles was investigated in detail. Black-Right-Pointing-Pointer Nanoparticles were used to selective recognize Tetracycline from water medium. - Abstract: In the work, we reported an effective method for the preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization (ATREP), and then as-prepared magnetic molecularly imprinted nanoparticles (MMINs) were evaluated as adsorbents for selective recognition of tetracycline (TC) molecules from aqueous medium. The resulting nanoparticles were characterized by FT-IR, TGA, VSM, SEM and TEM. The results demonstrated MMINs with a narrow diameter distribution were cross-linked with modified Fe{sub 3}O{sub 4} particles, composed of imprinted layer and exhibited good magnetic sensitivity, magnetic and thermal stability. Batch rebinding studies were carried out to determine the specific adsorption equilibrium, kinetics, and selective recognition. The estimated adsorption capacity of MMINs towards TC by the Langmuir isotherm model was 12.10 mg g{sup -1} at 298 K, which was 6.33 times higher than that of magnetic non-molecularly imprinted nanoparticles (MNINs). The kinetic property of MMINs was well-described by the pseudo-second-order rate equation. The results of selective recognition experiments demonstrated outstanding affinity and selectivity towards TC over competitive antibiotics. The reusability of MMINs showed no obviously deterioration at least five repeated cycles in performance. In addition, the MMINs prepared were successfully

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).

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

Formation of hyperbranched polymers in atom transfer radical copolymerization of MMA and DVB

Institute of Scientific and Technical Information of China (English)

无

2010-01-01

Hyperbranched poly(methyl methacrylate)s (HPMMAs) have been successfully prepared by atom transfer radical copolymerization of MMA and divinylbenzene (DVB).Kinetic study shows complete consumption of the initiator in 0.5 h,and relatively low polymerization rate when DVB content in the feed was high.By analyzing MALDI-TOF spectra of the resulting copolymers,the linear A n B (n=0,1,2,3) oligomers were formed in 0.5 h of polymerization,and then the oligomers reacted each other to form dimers,further reactions produced HPMMA.The SEC and NMR spectroscopies were used to trace the polymerization,and the results demonstrate that small amount of the branching reactions occur in the initial polymerization,and the branched polymers are significantly generated past a certain conversion depending upon the feed ratios.Raising the content of DVB in the monomer mixture can increase the pendent vinyl groups of the linear oligo-inimers,leading to gelation at low MMA conversion.

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

Novel Tertiary Amino Containing Blinding Composite Membranes via Raft Polymerization and Their Preliminary CO2 Permeation Performance.

Science.gov (United States)

Zhu, Lifang; Zhou, Mali; Yang, Shanshan; Shen, Jiangnan

2015-04-23

Facile synthesis of poly (N,N-dimethylaminoethyl methacrylate) (PDMAEMA) star polymers on the basis of the prepolymer chains, PDMAEMA as the macro chain transfer agent and divinyl benzene (DVB) as the cross-linking reagent by reversible addition-fragmentation chain transfer (RAFT) polymerization was described. The RAFT polymerizations of DMAEMA at 70 °C using four RAFT agents with different R and Z group were investigated. The RAFT agents used in these polymerizations were dibenzyl trithiocarbonate (DBTTC), s-1-dodecyl-s'-(α,α'-dimethyl-α-acetic acid) trithiocarbonate (MTTCD), s,s'-bis (2-hydroxyethyl-2'-dimethylacrylate) trithiocarbonate (BDATC) and s-(2-cyanoprop-2-yl)-s-dodecyltrithiocarbonate (CPTCD). The results indicated that the structure of the end-group of RAFT agents had significant effects on the ability to control polymerization. Compared with the above-mentioned RAFT agents, CPTCD provides better control over the molecular weight and molecular weight distribution. The polydispersity index (PDI) was determined to be within the scope of 1.26 to 1.36. The yields, molecular weight, and distribution of the star polymers can be tuned by changing the molar ratio of DVB/PDMAEMA-CPTCD. The chemical composition and structure of the linear and star polymers were characterized by GPC, FTIR, 1H NMR, XRD analysis. For the pure Chitosan membrane, a great improvement was observed for both CO₂ permeation rate and ideal selectivity of the blending composite membrane upon increasing the content of SPDMAEMA-8. At a feed gas pressure of 37.5 cmHg and 30 °C, the blinding composite membrane (Cs: SPDMAEMA-8 = 4:4) has a CO₂ permeation rate of 8.54 × 10⁻⁴ cm³ (STP) cm⁻²∙s⁻¹∙cm∙Hg⁻¹ and a N₂ permeation rate of 6.76 × 10⁻⁵ cm³ (STP) cm⁻²∙s⁻¹∙cm∙Hg⁻¹, and an ideal CO₂/N₂ selectivity of 35.2.

Gamma-ray-induced polymerization of mixed liposomes consisting of 2,4-octadecadienoyl groups of phospholipids and unpolymerizable components

Energy Technology Data Exchange (ETDEWEB)

Akama, Kazuhiro; Awai, Kouji; Yano, Yoshihiro; Tokuyama, Satoru; Nakano, Yoshio [Tsukuba Research Laboratory, NOF Corporation, Tsukuba, Ibaraki (Japan); Hosoi, Fumio; Omichi, Hideki [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan). Takasaki Radiation Chemistry Research Establishment

2000-06-01

We studied the {gamma}-ray-induced polymerization of two mixed-liposome systems containing 1,2-bis-[(2E,4E)-octadecadienoyl]-sn-glycero-3-phosphocholine (DODPC) to clarify its mechanism; (a) containing DODPC and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), or DODPC/DPPC liposome, and (b) containing DODPC, DPPC, Cholesterol (Chol), and stearic acid (SA), or DODPC/DPPC/Chol/SA liposomes was carried out. For each system, various molar ratios of DODPC/DPPC were studied. For DODPC/DPPC/Chol/SA liposomes, the molar ratio of phospholipid/Chol/SA was 7/7/2. Liposomes were prepared by extrusion through a 0.2-{mu}m-pore polycarbonate filter and polymerized by {gamma}-irradiation at a dose rate of 3.3 kGy/h at 4degC. Polymerization rate increased when DODPC/DPPC was 5/5 in DODPC/DPPC liposomes and when it was 9/1, 8/2, 7/3, and 5/5 in DODPC/DPPC/Chol/SA liposomes. The degree of polymerization at molar ratio 5/5 for each mixed-liposome system significantly increased compared with that of DODPC liposomes containing no DPPC. For polymerized mixed liposomes stability, mean diameter after one freeze-thaw cycle remained unchanged for molar ratios from 10/0 to 8/2 of either DODPC/DPPC or DODPC/DPPC/Chol/SA liposomes. {gamma}-Ray-induced polymerization of each mixed-liposome system was analyzed using kinetic treatment of polymerization. Although the rate of polymerization for either systems differed from that of DODPC liposomes, the polymerization mechanism was the same. Immiscibility between DODPC and unpolymerizable components was estimated based on the kinetic data of polymerization. Hydrophobic interactions of DPPC and/or Chol with DODPC significantly affected the conformation of DODPC, which rearranges into an easily polymerizable conformation. The rate and degree of polymerization thus increased. (author)

Synthesis, Characterization and Bulk Properties of Amphiphilic Copolymers Containing Fluorinated Methacrylates from Sequential Copper-Mediated Radical Polymerization

DEFF Research Database (Denmark)

Hansen, Natanya Majbritt Louie; Gerstenberg, Michael; Haddleton, David M.

2008-01-01

acrylate (MEA), and poly(ethylene glycol) methyl ether methacrylate (PEGMA) by Atom Transfer Radical Polymerization. A kinetic study of the 3FM homopolymerization initiated with ethyl bromoisobutyrate and Cu(I)Br/N-(n-propyl)-2-pyridylmethanimine reveals a living/ controlled polymerization in the range 80...

DOWNER (version 79-1): group collapse cross section and transfer matrices

International Nuclear Information System (INIS)

Cullen, D.E.

1979-01-01

FORTRAN-callable subroutines are provided to allow a user to group-collapse cross sections and/or transfer matrices from any arbitrary initial group structure to any arbitrary final group structure. 3 figures

Polymerization of Phenylacetylene-Based Monodendrons with Alkoxy Peripheral Groups and Oxygen/Nitrogen Permeation Behavior of Their Membranes

Directory of Open Access Journals (Sweden)

Takashi Kaneko

2012-01-01

Full Text Available Monodendron monomers with alkoxy peripheral groups were synthesized, and the focal point of monodendrons, terminal acetylene, was polymerized with rhodium catalyst to yield corresponding polydendrons with a high molecular weight. The polydendrons were soluble in common organic solvents and readily formed membranes. Oxygen permselectivity was improved in the polydendrons with a space-persistent dendritic crowd. It was found that the well-defined dendritic and rod-like structure of the polydendrons was useful for permselective membrane.

Final Technical Report: Collaborative Research. Polymeric Muliferroics

Energy Technology Data Exchange (ETDEWEB)

Ren, Shenqiang [Univ. of Kansas, Lawrence, KS (United States)

2015-06-05

The goal of this project is to investigate room temperature magnetism and magnetoelectric coupling of polymeric multiferroics. A new family of organic charge-transfer complexes has been emerged as a fascinating opportunity for the development of all-organic electrics and spintronics due to its weak hyperfine interaction and low spin-orbit coupling; nevertheless, direct observations of room temperature magnetic spin ordering have yet to be accomplished in organic charge-transfer complexes. Furthermore, room temperature magnetoelectric coupling effect hitherto known multiferroics, is anticipated in organic donor-acceptor complexes because of magnetic field effects on charge-transfer dipoles, yet this is also unexplored. The PIs seek to fundamental understanding of the synthetic control of organic complexes to demonstrate and explore room temperature multiferroicity.

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).

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.

Relation Entropy and Transferable Entropy Think of Aggregation on Group Decision Making

Institute of Scientific and Technical Information of China (English)

CHENG Qi-yue; QIU Wan-hua; LIU Xiao-feng

2002-01-01

In this paper, aggregation question based on group decision making and a single decision making is studied. The theory of entropy is applied to the sets pair analysis. The system of relation entropy and the transferable entropy notion are put. The character is studied. An potential by the relation entropy and transferable entropy are defined. It is the consistency measure on the group between a single decision making. We gained a new aggregation effective definition on the group misjudge.

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

International Nuclear Information System (INIS)

Aikins, J.A.; Williams, F.

1985-01-01

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 weights. A high frequency of chain (proton) transfer to monomer is indicated by the fact that the kinetic chain lengths are estimated to be several hundred times larger than the range of DP/sub n/ values (12-4). 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 the opening of the epoxide ring for these monomers is generally accompanied by the concomitant ring opening of the cyclobutane ring structure to yield a gem-di-methyl group in the main chain

Synthesis of Photocrosslinkable and Amine Containing Multifunctional Nanoparticles via Polymerization-Induced Self-Assembly.

Science.gov (United States)

Huang, Jianbing; Li, Decai; Liang, Hui; Lu, Jiang

2017-08-01

Photo-crosslinkable and amine-containing block copolymer nanoparticles are synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly of a multifunctional core-forming monomer, 2-((3-(4-(diethylamino)phenyl)acryloyl)oxy)ethyl methacrylate (DEMA), using poly(2-hydroxypropyl methacrylate) macromolecular chain transfer agent as a steric stabilizer in methanol at 65 °C. By tuning the chain length of PDEMA, a range of nanoparticle morphologies (sphere, worm, and vesicle) can be obtained. Since cinnamate groups can easily undergo a [2 + 2] cycloaddition of the carbon-carbon double bonds upon UV irradiation, the as-prepared block copolymer nanoparticles are readily stabilized by photo-crosslinking to produce anisotropic nanoparticles. The crosslinked block copolymer nanoparticles can be used as templates for in situ formation polymer/gold hybrid nanoparticles. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Cognitive synergy in groups and group-to-individual transfer of decision-making competencies

Science.gov (United States)

Curşeu, Petru L.; Meslec, Nicoleta; Pluut, Helen; Lucas, Gerardus J. M.

2015-01-01

In a field study (148 participants organized in 38 groups) we tested the effect of group synergy and one's position in relation to the collaborative zone of proximal development (CZPD) on the change of individual decision-making competencies. We used two parallel sets of decision tasks reported in previous research to test rationality and we evaluated individual decision-making competencies in the pre-group and post-group conditions as well as group rationality (as an emergent group level phenomenon). We used multilevel modeling to analyze the data and the results showed that members of synergetic groups had a higher cognitive gain as compared to members of non-synergetic groups, while highly rational members (members above the CZPD) had lower cognitive gains compared to less rational group members (members situated below the CZPD). These insights extend the literature on group-to-individual transfer of learning and have important practical implications as they show that group dynamics influence the development of individual decision-making competencies. PMID:26441750

Cognitive synergy in groups and group-to-individual transfer of decision-making competencies.

Science.gov (United States)

Curşeu, Petru L; Meslec, Nicoleta; Pluut, Helen; Lucas, Gerardus J M

2015-01-01

In a field study (148 participants organized in 38 groups) we tested the effect of group synergy and one's position in relation to the collaborative zone of proximal development (CZPD) on the change of individual decision-making competencies. We used two parallel sets of decision tasks reported in previous research to test rationality and we evaluated individual decision-making competencies in the pre-group and post-group conditions as well as group rationality (as an emergent group level phenomenon). We used multilevel modeling to analyze the data and the results showed that members of synergetic groups had a higher cognitive gain as compared to members of non-synergetic groups, while highly rational members (members above the CZPD) had lower cognitive gains compared to less rational group members (members situated below the CZPD). These insights extend the literature on group-to-individual transfer of learning and have important practical implications as they show that group dynamics influence the development of individual decision-making competencies.

All solid-state polymer electrolytes prepared from a hyper-branched graft polymer using atom transfer radical polymerization

International Nuclear Information System (INIS)

Higa, Mitsuru; Fujino, Yukiko; Koumoto, Taihei; Kitani, Ryousuke; Egashira, Satsuki

2005-01-01

We propose an all solid-state (liquid free) polymer electrolyte (SPE) prepared from a hyper-branched graft copolymer. The graft copolymer consisting of a poly(methyl methacrylate) main chain and poly(ethylene glycol) methyl ether methacrylate side chains was synthesized by atom transfer radical polymerization changing the average chain distance between side chains, side chain length and branched chain length of the proposed structure of the graft copolymer. The ionic conductivity of the SPEs increases with increasing the side chain length, branched chain length and/or average distance between the side chains. The ionic conductivity of the SPE prepared from POEM 9 whose POEM content = 51 wt% shows 2 x 10 -5 S/cm at 30 deg. C. The tensile strength of the SPEs decreases with increases the side chain length, branched chain length and/or average distance between the side chains. These results indicate that a SPE prepared from the hyper-branched graft copolymer has potential to be applied to an all-solid polymer electrolyte

Application of adult attachment theory to group member transference and the group therapy process.

Science.gov (United States)

Markin, Rayna D; Marmarosh, Cheri

2010-03-01

Although clinical researchers have applied attachment theory to client conceptualization and treatment in individual therapy, few researchers have applied this theory to group therapy. The purpose of this article is to begin to apply theory and research on adult dyadic and group attachment styles to our understanding of group dynamics and processes in adult therapy groups. In particular, we set forth theoretical propositions on how group members' attachment styles affect relationships within the group. Specifically, this article offers some predictions on how identifying group member dyadic and group attachment styles could help leaders predict member transference within the therapy group. Implications of group member attachment for the selection and composition of a group and the different group stages are discussed. Recommendations for group clinicians and researchers are offered. PsycINFO Database Record (c) 2010 APA, all rights reserved

Rational preparation of dibenzothiophene-imprinted polymers by surface imprinting technique combined with atom transfer radical polymerization

International Nuclear Information System (INIS)

Yang, Wenming; Liu, Lukuan; Zhou, Zhiping; Liu, Hong; Xie, Binze; Xu, Wanzhen

2013-01-01

A computational simulation method is introduced to simulate the dibenzothiophene-monomer pre-assembly system of molecular imprinted polymers. The interaction type and intensity between dibenzothiophene and monomer are discussed from the binding energy and spatial position distribution. The simulation and analysis results indicate that the amount of the function monomer is not the more the better in preparing molecular imprinted polymers. Based on the above results, a novel dibenzothiophene-imprinted polymers with the favorable specific adsorption effect was prepared by surface imprinting technique combined with atom transfer radical polymerization. This combined technologies are used for preparing a desulfurization adsorbent for the first time. Various measures were selected to characterize the structure and morphology of the prepared adsorbent. The characterization results show that the adsorbent has suitable features for further adsorption process. A series of static adsorption experiments were conducted to analyze its adsorption performance. The adsorption process follows Elovich model by the kinetic analysis and Sips equation by the isothermal analysis. The approach we described will provide another opportunity in the deep desulfurization field.

In situ development of self-reinforced cellulose nanocrystals based thermoplastic elastomers by atom transfer radical polymerization.

Science.gov (United States)

Yu, Juan; Wang, Chunpeng; Wang, Jifu; Chu, Fuxiang

2016-05-05

Recently, the utilization of cellulose nanocrystals (CNCs) as a reinforcing material has received a great attention due to its high elastic modulus. In this article, a novel strategy for the synthesis of self-reinforced CNCs based thermoplastic elastomers (CTPEs) is presented. CNCs were first surface functionalized with an initiator for surface-initiated atom transfer radical polymerization (SI-ATRP). Subsequently, SI-ATRP of methyl methacrylate (MMA) and butyl acrylate (BA) was carried out in the presence of sacrificial initiator to form CTPEs in situ. The CTPEs together with the simple blends of CNCs and linear poly(MMA-co-BA) copolymer (P(MMA-co-BA)) were characterized for comparative study. The results indicated that P(MMA-co-BA) was successfully grafted onto the surface of CNCs and the compatibility between CNCs and the polymer matrix in CTPEs was greatly enhanced. Specially, the CTPEs containing 2.15wt% CNCs increased Tg by 19.2°C and tensile strength by 100% as compared to the linear P(MMA-co-BA). Copyright © 2016 Elsevier Ltd. All rights reserved.

Surface-Confined Aqueous Reversible Addition-Fragmentation Chain Transfer (SCARAFT) Polymerization Method for Preparation of Coated Capillary Leads to over 10 000 Peptides Identified from 25 ng HeLa Digest by Using Capillary Zone Electrophoresis-Tandem Mass Spectrometry.

Science.gov (United States)

Zhang, Zhenbin; Peuchen, Elizabeth H; Dovichi, Norman J

2017-06-20

A surface-confined aqueous reversible addition-fragmentation chain transfer (SCARAFT) polymerization method was developed to coat capillaries for use in capillary zone electrophoresis (CZE). SCARAFT polymerization primarily takes place on the inner surface of the capillary instead of in solution, which greatly improves the homogeneity of the coating. Capillaries treated with this coating produced an electroosmotic mobility of 2.8 ± 0.2 × 10 -6 cm 2 ·V -1 ·s -1 (N = 3), which is roughly an order of magnitude lower than that of commercial linear polyacrylamide (LPA)-coated capillaries. Coated capillaries were evaluated for bottom-up proteomic analysis using CZE. The very low electroosmotic mobility results in a 200 min separation and improved single-shot analysis. An average of 977 protein groups and 5605 unique peptides were identified from 50 ng of an E. coli digest, and 2158 protein groups and 10 005 peptides were identified from 25 ng of a HeLa digest using single-shot analysis with a SCARAFT-acrylamide capillary coupled to a Q Exactive HF mass spectrometer. The coating is stable. A single capillary was used for over 200 h (8.4 days) of continuous operation. RSD in migration time was between 2 and 3% for selected ion electropherograms (SIEs) generated for six ions; median theoretical plate counts ranged from 240 000 to 600 000 for these SIEs. Various types of coatings could be prepared by simply changing the functional vinyl monomers in the polymerization mixture. Positively charged coatings using direct attachment and formation of a block copolymer were prepared and demonstrated for the separation of mixtures of intact proteins.

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.

Polymeric film application for phase change heat transfer

Science.gov (United States)

Bart, Hans-Jörg; Dreiser, Christian

2018-06-01

The paper gives a concise review on polymer film heat exchangers (PFHX) with a focus on polyether ether ketone (PEEK) foil as heat transfer element, mechanically supported by a grid structure. In order to promote PFHX applications, heat transfer performance and wetting behavior are studied in detail. Surface modifications to improve wetting are discussed and correlations are presented for critical Reynolds numbers to sustain a stable liquid film. Scaling phenomena related to surface properties and easily adaptable cleaning-in-place (CIP) procedures are further content. The contribution of the foil thickness and material selection on thermal performance is quantified and a correlation for enhanced aqueous film heat transfer for the grid supported PFHX is given. The basic research results and the design criteria enable early stage material selection and conceptual apparatus design.

Polymeric film application for phase change heat transfer

Science.gov (United States)

Bart, Hans-Jörg; Dreiser, Christian

2018-01-01

The paper gives a concise review on polymer film heat exchangers (PFHX) with a focus on polyether ether ketone (PEEK) foil as heat transfer element, mechanically supported by a grid structure. In order to promote PFHX applications, heat transfer performance and wetting behavior are studied in detail. Surface modifications to improve wetting are discussed and correlations are presented for critical Reynolds numbers to sustain a stable liquid film. Scaling phenomena related to surface properties and easily adaptable cleaning-in-place (CIP) procedures are further content. The contribution of the foil thickness and material selection on thermal performance is quantified and a correlation for enhanced aqueous film heat transfer for the grid supported PFHX is given. The basic research results and the design criteria enable early stage material selection and conceptual apparatus design.

Mechanism and kinetics of dithiobenzoate-mediated RAFT polymerization. I. The current situation

NARCIS (Netherlands)

Barner-Kowollik, C.; Buback, M.; Charleux, B.; Coote, M.L.; Drache, M.; Fukuda, T.; Goto, A.; Klumperman, B.; Lowe, A.B.; McLeary, J.B.; Moad, G.; Monteiro, M.J.; Sanderson, R.D.; Tonge, M.P.; Vana, P.

2006-01-01

Investigations into the kinetics and mechanism of dithiobenzoate-mediated Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerizations, which exhibit nonideal kinetic behavior, such as induction periods and rate retardation, are comprehensively reviewed. The appreciable uncertainty in the

Preparation of high-capacity, weak anion-exchange membranes by surface-initiated atom transfer radical polymerization of poly(glycidyl methacrylate) and subsequent derivatization with diethylamine

International Nuclear Information System (INIS)

Qian, Xiaolei; Fan, Hua; Wang, Chaozhan; Wei, Yinmao

2013-01-01

Ion-exchange membrane is of importance for the development of membrane chromatography. In this work, a high-capacity anion-exchange membrane was prepared by grafting of glycidyl methacrylate (GMA) onto the surface of regenerated cellulose (RC) membranes via surface-initiated atom transfer radical polymerization (SI-ATRP) and subsequent derivatization with diethylamine. Attenuated total reflectance Fourier-transform infrared (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to characterize changes in the chemical functionality, surface topography and pore morphology of the modified membranes. The static capacity of the prepared anion-exchange membrane was evaluated with bovine serum albumin (BSA) as a model protein. The results indicated that the anion-exchange membrane which could reach a maximum capacity of 96 mg/mL for static adsorption possesses a higher adsorption capacity, and the adsorption capacity increases with the polymerization time. The effect of pH and salt concentration confirmed that the adsorption of BSA followed ion-exchange mechanism. The established method would have potential application in the preparation of anion-exchange membrane.

Effect of telechelic ionic groups on the dispersion of organically modified clays in bisphenol A polycarbonate nanocomposites by in-situ polymerization using activated carbonates

Directory of Open Access Journals (Sweden)

M. Colonna

2017-05-01

Full Text Available Nanocomposites of bisphenol A polycarbonate with organically modified clays have been prepared for the first time by in-situ polymerization using bis(methyl salicyl carbonate as activated carbonate. The use of the activated carbonate permits to conduct the polymerization reaction at lower temperature and with shorter polymerization time with respect to those necessary for traditional melt methods that uses diphenyl carbonate, affording a nanocomposite with improved color. Moreover, an imidazolium salt with two long alkyl chains has been used to modify the montmorillonite, providing an organically modified clay with high thermal stability and wide d-spacing. The addition of ionic groups at the end of the polymer chain increases the interaction between the clay surface and the polymer producing a better dispersion of the clay. The presence of the clay increases the thermal stability of the polymer.

Preparation of Macroporous Poly (vinyl alcohol-co-triallyl isocyanurate) Beads Bearing Aminocarboxylic Acid as Functional Groups by Suspension Polymerization

Institute of Scientific and Technical Information of China (English)

无

2003-01-01

Macroporous poly (vinyl acetate-co-triallyl isocyanurate) beads were prepared with suspension polymerization method. The copolymer beads were then transformed into poly (vinyl alcohol-co-triallyl isocyanurate) by ester exchange reaction. Aminocarboxylic acids were immobilized on the copolymer beads by the esterification of hydroxyl groups with diethyl-lenetriaminepentaacetic bisanhydride. The weak acid exchange capacities, specific surface areas and mean pore diameters of the resultant resin beads were measured.

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.

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.)

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.

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)

Transferência e psicoterapia de grupo Transferencia y psicoterapia de grupo Transference and group psychotherapy

Directory of Open Access Journals (Sweden)

Luiz Paulo de C. Bechelli

2006-02-01

, coexisten múltiples transferencias que los miembros del grupo establecen entre sí, potencializando un gama de posibilidades de sentimientos. Ambas modalidades mantienen en común el presupuesto de que los conflictos psíquicos que impulsaron el paciente a buscar ayuda se pueden reducir o inclusive suprimir mediante la interpretación y la elaboración de la transferencia, que funcionan como procedimientos de cambio en el decurso del proceso terapéutico.This study examines the concept of transference, focusing on its peculiarities in the group context. The nature of the therapeutic situation and the broad freedom given to patients in order to access the unconscious material at their own pace, within a safe environment and with as little censorship as can be managed, transference gradually takes place. Through displacement, the psychotherapist and group members are perceived not as they are, with their real attributes, but as one or more objects that arouse emotions coming from the infant world, more precisely from the collection of deep affective influences. One peculiarity of the group situation when compared to individual psychotherapy is that, in the former, multiple transferences coexist, which group members establish among themselves, enabling a wide range of possible feelings. Both treatment modes share the assumption that unresolved conflicts which stimulated patients to seek for help can be reduced or even abolished through the interpretation and working through of transference, which functions as a process of change throughout the psychotherapy.

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.

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)

Synthesis of α-Bromine- Terminated Polystyrene Macroinitiator and Its Initiation of MMA Polymerization by ATRP

Institute of Scientific and Technical Information of China (English)

无

2000-01-01

In the present paper the synthesis of block copolymers via the transformation from living anionic polymerization (LAP) to atom transfer radical polymerization (ATRP) was described. Α-Bromine-terminated polystyrenes(PStBr) in the LAP step was prepared by using n-BuLi as initiator, tetrahydrofuran (THF) as the activator, α-methylstyrene (α-MeSt) as the capping group and liquid bromine (Br2) as the bromating agent. The effects of reaction conditions such as the amounts of α-MeSt, THF, and Br2 as well as molecular weight of polystyrene on the bromating efficiency (BE) and coupling extent (CE) were examined. The present results show that the yield of PStBr obtained was more than 93.8% and the coupling reaction was substantially absent. PStBr was further used as the macroinitiator in the polymerization of methyl-methacrylate(MMA) in the presence of copper(Ⅰ) halogen and 2,2-bipyridine(bpy) complexes. It was found that the molecular weight of the resulted PSt-b-PMMA increased linearly with the increase of the conversion of MMA and the polydispersity was 1.2-1.6. The structures of PStBr and P(St-b-MMA) were characterized by 1H NMR spectra.

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

Comparison of a polymeric pseudostationary phase in EKC with ODS stationary phase in RP-HPLC.

Science.gov (United States)

Ni, Xinjiong; Zhang, Min; Xing, Xiaoping; Cao, Yuhua; Cao, Guangqun

2018-01-01

Poly(stearyl methacrylate-co-methacrylic acid) (P(SMA-co-MAA)) was induced as pseudostationary phase (PSP) in electrokinetic chromatography (EKC). The n-octadecyl groups in SMA were the same as that in octadecylsilane (ODS) C18 column. Thus, the present work focused on the comparison of selectivity between polymeric PSP and ODS stationary phase (SP), and the effect of organic modifiers on the selectivity of polymeric PSP and ODS SP. 1-butanol could directly interacted with PSP as a Class I modifier, and improved both of the methylene selectivity and polar group selectivity. When the analysis times were similar, the polymeric PSP exhibited better methylene selectivity and polar group selectivity. Although the hydrophobic groups were similar, the substituted benzenes elution order was different between polymeric PSP and ODS SP. Linear solvation energy relationships (LSER) model analysis found that polymeric PSP and ODS SP exhibited two same key factors in selectivity: hydrophobic interaction and hydrogen bonding acidity. But polymeric PSP exhibited relatively strong n- and π-electrons interaction to the analytes. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of β-h elimination in rhodium-mediated carbene insertion polymerization

NARCIS (Netherlands)

Finger, M.; Reek, J.N.H.; de Bruin, B.

2011-01-01

The importance of β-H elimination as a possible mechanism to induce chain termination/transfer and/or the formation of stereodefects in the Rh(diene)-mediated oligomerization and polymerization of carbenes has been studied by means of different approaches. As a remarkable feature, this reaction is

A Green Platform for Preparation of the Well-Defined Polyacrylonitrile: 60Co γ-ray Irradiation-Initiated RAFT Polymerization at Room Temperature

Directory of Open Access Journals (Sweden)

Shuangshuang Zhang

2017-01-01

Full Text Available 60Co γ-ray irradiation-initiated reversible addition–fragmentation chain transfer (RAFT polymerization at room temperature with 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN as the chain transfer agent was first applied to acrylonitrile (AN polymerization, providing a “green” platform for preparing polyacrylonitrile (PAN-based carbon fibers using an environment-friendly energy source. Various effects of dose rate, molar ratio of the monomer to the chain transfer agent, monomer concentration and reaction time on the AN polymerization behaviors were performed to improve the controllability of molecular the weight and molecular weight distribution of the obtained PAN. The feature of the controlled polymerization was proven by the first-order kinetics, linear increase of the molecular weight with the monomer conversion and a successful chain-extension experiment. The molecular weight and molecular weight distribution of PAN were characterized by size exclusion chromatography (SEC. 1H NMR and Matrix assisted laser desorption ionization/time of flight mass spectra (MALDI-TOF-MS confirmed the chain-end functionality of PAN, which also was supported by the successful chain-extension experiments of original PANs with acrylonitrile and styrene as the second monomers respectively.

Neutral hydrophilic coatings for capillary electrophoresis prepared by controlled radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Navarro, Fabián H.; Gómez, Jorge E.; Espinal, José H.; Sandoval, Junior E., E-mail: junior.sandoval@correounivalle.edu.co

2016-12-15

In the present study, porous silica particles as well as impervious fused-silica wafers and capillary tubes were modified with hydrophilic polymers (hydroxylated polyacrylamides and polyacrylates), using a surface-confined grafting procedure based on atom transfer radical polymerization (ATRP) which was also surface-initiated from α-bromoisobutyryl groups. Initiator immobilization was achieved by hydrosilylation of allyl alcohol on hydride silica followed by esterification of the resulting propanol-bonded surface with α-bromoisobutyryl bromide. Elemental analysis, IR and NMR spectroscopies on silica micro-particles, atomic force microscopy, ellipsometry and profilometry on fused-silica wafers, as well as CE on fused-silica tubes were used to characterize the chemically modified silica substrate at different stages. We studied the effect of monomer concentration as well as cross-linker on the ability of the polymer film to reduce electroosmosis and to prevent protein adsorption (i. e., its non-fouling capabilities) and found that the former was rather insensitive to both parameters. Surface deactivation towards adsorption was somewhat more susceptible to monomer concentration and appeared also to be favored by a low concentration of the cross-linker. The results show that hydrophilic polyacrylamide and polyacrylate coatings of controlled thickness can be prepared by ATRP under very mild polymerization conditions (aqueous solvent, room temperature and short reaction times) and that the coated capillary tubes exhibit high efficiencies for protein separations (0.3–0.6 million theoretical plates per meter) as well as long-term hydrolytic stability under the inherently harsh conditions of capillary isoelectric focusing. Additionally, there was no adsorption of lysozyme on the coated surface as indicated by a complete recovery of the basic enzyme. Furthermore, since polymerization is confined to the inner capillary surface, simple precautions (e.g., solution

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.

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...

Hydrogel brushes grafted from stainless steel via surface-initiated atom transfer radical polymerization for marine antifouling

Science.gov (United States)

Wang, Jingjing; Wei, Jun

2016-09-01

Crosslinked hydrogel brushes were grafted from stainless steel (SS) surfaces for marine antifouling. The brushes were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) respectively with different fractions of crosslinker in the feed. The grafted layers prepared with different thickness were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), ellipsometry and water contact angle measurements. With the increase in the fraction of crosslinker in the feed, the thickness of the grafted layer increased and the surface became smooth. All the brush-coated SS surfaces could effectively reduce the adhesion of bacteria and microalgae and settlement of barnacle cyprids, as compared to the pristine SS surface. The antifouling efficacy of the PEGMA polymer (PPEGMA)-grafted surface was higher than that of the MPC polymer (PMPC)-grafted surfaces. Furthermore, the crosslinked hydrogel brush-grafted surfaces exhibited better fouling resistance than the non-crosslinked polymer brush-grafted surfaces, and the antifouling efficacy increased with the crosslinking density. These hydrogel coatings of low toxicity and excellent anti-adhesive characteristics suggested their useful applications as environmentally friendly antifouling coatings.

Possible Involvement of Hydrosulfide in B12-Dependent Methyl Group Transfer

Directory of Open Access Journals (Sweden)

John I. Toohey

2017-04-01

Full Text Available Evidence from several fields of investigation lead to the hypothesis that the sulfur atom is involved in vitamin B12-dependent methyl group transfer. To compile the evidence, it is necessary to briefly review the following fields: methylation, the new field of sulfane sulfur/hydrogen sulfide (S°/H2S, hydrosulfide derivatives of cobalamins, autoxidation of hydrosulfide radical, radical S-adenosylmethionine methyl transfer (RSMT, and methionine synthase (MS. Then, new reaction mechanisms for B12-dependent methyl group transfer are proposed; the mechanisms are facile and overcome difficulties that existed in previously-accepted mechanisms. Finally, the theory is applied to the effect of S°/H2S in nerve tissue involving the “hypomethylation theory” that was proposed 50 years ago to explain the neuropathology resulting from deficiency of vitamin B12 or folic acid. The conclusions are consistent with emerging evidence that sulfane sulfur/hydrogen sulfide may be beneficial in treating Alzheimer’s disease.

Highly sensitive measurement in two-photon absorption cross section and investigation of the mechanism of two-photon-induced polymerization

Energy Technology Data Exchange (ETDEWEB)

Lu Youmei E-mail: luym19@cc.tuat.ac.jp; Hasegawa, Fuyuki; Goto, Takamichi; Ohkuma, Satoshi; Fukuhara, Setsuko; Kawazu, Yukie; Totani, Kenro; Yamashita, Takashi; Watanabe, Toshiyuki E-mail: toshi@cc.tuat.ac.jp

2004-10-01

A novel two-photon initiator, 4,4'-bis[4-(di-n-butylamino)styryl]-benzene with the side-group methyl (Me) (abbreviated as Chromophore 1), was synthesized in comparison with the chromophore with the side group methoxy (MeO) (abbreviated as Chromophore 2). Femtosecond laser-induced fluorescence intensity was used to evaluate two-photon absorption (TPA) cross section, {delta}, by means of a charge-coupled device, USB-2000 (abbreviated as CCD). Results showed that changing the side group from Me to MeO led to a significant red-shift of the two-photon absorption ({sup 2}{lambda}{sub max}). However, the microstructures obtained by two-photon-induced polymerization (TPIP) demonstrated that the sensitivities of Chromophore 1 increased despite a two-fold decrease in the two-photon cross section {delta}{sub max,} relative to Chromophore 2. Correlated with the appearance that the long-lived charge transfer emission of the chromophore in the monomer bulk, we suggest that the intramolecular charge transfer (intra-CT) takes place within the excited dye. Then intermolecular charge transfer was successive as a result of the formation of an exciplex between the dye and the monomer. The Me group was favorable for the intra-CT, relative to MeO, which contributed to the enhancement of the sensitivity of TPIP.

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...

Polyacrylamide grafting of modified graphene oxides by in situ free radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Tang, Mingyi [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Xu, Xiaoyang, E-mail: xiaoyangxu2012@163.com [School of Science, Tianjin University, Tianjin 30072 (China); Wu, Tao [School of Science, Tianjin University, Tianjin 30072 (China); Zhang, Sai; Li, Xianxian [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Li, Yi, E-mail: liyi@tju.edu.cn [School of Science, Tianjin University, Tianjin 30072 (China)

2014-12-15

Highlights: • Graphene oxide (GO) was modified by chemical reactions to functionalized GO (FGO). • The FGOs and the GO were then subjected to in situ free radical polymerization. • Hydroxyl groups of GO were the most reactive grafting sites. - Abstract: Graphene oxide (GO) was modified using chemical reactions to obtain three types of functionalized GO sheets (FGO). The FGO sheets and the GO were then subjected to in situ free radical polymerization in order to study the grafting polymerization. The FGO and grafted-.FGO were analyzed with Fourier transform infrared spectroscopy, scanning electronic microscopy, thermo-gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The grafting percentages in the materials were calculated using the TGA and XPS results. The FGO sheets with different functional groups exhibited different grafting abilities, and hydroxyl groups were proven to be the most reactive grafting sites for the in situ free radical grafting polymerization of polyacrylamide.

Polyacrylamide grafting of modified graphene oxides by in situ free radical polymerization

International Nuclear Information System (INIS)

Tang, Mingyi; Xu, Xiaoyang; Wu, Tao; Zhang, Sai; Li, Xianxian; Li, Yi

2014-01-01

Highlights: • Graphene oxide (GO) was modified by chemical reactions to functionalized GO (FGO). • The FGOs and the GO were then subjected to in situ free radical polymerization. • Hydroxyl groups of GO were the most reactive grafting sites. - Abstract: Graphene oxide (GO) was modified using chemical reactions to obtain three types of functionalized GO sheets (FGO). The FGO sheets and the GO were then subjected to in situ free radical polymerization in order to study the grafting polymerization. The FGO and grafted-.FGO were analyzed with Fourier transform infrared spectroscopy, scanning electronic microscopy, thermo-gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The grafting percentages in the materials were calculated using the TGA and XPS results. The FGO sheets with different functional groups exhibited different grafting abilities, and hydroxyl groups were proven to be the most reactive grafting sites for the in situ free radical grafting polymerization of polyacrylamide

A Versatile Approach to Unimolecular Water-Soluble Carriers: ATRP of PEGMA with Hydrophobic Star-Shaped Polymeric Core Molecules as an Alternative for PEGylation

NARCIS (Netherlands)

Schramm, O.G.; Pavlov, G.M.; Erp, van H.H.P; Meier, M.A.R.; Hoogenboom, R.; Schubert, U.S.

2009-01-01

New amphiphilic star-shaped architectures with dense hydrophilic shells were synthesized by a combination of ring-opening polymerization (ROP) of e-caprolactone (CL) and atom transfer radical polymerization (ATRP) of different poly(ethylene glycol) methacrylates (PEGMAs). The PCL hydrophobic cores

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.

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.

Enhanced protein retention on poly(caprolactone) via surface initiated polymerization of acrylamide

International Nuclear Information System (INIS)

Ma, Yuhao; Cai, Mengtan; He, Liu; Luo, Xianglin

2016-01-01

Graphical abstract: - Highlights: • Dense package of poly(acrylamide) on poly(caprolactone) surface was achieved by surface-initiated atom transfer radical polymerization. • Poly(acrylamide) grafted surface exhibited high protein retention ability. • Loaded protein was resistant to detachment and maintained its structure without denaturation. - Abstract: To enhance the biocompatibility or extend the biomedical application of poly(caprolactone) (PCL), protein retention on PCL surface is often required. In this study, poly(acrylamide) (PAAm) brushes were grown from PCL surface via surface-initiated atom transfer radical polymerization (SI-ATRP) and served as a protein-capturing platform. Grafted PAAm was densely packed on surface and exhibited superior protein retention ability. Captured protein was found to be resistant to washing under detergent environment. Furthermore, protein structure after being captured was investigated by circular dichroism (CD) spectroscopy, and the CD spectra verified that secondary structure of captured proteins was maintained, indicating no denaturation of protein happened for retention process.

Transferable tight binding model for strained group IV and III-V heterostructures

Science.gov (United States)

Tan, Yaohua; Povolotskyi, Micheal; Kubis, Tillmann; Boykin, Timothy; Klimeck, Gerhard

Modern semiconductor devices have reached critical device dimensions in the range of several nanometers. For reliable prediction of device performance, it is critical to have a numerical efficient model that are transferable to material interfaces. In this work, we present an empirical tight binding (ETB) model with transferable parameters for strained IV and III-V group semiconductors. The ETB model is numerically highly efficient as it make use of an orthogonal sp3d5s* basis set with nearest neighbor inter-atomic interactions. The ETB parameters are generated from HSE06 hybrid functional calculations. Band structures of strained group IV and III-V materials by ETB model are in good agreement with corresponding HSE06 calculations. Furthermore, the ETB model is applied to strained superlattices which consist of group IV and III-V elements. The ETB model turns out to be transferable to nano-scale hetero-structure. The ETB band structures agree with the corresponding HSE06 results in the whole Brillouin zone. The ETB band gaps of superlattices with common cations or common anions have discrepancies within 0.05eV.

Luminescent sensing of organophosphates using europium(III) containing imprinted polymers prepared by RAFT polymerization

International Nuclear Information System (INIS)

Southard, Glen E.; Van Houten, Kelly A.; Ott, Edward W.; Murray, George M.

2007-01-01

Molecularly imprinted polymers capable of sensing organophosphorous compounds by luminescence have been prepared by reversible addition fragmentation chain transfer (RAFT) polymerization. The polymer contained a dithiobenzoate substituted tris(β-diketonate) europium(III) complex which served as a polymerization substrate and as a luminescent binding site for pinacolyl methylphosphonate (PMP), the hydrolysis product of the nerve agent Soman. The resultant polymer allowed quantitation of PMP in the low ppb range with minimal interference from similar compounds. Polymers were characterized by luminescence spectroscopy and scanning electron microscopy

Radical polymerization by a supramolecular catalyst: cyclodextrin with a RAFT reagent

Directory of Open Access Journals (Sweden)

Kohei Koyanagi

2016-11-01

Full Text Available Supramolecular catalysts have received a great deal of attention because they improve the selectivity and efficiency of reactions. Catalysts with host molecules exhibit specific reaction properties and recognize substrates via host–guest interactions. Here, we examined radical polymerization reactions with a chain transfer agent (CTA that has α-cyclodextrin (α-CD as a host molecule (α-CD-CTA. Prior to the polymerization of N,N-dimethylacrylamide (DMA, we investigated the complex formation of α-CD with DMA. Single X-ray analysis demonstrated that α-CD includes DMA inside its cavity. When DMA was polymerized in the presence of α-CD-CTA using 2,2'-azobis[2-(2-imidazolin-2-ylpropane dihydrochloride (VA-044 as an initiator in an aqueous solution, poly(DMA was obtained in good yield and with narrow molecular weight distribution. In contrast, the polymerization of DMA without α-CD-CTA produced more widely distributed polymers. In the presence of 1,6-hexanediol (C6 diol which works as a competitive molecule by being included in the α-CD cavity, the reaction yield was lower than that without C6 diol.

Preparation of Mg(OH)_2 hybrid pigment by direct precipitation and graft onto cellulose fiber via surface-initiated atom transfer radical polymerization

International Nuclear Information System (INIS)

Wang, Xiao; Zhang, Yue; Lv, Lihua; Cui, Yongzhu; Wei, Chunyan; Pang, Guibing

2016-01-01

Graphical abstract: - Highlights: • Adsorbed anionic dye molecules are conducive to preferential growth of (0 0 1) plane of Mg(OH)_2 crystal for Mg(OH)_2 pigments. • Uniform coverage of nanosized Mg(OH)_2 pigments on fiber surface is achieved via surface-initiated ATRP. • About 4 wt% of Mg(OH)_2 pigment on fiber surface shortens nearly half of burning time of cellulose. - Abstract: Mg(OH)_2 flame retardant hybrid pigment is synthesized through simultaneous solution precipitation and adsorption of anionic dyes (C.I. Acid Red 6). The Mg(OH)_2 hybrid pigment bearing vinyl groups after surface silane modification is immobilized onto the surface of bromo end-functional cellulose fiber by atom transfer radical polymerization (ATRP). The morphology and structure of Mg(OH)_2 pigments and cellulose fibers grafted with modified pigments are characterized. The thermal properties, flammability and color fastness of cellulose fibers grafted with modified pigments are measured. The results reveal that anionic dye molecules are adsorbed onto Mg(OH)_2 crystals and affect the formation of lamella-like Mg(OH)_2 crystals. The cellulose fiber grafted with modified Mg(OH)_2 hybrid pigment absorbs about four times heat more than original cellulose fiber with about 4% immobilization ratio of pigment, which shortens nearly half of afterflame time and afterglow time.

KINETICS OF POLYMERIZATION OF METHYL METHACRYLATE INITIATED BY COPPER POLYPROPYLENE-BASED POLYAMIDOXIME-SODIUM SULFITE SYSTEM

Institute of Scientific and Technical Information of China (English)

WU Jinyuan; YANG Yiguang; YANG Chaoxiong

1992-01-01

The aqueous polymerization of methyl methacrylate initiated by copper polypropylene-based polyamidoxime ( PPAO - Cu ) - sodium sulfite system was investigated . The overall rate of polymerization (Rp) is Rp=9.7 × 1012 e-21, 200/RT [MMA]0.88 [ Na2 SO 3 ]0.50 The length of the induction period (τ) is inversely proportional to the concentration of sodium sulfite and independent of the amount of polymer supported copper and the concentration of monomer. It could be expressed as follows:1τ=1.2× 1012e-15,600/RT[ Na2SO3] =KτRi The polymerization is initiated by a primary radical generated from the redox reaction rather than induced by "coordination-proton transfer" mechanism.

Olefin copolymerization via controlled radical polymerization : copolymerization of methyl methacrylate and 1-octene

NARCIS (Netherlands)

Venkatesh, R.; Klumperman, B.

2004-01-01

The atom transfer radical (co)polymerization (ATRP) of methyl methacrylate (MMA) with 1-octene was investigated. Well controlled homopolymer of MMA was obtained with 2,2,2-trichoroethanol (TCE) and p-toluenesulfonyl chloride (pTsCl), although, uncontrolled copolymerization occurred when pTsCl was

Polymerization catalysts containing electron-withdrawing amide ligands

Science.gov (United States)

Watkin, John G.; Click, Damon R.

2002-01-01

The present invention describes methods of making a series of amine-containing organic compounds which are used as ligands for group 3-10 and lanthanide metal compounds. The ligands have electron-withdrawing groups bonded to them. The metal compounds, when combined with a cocatalyst, are catalysts for the polymerization of olefins.

Vapor phase reactions in polymerization plasma for divinylsiloxane-bis-benzocyclobutene film deposition

International Nuclear Information System (INIS)

Kinoshita, Keizo; Nakano, Akinori; Kawahara, Jun; Kunimi, Nobutaka; Hayashi, Yoshihiro; Kiso, Osamu; Saito, Naoaki; Nakamura, Keiji; Kikkawa, Takamaro

2006-01-01

Vapor phase reactions in plasma polymerization of divinylsiloxane-bis-benzocyclobutene (DVS-BCB) low-k film depositions on 300 mm wafers were studied using mass spectrometry, in situ Fourier transform infrared, and a surface wave probe. Polymerization via Diels-Alder cycloaddition reaction was identified by the detection of the benzocyclohexene group. Hydrogen addition and methyl group desorption were also detected in DVS-BCB monomer and related large molecules. The dielectric constant k of plasma polymerized DVS-BCB with a plasma source power range up to 250 W was close to ∼2.7 of thermally polymerized DVS-BCB, and increased gradually over 250 W. The electron density at 250 W was about 1.5x10 10 cm -3 . The increase of the k value at higher power was explained by the decrease of both large molecular species via multistep dissociation and incorporation of silica components into the polymer. It was found that the reduction of electron density as well as precursor residence time is important for the plasma polymerization process to prevent the excess dissociation of the precursor

Possible mechanisms for the interaction of polymeric composite resins with Cu(II) ions in aqueous solution

International Nuclear Information System (INIS)

El-Zahhhar, A.A.; Abdel-Aziz, H.M.; Siyam, T.

2005-01-01

The interaction between the active groups of polymeric composite resins such as Poly(acrylamide-acrylic acid)-ethylenediaminetetra acetic acid disodium salt P(AM-AA)EDTANa 2 , Poly(acrylamide-acrylic acid)- montmorillonite P(AM-AA)-montmorillonite, and Poly(acrylamide-acrylic acid)-potassium nickel hexacyanoferrate P(AM-AA)-KNiHCF, with copper sulfate as a test ion has been studied. The spectroscopic studies show that the mechanism of interaction between polymeric composite resins and copper sulfate is a bond formation between the active groups of polymeric chains and copper ion. The bond formation depends on nature of polymeric chains. It was also found that the amide groups form complexes with hydrated cations, while carboxylate group interact by ion exchange mechanism through complex formation. Montmorillonite and hexacyanoferrate of the resins interact with metal ions by ion exchange mechanism

Crosslink the Novel Group of Polymeric Binders BioCo by the UV-radiation

Directory of Open Access Journals (Sweden)

Grabowska B.

2016-06-01

Full Text Available The spectroscopic FT-IR and FT-Raman methods allowed to identify the cross-linking process of the aqueous composition of poly(acrylic acid/sodium salt of carboxymethyl starch (PAA/CMS-Na applied as a binder for moulding sands (as a novel group binders BioCo. The cross-linking was performed by physical agent, applying the UV-radiation. The results of structural studies (IR, Raman confirm the overlapping of the process of cross-linking polymer composition PAA/CMS-Na in UV radiation. Taking into account the ingredients and structure of the polymeric composition can also refer to a curing process in a binder - mineral matrix mixture. In the system of binder-mineral matrix under the influence of ultraviolet radiation is also observed effect of binding. However, the bonding process does not occur in the entire volume of the investigated system, but only on the surface, which gives some possibilities for application in the use of UV curing surface of cores, and also to cure sand moulds in 3D printing technology.

Effect of tamoxifen in RAFT miniemulsion polymerization during the synthesis of polymer nanoparticles

Directory of Open Access Journals (Sweden)

Tailane Sant'Anna Moreira

2014-01-01

Full Text Available Tamoxifen (TXF is currently the only hormonal agent used for treatment of breast cancer. Although very effective, TXF presents low solubility in water, which affects its absorption and bioavailability. A common strategy to overcome this barrier is the formulation of a drug delivery system (DDS in order to increase the drug stability and improve the treatment effectiveness. Reversible addition-fragmentation chain transfer (RAFT polymerization is the most versatile method of controlled/living radical polymerization (CLRP, allowing for synthesis of well-defined polymers and being adapted to a wide range of polymerization systems. Miniemulsion polymerization is a dispersed system that is commonly used to prepare nanoparticles (NP with 50 to 500 nm of diameter. The aim of this work was to evaluate the effect of the in situ incorporation of TXF during miniemulsion conventional and RAFT polymerizations, using methyl methacrylate (MMA as monomer. Although the in situ addition of TXF promoted a slight reduction of the reaction rate, it did not affect the final particle size distribution of the latex or the molecular weight control exerted by the RAFT agent. The obtained results suggest that in situ incorporation of TXF during the synthesis of polymer NP via RAFT polymerization allows for production of a polymer DDS for different uses, such as the breast cancer treatment.

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.)

Polymer Light-Emitting Diode Prepared by Floating-Off Film-Transfer Technique

KAUST Repository

Park, Jihoon

2015-12-22

© 2015 Copyright Taylor & Francis Group, LLC. Floating-off film-transfer technique was used for the formation of semiconducting polymer multi-layers and the effect on the performance of polymer light-emitting diode (PLED) was studied. This method made it possible to avoid the solvent compatibility problem that was typically encountered in successive coating of polymeric multilayer by solution processing. F8BT and MEH-PPV were used for electron transporting layer (ETL) and for emissive layer, respectively. Current-voltage-luminance characteristics and luminescence efficiency results showed that the insertion of ETL by floating-off film-transfer technique followed by proper heat treatment resulted in a significant improvement in PLED operation due to its electron-transporting and hole-blocking abilities.

Synthesis of thermoresponsive poly(N-isopropylacrylamide) brush on silicon wafer surface via atom transfer radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Turan, Eylem; Demirci, Serkan [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey); Caykara, Tuncer, E-mail: caykara@gazi.edu.t [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey)

2010-08-31

Thermoresponsive poly(N-isopropylacrylamide) [poly(NIPAM)] brush on silicon wafer surface was prepared by combining the self-assembled monolayer of initiator and atom transfer radical polymerization (ATRP). The resulting polymer brush was characterized by in situ reflectance Fourier transform infrared spectroscopy, atomic force microscopy and ellipsometry techniques. Gel permeation chromatography determination of the number-average molecular weight and polydispersity index of the brush detached from the silicon wafer surface suggested that the surface-initiated ATRP method can provide relatively homogeneous polymer brush. Contact angle measurements exhibited a two-stage increase upon heating over the board temperature range 25-45 {sup o}C, which is in contrast to the fact that free poly(NIPAM) homopolymer in aqueous solution exhibits a phase transition at ca. 34 {sup o}C within a narrow temperature range. The first de-wetting transition takes place at 27 {sup o}C, which can be tentatively attributed to the n-cluster induced collapse of the inner region of poly(NIPAM) brush close to the silicon surface; the second de-wetting transition occurs at 38 {sup o}C, which can be attributed to the outer region of poly(NIPAM) brush, possessing much lower chain density compared to that of the inner part.

A phenomenological approach of solidification of polymeric phase change materials

Science.gov (United States)

Bahrani, Seyed Amir; Royon, Laurent; Abou, Bérengère; Osipian, Rémy; Azzouz, Kamel; Bontemps, André

2017-01-01

Phase Change Materials (PCMs) are widely used in thermal energy storage and thermal management systems due to their small volume for a given stored energy and their capability for maintaining nearly constant temperatures. However, their performance is limited by their low thermal conductivity and possible leaks while in the liquid phase. One solution is to imprison the PCM inside a polymer mesh to create a Polymeric Phase Change Material (PPCM). In this work, we have studied the cooling and solidification of five PPCMs with different PCMs and polymer fractions. To understand the heat transfer mechanisms involved, we have carried out micro- and macrorheological measurements in which Brownian motion of tracers embedded in PPCMs has been depicted and viscoelastic moduli have been measured, respectively. Beyond a given polymer concentration, it was shown that the Brownian motion of the tracers is limited by the polymeric chains and that the material exhibits an elastic behavior. This would suggest that heat transfer essentially occurs by conduction, instead of convection. Experiments were conducted to measure temperature variation during cooling of the five samples, and a semi-empirical model based on a phenomenological approach was proposed as a practical tool to choose and size PPCMs.

Effects of Molecular Iodine and 4-tert-Butylcatechol Radical Inhibitor on the Radical Polymerization of Styrene

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Mojtaba Bozorg

2017-05-01

Full Text Available The presence of molecular iodine was studied in relation the molecular weight and molecular weight distribution of polystyrene, produced by radical poly merization. Radical polymerization of styrene initiated by 2,2׳-azobisisobutyronitrile (AIBN was performed at 70°C in the presence of molecular iodine. The synthesized polymers were characterized by gel permeation chromatography (GPC and proton- nuclear magnetic resonance (1H NMR techniques. The results of these reactions including conversion data, number-average molecular weight and molecular weight distribution were compared with those obtained for styrene radical polymerization initiated by AIBN at the same temperature in the absence of molecular iodine. It was found that the presence of iodine had a profound effect on the molecular weight and its distribution in the produced polystyrene. This was attributed to the ability of iodine to control the polymerization of styrene initiated by AIBN via reverse iodine transfer polymerization (RITP mechanism. The polymer produced by this method had a molecular weight of 10600 g/mol with a molecular weight polydispersity index of 1.3. Due to the importance of induction period in reverse iodine transfer radical polymerization, increasing the temperature to 120°C during the induction period resulted in shorter induction periods and the produced species led to better control of the molecular weight. Also, due to the role of iodine molecules as a radical inhibitor, the presence of a secondary radical inhibitor, i.e. 4-tert-butylcatechol, along with the iodine was investigated in radical polymerization of polystyrene initiated by AIBN. It was observed that the secondary radical inhibitor prevented the consumption of the iodine molecules by the radicals produced from decomposition of the AIBN initiator; therefore, alkyl halides were not produced during the induction period.

Designing of fluorescent and magnetic imprinted polymer for rapid, selective and sensitive detection of imidacloprid via activators regenerated by the electron transfer-atom transfer radical polymerization (ARGET-ATRP) technique

Science.gov (United States)

Kumar, Sunil; Karfa, Paramita; Madhuri, Rashmi; Sharma, Prashant K.

2018-05-01

In this work, we report on a dual-behavior electrochemical/optical sensor for sensitive determination of Imidacloprid by fluorescent dye (fluorescein, FL) and imprinted polymer modified europium doped superparamagnetic iron oxide nanoparticles (FL@SPIONs@MIP). The imidacloprid (IMD)-imprinted polymer was directly synthesized on the Eu-SPIONs surface via Activators regenerated by the electron transfer-atom transfer radical polymerization (ARGET-ATRP) technique. Preparation, characterization and application of the prepared FL@SPIONs@MIP were systematically investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), fluorescence spectroscopy and electrochemical techniques. The electrochemical experiments exhibited a remarkable selectivity of the prepared sensor towards IMD. Determination of IMD by the square wave stripping voltammetry method represented a wide linear range of 0.059-0.791 μg L-1 with a detection limit of 0.0125 μg L-1. In addition, the fluorescence method shows a linear range of 0.039-0.942 μg L-1 and LOD of 0.0108 μg L-1. The fluorescence property of prepared FL@SPIONs@MIP was used for rapid, on-spot but selective detection of IMD in real samples. The proposed electrode displayed excellent repeatability and long-term stability and was successfully applied for quantitative and trace level determination of IMD in several real samples.

Concentration and measuring Platinum Group Elements (PGE) Transfer Factor in soil and vegetations

International Nuclear Information System (INIS)

Adibah Sakinah Oyub

2012-01-01

This study was conducted to determine the concentration and to measure platinum group elements (PGE) transfer factor in environmental samples of roadside soil and vegetation. The use of vehicle catalytic converter has released platinum group elements (PGE) and other gases into the environment. Thus, roadside soil and plants were exposed to this element and has become the medium for the movement of this elements. Samples of roadside soil and vegetation were taken at various locations in UKM Bangi Toll and the concentration of platinum group elements (PGE) is determined using mass spectrometry-inductively coupled plasma (ICP-MS). Overall, the concentrations of platinum group elements (PGE), which is the element platinum (Pt) in soil was 0.016 ± 0.036 μgg -1 . While the concentration of the elements palladium (Pd) was 0.079 ± 0.019 μgg -1 and element rhodium (Rh) is at a concentration of 0.013 ± 0.020 μgg -1 . Overall, the transfer factor for the element platinum (Pt) is 1. While the transfer factor of the element palladium (Pd) is 0.96 and the element rhodium (Rh) is 1.11. In conclusion, the concentration of platinum group elements (PGE) in soils have increased. (author)

A One-Step Route to CO2 -Based Block Copolymers by Simultaneous ROCOP of CO2 /Epoxides and RAFT Polymerization of Vinyl Monomers.

Science.gov (United States)

Wang, Yong; Zhao, Yajun; Ye, Yunsheng; Peng, Haiyan; Zhou, Xingping; Xie, Xiaolin; Wang, Xianhong; Wang, Fosong

2018-03-26

The one-step synthesis of well-defined CO 2 -based diblock copolymers was achieved by simultaneous ring-opening copolymerization (ROCOP) of CO 2 /epoxides and RAFT polymerization of vinyl monomers using a trithiocarbonate compound bearing a carboxylic group (TTC-COOH) as the bifunctional chain transfer agent (CTA). The double chain-transfer effect allows for independent and precise control over the molecular weight of the two blocks and ensures narrow polydispersities of the resultant block copolymers (1.09-1.14). Notably, an unusual axial group exchange reaction between the aluminum porphyrin catalyst and TTC-COOH impedes the formation of homopolycarbonates. By taking advantage of the RAFT technique, it is able to meet the stringent demand for functionality control to well expand the application scopes of CO 2 -based polycarbonates. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Sonolytic and Silent Polymerization of Methacrlyic Acid Butyl Ester Catalyzed by a New Onium Salt with bis-Active Sites in a Biphasic System — A Comparative Investigation

Directory of Open Access Journals (Sweden)

Perumberkandgai A. Vivekanand

2013-02-01

Full Text Available Currently, ingenious new analytical and process experimental techniques which are environmentally benign techniques, viz., ultrasound irradiation, have become immensely popular in promoting various reactions. In this work, a novel soluble multi-site phase transfer catalyst (PTC viz., 1,4-bis-(propylmethyleneammounium chloridebenzene (BPMACB was synthesized and its catalytic efficiency was assessed by observing the kinetics of sonolytic polymerization of methacrylic acid butyl ester (MABE using potassium persulphate (PPS as an initiator. The ultrasound–multi-site phase transfer catalysis (US-MPTC-assisted polymerization reaction was compared with the silent (non-ultrasonic polymerization reaction. The effects of the catalyst and various reaction parameters on the catalytic performance were in detail investigated by following the kinetics of polymerization of MABE in an ethyl acetate-water biphasic system. From the detailed kinetic investigation we propose a plausible mechanism. Further the kinetic results demonstrate clearly that ultrasound-assisted phase-transfer catalysis significantly increased the reaction rate when compared to silent reactions. Notably, this environmentally benign and cost-effective process has great potential to be applied in various polymer industries.

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

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

Electrospun polymeric nanofibers for transdermal drug delivery

Directory of Open Access Journals (Sweden)

Mahya Rahmani

2017-04-01

Full Text Available Conventional transdermal drug delivery systems (TDDS have been designed for drug delivery through the skin. These systems use the permeability property of stratum corneum, the outermost surface layer of the skin. Applying polymeric micro and nanofibers in drug delivery has recently attracted great attention and the electrospinning technique is the preferred method for polymeric micro-nanofibers fabrication with a great potential for drug delivery. More studies in the field of nanofibers containing drug are divided two categories: first, preparation and characterization of nanofibers containing drug and second, investigation of their therapeutic applications. Drugs used in electrospun nanofibers can be categorized into three main groups, including antibiotics and antimicrobial agents, anti-inflammatory agents and vitamins with therapeutic applications. In this paper, we review the application of electrospun polymeric scaffolds in TDDS and also introduce several pharmaceutical and therapeutic agents which have been used in polymer nanofibrous patches.

Imidazoline and imidazolidine nitroxides as controlling agents in nitroxide-mediated pseudoliving radical polymerization

Science.gov (United States)

Edeleva, M. V.; Marque, S. R. A.; Bagryanskaya, E. G.

2018-04-01

Controlled, or pseudoliving, radical polymerization provides unique opportunities for the synthesis of structurally diverse polymers with a narrow molecular-weight distribution. These reactions occur under relatively mild conditions with broad tolerance to functional groups in the monomers. The nitroxide-mediated pseudoliving radical polymerization is of particular interest for the synthesis of polymers for biomedical applications. This review briefly describes one of the mechanisms of controlled radical polymerization. The studies dealing with the use of imidazoline and imidazolidine nitroxides as controlling agents for nitroxide-mediated pseudoliving radical polymerization of various monomers are summarized and analyzed. The publications addressing the key steps of the controlled radical polymerization in the presence of imidazoline and imidazolidine nitroxides and new approaches to nitroxide-mediated polymerization based on protonation of both nitroxides and monomers are considered. The bibliography includes 154 references.

Transferable tight-binding model for strained group IV and III-V materials and heterostructures

Science.gov (United States)

Tan, Yaohua; Povolotskyi, Michael; Kubis, Tillmann; Boykin, Timothy B.; Klimeck, Gerhard

2016-07-01

It is critical to capture the effect due to strain and material interface for device level transistor modeling. We introduce a transferable s p3d5s* tight-binding model with nearest-neighbor interactions for arbitrarily strained group IV and III-V materials. The tight-binding model is parametrized with respect to hybrid functional (HSE06) calculations for varieties of strained systems. The tight-binding calculations of ultrasmall superlattices formed by group IV and group III-V materials show good agreement with the corresponding HSE06 calculations. The application of the tight-binding model to superlattices demonstrates that the transferable tight-binding model with nearest-neighbor interactions can be obtained for group IV and III-V materials.

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.

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.

Controlled radical polymerization of an acrylamide containing L-alanine moiety via ATRP.

Science.gov (United States)

Rafiee, Zahra

2016-02-01

Homopolymerization of an optically active acrylamide having an amino acid moiety in the side chain, N-acryloyl-L-alanine (AAla) was carried out via atom transfer radical polymerization (ATRP) at room temperature using 2-hydroxyethyl-2'-methyl-2'-bromopropionate (HMB) or sodium-4-(bromomethyl)benzoate (SBB) as initiator in pure water, methanol/water mixture and pure methanol solvents. The polymerization reaction resulted in the optically active biocompatible amino acid-based homopolymer in good yield with narrow molecular weight distribution. The number average molecular weight increased with conversion and polydispersity was low. The structure and molecular weight of synthesized polymer were characterized by (1)H NMR, FT-IR spectroscopic techniques and size-exclusion chromatography.

Study by neutron diffusion of local order liquid sulfur around the polymerization transition

International Nuclear Information System (INIS)

Descotes, L.

1994-05-01

We studied the liquid sulfur according to the temperature. The sulfur is one of the most complicated elementary liquid. We experimented the neutron diffusion by the powder orthorhombic sulfur. The complexity at the polymerization transition are only accompanied by weak local structural transfer. 231 refs., 48 figs., 8 tabs., 3 annexes

Synthesis of amphiphilic poly(ε-caprolactone)-b-poly( N-vinylcaprolactam) block copolymers via the combination of RAFT polymerization and click chemistry

International Nuclear Information System (INIS)

Assis, Paulo Henrique; Aguiar, Graziele Aparecida de Jesus; Moraes, Rodolfo Minto de; Medeiros, Simone de Fatima; Santos, Amilton Martins

2016-01-01

Full text: In recent years, well-defined block copolymers composed of a hydrophilic and hydrophobic segments have gained much interest as drug carriers, because of their enhanced solubility and sustained release of the drug in controlled delivery systems [1]. The development of strategies to obtain block copolymers has attracted considerable attention, due to the possibility to combine characteristic properties of the homopolymers. A wide variety of well-defined block copolymers have been successfully synthesized by combining the efficiency and selectivity of click chemistry with the powerful RAFT polymerization mechanism. In the present work, well-defined amphiphilic, biocompatible, partially biodegradable, and thermosensitive poly(ε-caprolactone)-b-poly(N-vinylcaprolactam) (PCL-b-PNVCL) block copolymers were synthesized by combining ring opening polymerization (ROP), reversible addition-fragmentation chain transfer (RAFT) polymerization and subsequent click chemistry reaction. Alkyne-terminated poly(ε-caprolactone) (alkyne-PCL) was obtained by the ring opening polymerization of ε-caprolactone (ε-CL) using propargyl alcohol as initiator and stannous-2-ethylhexanoate [Sn(Oct) 2 ] as catalyst. The azide end-capped-poly(N-vinylcaprolactam) (PNVCL-N 3 ) was synthesized by reversible addition-fragmentation chain transfer/macromolecular design via interchange of xanthates (RAFT/MADIX) polymerization of the N-vinylcaprolactam (NVCL) mediated by a novel chain transfer agent comprising an azide function , 2-azidoethyl[(ethoxycarbonothioyl)thio](phenyl)acetate. These functionalized homopolymers, alkyne-PCL and PNVCL-N 3 , were coupled by the 1,3 dipolar cycloaddition reaction in order to obtain the corresponding block copolymers. These (co)polymers were characterized by FTIR, 1 H NMR and GPC measurements. Reference: 1. RAMESH, K., SINGH, S., MITRA, K., CHATTOPADHYAY, D., MISRA, N., & RAY, B. (2015). Colloid and Polymer Science, 1-9. (author)

Rapid long range intramolecular electron transfer within a steroid molecule with two electron binding groups

International Nuclear Information System (INIS)

Huddleston, R.K.; Miller, J.R.

1983-01-01

Intramolecular electron transfer has been observed to have occurred in less than 100 ns in a steroid molecule having two distinct electron binding groups separated by distances distributed from 7--11 A. Experiments were carried out in organic glasses at 77 K with pulse radiolysis techniques to create trapped electrons which were captured by a group on one end of the steroid molecule. Although one of the groups, benzoate, is held to the steroid spacer by a flexible linkage, the rigidity of the glassy matrices prevented movement to alter the initial distance. Interestingly, no effects of distance were seen: all ET processes appeared to have occurred much faster than our 100 ns time resolution, consistent with measurements of the rate of intermolecular electron transfer between the same functional groups in random solutions. Solvation energetics, on the other hand, had a remarkable influence on the extent and direction of electron transfer. A change in solvent polarity was observed to reverse the direction of electron transfer. Evidence was obtained for a distribution of solvation environments for ions in glasses which may be as broad as 0.15 eV

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

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.

Precise synthesis of thermoreversible block copolymers containing reactive furfuryl groups via living anionic polymerization: the countercation effect on block copolymerization behavior

Energy Technology Data Exchange (ETDEWEB)

Kang, Beom-Goo [ORNL; Pramanik, Nabendu [Indian Institute of Technology, Kharagpur; Singha, Nikhil K [ORNL; Lee, Jae-Suk [ORNL; Mays, Jimmy [University of Tennessee, Knoxville (UTK)

2015-08-07

The anionic block copolymerization of 4,4' -vinylphenyl-N,N-bis(4-tert-butylphenyl)benzenamine (A) with furfuryl isocyanate (B) was carried out using potassium naphthalenide (K-Naph) in tetrahydrofuran at -78 and -98 °C to prepare well-defined block copolymers containing furan groups for the formation of thermoreversible networks via a Diels Alder (DA) reaction. While no block copolymerization was observed in the absence of sodium tetraphenylborate (NaBPh₄) due to side reactions, well-defined poly-(B-b-A-b-B) (PBAB) copolymers with controlled molecular weights (M_n = 18 700 19 500 g mol ^-1) and narrow molecular weight distributions (M_w/M_n = 1.08 -1.17) were successfully synthesized in the presence of excess NaBPh₄. We prevented the occurrence of the undesirable side reactions during polymerization of B of NaBPh₄, which results in the change in the countercation from K⁺ to Na⁺ for further polymerization of B. Moreover, the cross-linking via the DA reaction between the furan groups of PBAB and bismaleimide was proved by FT-IR and differential scanning calorimetry (DSC), and the thermoreversible properties of the cross-linked polymer were subsequently investigated using DSC and solubility testing.

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.

Development of polymeric nanoparticles showing tuneable pH-responsive precipitation

Energy Technology Data Exchange (ETDEWEB)

Vakurov, Alexander, E-mail: a.v.vakourov@bmb.leeds.ac.uk; Pchelintsev, Nikolay A., E-mail: n.a.pchelintsev@googlemail.com; Gibson, Tim, E-mail: timdgibson@merchab.fsnet.co.uk; Millner, Paul, E-mail: p.a.millner@leeds.ac.uk [Research Institute of Membrane and Systems Biology, University of Leeds (United Kingdom)

2012-12-15

A reverse micellar system comprising dioctyl-sulfosuccinate (AOT)/toluene was used as a template for polymerization of acrylamide/bisacrylamide-based functionalized polymeric nanoparticles. Such nanoparticles were typically sized between 20 and 90 nm and could be synthesized with a wide range of functional groups according to the monomers added to the polymerization mixture. Carboxy nanoparticles with acrylic acid as the functional monomer were synthesized in the reported work. The carboxy nanoparticles were pH sensitive and precipitated at pHs below 4. Modification of carboxy-functionalized polymeric nanoparticles with polyetheleneimine (PEI) resulted in the fabrication of a series of pH-responsive nanoparticles which could precipitate at different pHs and ionic strengths according to the PEI/carboxy ratio in the system. Both non-covalent PEI-nanoparticles conjugates and nanoparticles with covalently linked PEI behaved in this way.

Development of polymeric nanoparticles showing tuneable pH-responsive precipitation

International Nuclear Information System (INIS)

Vakurov, Alexander; Pchelintsev, Nikolay A.; Gibson, Tim; Millner, Paul

2012-01-01

A reverse micellar system comprising dioctyl-sulfosuccinate (AOT)/toluene was used as a template for polymerization of acrylamide/bisacrylamide-based functionalized polymeric nanoparticles. Such nanoparticles were typically sized between 20 and 90 nm and could be synthesized with a wide range of functional groups according to the monomers added to the polymerization mixture. Carboxy nanoparticles with acrylic acid as the functional monomer were synthesized in the reported work. The carboxy nanoparticles were pH sensitive and precipitated at pHs below 4. Modification of carboxy-functionalized polymeric nanoparticles with polyetheleneimine (PEI) resulted in the fabrication of a series of pH-responsive nanoparticles which could precipitate at different pHs and ionic strengths according to the PEI/carboxy ratio in the system. Both non-covalent PEI-nanoparticles conjugates and nanoparticles with covalently linked PEI behaved in this way.

Hydrogel brushes grafted from stainless steel via surface-initiated atom transfer radical polymerization for marine antifouling

Energy Technology Data Exchange (ETDEWEB)

Wang, Jingjing, E-mail: jjwang1@hotmail.com; Wei, Jun

2016-09-30

Highlights: • Crosslinked hydrogel brushes were grafted from SS surfaces for marine antifouling. • All brush-coated SS surfaces could effectively reduce the adhesion of biofouling. • The antifouling efficacy increased with the crosslinking density of hydrogels. - Abstract: Crosslinked hydrogel brushes were grafted from stainless steel (SS) surfaces for marine antifouling. The brushes were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) respectively with different fractions of crosslinker in the feed. The grafted layers prepared with different thickness were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), ellipsometry and water contact angle measurements. With the increase in the fraction of crosslinker in the feed, the thickness of the grafted layer increased and the surface became smooth. All the brush-coated SS surfaces could effectively reduce the adhesion of bacteria and microalgae and settlement of barnacle cyprids, as compared to the pristine SS surface. The antifouling efficacy of the PEGMA polymer (PPEGMA)-grafted surface was higher than that of the MPC polymer (PMPC)-grafted surfaces. Furthermore, the crosslinked hydrogel brush-grafted surfaces exhibited better fouling resistance than the non-crosslinked polymer brush-grafted surfaces, and the antifouling efficacy increased with the crosslinking density. These hydrogel coatings of low toxicity and excellent anti-adhesive characteristics suggested their useful applications as environmentally friendly antifouling coatings.

Hydrogel brushes grafted from stainless steel via surface-initiated atom transfer radical polymerization for marine antifouling

International Nuclear Information System (INIS)

Wang, Jingjing; Wei, Jun

2016-01-01

Highlights: • Crosslinked hydrogel brushes were grafted from SS surfaces for marine antifouling. • All brush-coated SS surfaces could effectively reduce the adhesion of biofouling. • The antifouling efficacy increased with the crosslinking density of hydrogels. - Abstract: Crosslinked hydrogel brushes were grafted from stainless steel (SS) surfaces for marine antifouling. The brushes were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) respectively with different fractions of crosslinker in the feed. The grafted layers prepared with different thickness were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), ellipsometry and water contact angle measurements. With the increase in the fraction of crosslinker in the feed, the thickness of the grafted layer increased and the surface became smooth. All the brush-coated SS surfaces could effectively reduce the adhesion of bacteria and microalgae and settlement of barnacle cyprids, as compared to the pristine SS surface. The antifouling efficacy of the PEGMA polymer (PPEGMA)-grafted surface was higher than that of the MPC polymer (PMPC)-grafted surfaces. Furthermore, the crosslinked hydrogel brush-grafted surfaces exhibited better fouling resistance than the non-crosslinked polymer brush-grafted surfaces, and the antifouling efficacy increased with the crosslinking density. These hydrogel coatings of low toxicity and excellent anti-adhesive characteristics suggested their useful applications as environmentally friendly antifouling coatings.

Endogenous Oxytocin Release Eliminates In-Group Bias in Monetary Transfers With Perspective-Taking

Directory of Open Access Journals (Sweden)

Elizabeth T. Terris

2018-03-01

Full Text Available Oxytocin (OT has been shown to facilitate trust, empathy and other prosocial behaviors. At the same time, there is evidence that exogenous OT infusion may not result in prosocial behaviors in all contexts, increasing in-group biases in a number of studies. The current investigation seeks to resolve this inconsistency by examining if endogenous OT release is associated with in-group bias. We studied a large group of participants (N = 399 in existing groups and randomly formed groups. Participants provided two blood samples to measure the change in OT after a group salience task and then made computer-mediated monetary transfer decisions to in-group and out-group members. Our results show that participants with an increase in endogenous OT showed no bias in monetary offers in the ultimatum game (UG to out-group members compared to in-groups. There was also no bias in accepting UG offers, though in-group bias persisted for a unilateral monetary transfer. Our analysis shows that the strength of identification with one’s group diminished the effects that an increase in OT had on reducing bias, but bias only recurred when group identification reached 87% of its maximum value. Our results indicate that the endogenous OT system appears to reduce in-group bias in some contexts, particularly those that require perspective-taking.

Endogenous Oxytocin Release Eliminates In-Group Bias in Monetary Transfers With Perspective-Taking.

Science.gov (United States)

Terris, Elizabeth T; Beavin, Laura E; Barraza, Jorge A; Schloss, Jeff; Zak, Paul J

2018-01-01

Oxytocin (OT) has been shown to facilitate trust, empathy and other prosocial behaviors. At the same time, there is evidence that exogenous OT infusion may not result in prosocial behaviors in all contexts, increasing in-group biases in a number of studies. The current investigation seeks to resolve this inconsistency by examining if endogenous OT release is associated with in-group bias. We studied a large group of participants ( N = 399) in existing groups and randomly formed groups. Participants provided two blood samples to measure the change in OT after a group salience task and then made computer-mediated monetary transfer decisions to in-group and out-group members. Our results show that participants with an increase in endogenous OT showed no bias in monetary offers in the ultimatum game (UG) to out-group members compared to in-groups. There was also no bias in accepting UG offers, though in-group bias persisted for a unilateral monetary transfer. Our analysis shows that the strength of identification with one's group diminished the effects that an increase in OT had on reducing bias, but bias only recurred when group identification reached 87% of its maximum value. Our results indicate that the endogenous OT system appears to reduce in-group bias in some contexts, particularly those that require perspective-taking.

Biodegradable Polyelectrolyte Obtained by Radiation Polymerization

International Nuclear Information System (INIS)

Craciun, G.; Martin, D.; Manaila, E.; Nemtanu, M.; Brasoveanu, M.; Ighigeanu, D.

2009-01-01

, due to the rapid, volumetric and selective MW energy transfer, the molecular weight dispersion of the polymeric material is very low. 2) Development of more efficacious methods for Pn application to potable water (PW) and waste water (WW) treatment. The Pan obtained by EB and EB + MW induced polymerization give the best results for TSS (total suspended solid) and T (turbidity) indicators in the PW case while Pn types obtained by MW induced polymerization give always the best results for OM (organic matters) and TOC (total organic carbon) indicators in the WW case. Also, each quality indicator is associated with a certain amount and a certain type of Pn, which exhibits the maximum ability to its reduction. For a given Pn type there is a different amount for each quality indicator, which gives the best result. These aspects have suggested to mix several Pn types (the best for each quality indicator) and to use their mixture (Mn) for water treatment. The use of mixture (Mn) of several Pn types demonstrated the ability in the simultaneous reduction of several quality indicators for PW as well as for WW

γ-Diimine palladium(II based complexes mediated polymerization of methyl methacrylate

Directory of Open Access Journals (Sweden)

Mahmoud Sunjuk

2017-02-01

Full Text Available The synthesis of new palladium(II complexes of the type [Pd(A–NC–ph–CN–ACl2] (4a–e (A = cyclohexyl (a, 2-isoprpropyl (b, pyrenyl (c, naphthyl (d, and 2,6-diisopropyl (e is described. The isolated γ-diimine ligands and their corresponding palladium(II complexes were characterized by their physical properties, elemental analysis, 1H NMR-, 13C NMR, and infrared spectroscopy. The palladium(II complexes (4a–e were employed successfully as catalysts for atom transfer radical polymerization (ATRP of methyl methacrylate (MMA in the presence of ethyl-2-bromoisobutyrate (EBIB as initiator at 90 °C. Polymerization with these catalyst systems afforded polymers with low molecular weight distribution (Mw/Mn and syndio-rich atactic poly (MMA with relatively higher [rr] diads.

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

Hydrophilic crosslinked-polymeric surface capable of effective suppression of protein adsorption

Energy Technology Data Exchange (ETDEWEB)

Kamon, Yuri; Inoue, Naoko; Mihara, Erika; Kitayama, Yukiya; Ooya, Tooru; Takeuchi, Toshifumi, E-mail: takeuchi@gold.kobe-u.ac.jp

2016-08-15

Highlights: • Three hydrophilic crosslinked polymers were examined for protein adsorption. • All polymers showed low nonspecific adsorption of negatively charged proteins. • Poly(MMPC) showed the lowest adsorption for positively charged proteins. • Poly(MMPC) is able to reduce nonspecific adsorption of a wide range of proteins. - Abstract: We investigated the nonspecific adsorption of proteins towards three hydrophilic crosslinked-polymeric thin layers prepared by surface-initiated atom transfer radical polymerization using N,N′-methylenebisacrylamide, 2-(methacryloyloxy)ethyl-[N-(2-methacryloyloxy)ethyl]phosphorylcholine (MMPC), or 6,6′-diacryloyl-trehalose crosslinkers. Protein binding experiments were performed by surface plasmon resonance with six proteins of different pI values including α-lactalbumin, bovine serum albumin (BSA), myoglobin, ribonuclease A, cytochrome C, and lysozyme in buffer solution at pH 7.4. All of the obtained crosslinked-polymeric thin layers showed low nonspecific adsorption of negatively charged proteins at pH 7.4 such as α-lactalbumin, BSA, and myoglobin. Nonspecific adsorption of positively charged proteins including ribonuclease A, cytochrome C, and lysozyme was the lowest for poly(MMPC). These results suggest poly(MMPC) can effectively reduce nonspecific adsorption of a wide range of proteins that are negatively or positively charged at pH 7.4. MMPC is a promising crosslinker for a wide range of polymeric materials requiring low nonspecific protein binding.

Grafting of Polystyrene Chains at the Edge of Graphene Nanolayers by "Grafting Through" Approach Using Reversible Addition-Fragmentation Chain Transfer Polymerization

Directory of Open Access Journals (Sweden)

Hossein Roghani-Mamaqani

2017-09-01

Full Text Available Edge-functionalized graphene nanolayers with polystyrene chains were prepared by a “grafting through” reversible addition-fragmentation chain transfer (RAFT polymerization. For this purpose, double-bond containing modifier (MD was prepared. After edge-functionalization of graphene oxide (GO by two different amounts of MD and preparation of modified graphenes (LFG and HFG, RAFT polymerization of styrene was applied for preparation of functionalized GO with different densities of polystyrene chains. Fourier transform infrared spectroscopy showed that MD and polystyrene chains were grafted at the edge of GO. Gas chromatography showed that conversion decreased by the addition of modified GO content and also grafting density of MD. Number-average molecular weight and polydispersity index of polystyrene chains were derived from gel permeation chromatography. Increase of modified graphene content results in a decrease in molecular weight of attached polystyrene chains and also an increase in their PDI value. Increase of grafting density of MD results in decrease of molecular weight of polystyrene chains with no considerable variation in PDI value. Thermogravimetric analysis results showed that char residue is about 45.1 and 46.8% for LFG and HFG, respectively. The content of degradation ascribed to polystyrene increased with increase of grafting density of MD and decreased with increase of modified graphene content. X-ray diffraction results were used for evaluation of interlayer spacing of graphene layers after functionalization process and also study of nanocomposites structure. The results of scanning electron microscopy and transmission electron microscopy show that graphene layers with high clarity turned to opaque layers with lots of creases by oxidation and attachment of polystyrene chains.

Donor-π-bridge-acceptor type polymeric materials with pendant electron-withdrawing groups for electrochromic applications

International Nuclear Information System (INIS)

Du, Qing; Wei, Youxiu; Zheng, Jianming; Xu, Chunye

2014-01-01

Highlights: • Donor-π-bridge-acceptor copolymers with different electrophilic groups were synthesized. • Electrochromic devices composed of PBDTTPAs layers, as the working electrode, and vanadium pentoxide, as the counter electrode, were fabricated and evaluated. • The PBDTTPA-CHO film and device show multicolor electrochromic behavior which exhibited vivid yellow, green, and gray with better electrochromic performance than PBDTTPA-COOH. - Abstract: A novel donor-π-bridge-acceptor copolymer, PBDTTPA-CHO, containing 4-(Bis(4-bromophenyl)-amino)benzaldehyde (TPA-CHO) and 4,8-bis-(2-ethyl- hexyloxy)-oxybenzo-[1,2-b:3,4-b’]dithiophene (BDT), was successfully synthesized using Stille coupling polymerization, and the pendant aldehyde group was modified with cyanoacetic acid to synthesize another polymer, PBDTTPA-COOH. Each of these new polymers are soluble in organic solvents and can be cast onto rigid or flexible substrates. The polymers with different electrophilic groups exhibit different electrochromic behaviors, including different colors, driving voltages and transmittances. The polymer film of PBDTTPA-CHO manifests reversible electrochemical oxidation and reduction accompanied by multicolor changes from its yellow neutral state to a highly absorbent green semi-oxidized state and a gray fully oxidized state, its transmittance change at 601 nm is 43%. PBDTTPA-COOH switches between orange and light green. We fabricated and evaluated electrochromic devices using a PBDTTPA layer as the working electrode and vanadium pentoxide as the counter electrode. With the contribution of counter electrodes, devices of both polymers show similar color changes but higher transmittance than their films

Group Differences in California Community College Transfers

Science.gov (United States)

Budd, Deborah; Stowers, Genie N. L.

2015-01-01

This study explores the extent to which community colleges succeed in assisting students to transfer to four-year colleges. The study uses data from the California Community College system to test hypotheses about overall transfers and transfers of underrepresented students, It utilizes a framework based upon social reproduction theory (Bowles…

Comb-like thermoresponsive polymeric materials : Synthesis and effect of macromolecular structure on solution properties

NARCIS (Netherlands)

Wever, D. A. Z.; Riemsma, E.; Picchioni, F.; Broekhuis, A. A.

2013-01-01

A series of comb-like block and random copolymers based on acrylamide (AM) and N-isopropylacrylamide (NIPAM) have been prepared by atom transfer radical polymerization (ATRP). The number of side-arms, the length of the AM and NIPAM blocks as well as the distribution of the two monomers (block or

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.

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.

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.

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.

Construction of dual-functional polymer nanomaterials with near-infrared fluorescence imaging and polymer prodrug by RAFT-mediated aqueous dispersion polymerization.

Science.gov (United States)

Tian, Chun; Niu, Jinyun; Wei, Xuerui; Xu, Yujie; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2018-05-31

The performance of functional polymer nanomaterials is a vigorously discussed topic in polymer science. We devoted ourselves to investigating polymer nanomaterials based on near-infrared (NIR) fluorescence imaging and polymer prodrug in this study. Aza-boron dipyrromethene (BODIPY) is an important organic dye, having characteristics such as environmental resistance, light resistance, high molar extinction coefficient, and fluorescence quantum yield. We incorporated it into our target monomer, which can be polymerized without changing its parent structure in a polar solvent and copolymerized with water-soluble monomer to improve the solubility of the dye in an aqueous solution. At the same time, the hydrophobic drug camptothecin (CPT) was designed as a prodrug monomer, and the polymeric nanoparticles (NPs) with NIR fluorescence imaging and prodrug were synthesized in situ in reversible addition-fragmentation chain transfer (RAFT)-mediated aqueous dispersion polymerization. The dynamic light scattering (DLS) and transmission electron microscopy (TEM) revealed the final uniform size of the dual-functional polymeric NPs morphology. The dual-functional polymeric NPs had a strong absorption and emission signal in the NIR region (>650 nm) based on the fluorescence tests. In consideration of the long-term biological toxicity, confocal laser scanning microscopy (CLSM) results indicated that the dual-functional NPs with controlled drug content exhibited effective capability of killing HeLa cells. In addition, in vivo imaging of the dual-functional NPs was observed in real time, and the fluorescent signals clearly demonstrated the dynamic process of prodrug transfer.

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...

Dynamic bioactive stimuli-responsive polymeric surfaces

Science.gov (United States)

Pearson, Heather Marie

This dissertation focuses on the design, synthesis, and development of antimicrobial and anticoagulant surfaces of polyethylene (PE), polypropylene (PP), and poly(tetrafluoroethylene) (PTFE) polymers. Aliphatic polymeric surfaces of PE and PP polymers functionalized using click chemistry reactions by the attachment of --COOH groups via microwave plasma reactions followed by functionalization with alkyne moieties. Azide containing ampicillin (AMP) was synthesized and subsequently clicked into the alkyne prepared PE and PP surfaces. Compared to non-functionalized PP and PE surfaces, the AMP clicked surfaces exhibited substantially enhanced antimicrobial activity against Staphylococcus aureus bacteria. To expand the biocompatibility of polymeric surface anticoagulant attributes, PE and PTFE surfaces were functionalized with pH-responsive poly(2-vinyl pyridine) (P2VP) and poly(acrylic acid) (PAA) polyelectrolyte tethers terminated with NH2 and COOH groups. The goal of these studies was to develop switchable stimuli-responsive polymeric surfaces that interact with biological environments and display simultaneous antimicrobial and anticoagulant properties. Antimicrobial AMP was covalently attached to --COOH terminal ends of protected PAA, while anticoagulant heparin (HEP) was attached to terminal --NH2 groups of P2VP. When pH 5.5, they collapse while the PAA segments extend. Such surfaces, when exposed to Staphylococcus aureus, inhibit bacterial growth due to the presence of AMP, as well as are effective anticoagulants due to the presence of covalently attached HEP. Comparison of these "dynamic" pH responsive surfaces with "static" surfaces terminated with AMP entities show significant enhancement of longevity and surface activity against microbial film formation. The last portion of this dissertation focuses on the covalent attachment of living T1 and Φ11 bacteriophages (phages) on PE and PTFE surface. This was accomplished by carbodiimide coupling between --COOH

Evaluation of polymerization shrinkage, polymerization shrinkage stress, wear resistance, and compressive strength of a silorane-based composite: A finite element analysis study

Directory of Open Access Journals (Sweden)

Suresh Mitthra

2017-01-01

Full Text Available Background: Understanding the mechanical properties is important in predicting the clinical behavior of composites. Finite element analysis (FEA evaluates properties of materials replicating clinical scenario. Aim: This study evaluated polymerization shrinkage and stress, wear resistance (WR, and compressive strength (CS of silorane in comparison with two methacrylate resins. Settings and Design: This study design was a numerical study using FEA. Materials and Methods: Three-dimensional (3D models of maxillary premolar with Class I cavities (2 mm depth, 4 mm length, and 2.5 mm width created and restored with silorane, nanohybrid, and microhybrid; Groups I, II, and III, respectively. Loads of 200–600 N were applied. Polymerization shrinkage was first determined by displacement produced in the X, Y, and Z planes. Maximum stress distribution due to shrinkage was calculated using AN SYS software. 3D cube models of composite resins were simulated with varying filler particle size. Similar loads were applied. WR and compressive stress were calculated: K W L/H and load/cross-sectional area, respectively. Statistical analysis done using one-way ANOVA, Kruskal–Wallis, and Tukey's honestly significant difference test (P < 0.05. Results: Polymerization shrinkage (0.99% and shrinkage stress (233.21 Mpa of silorane were less compared to microhybrid (2.14% and 472.43 Mpa and nanohybrid (2.32% and 464.88 Mpa. Silorane (7.92×/1011 μm/mm3 and nanohybrid (7.79×/1011 showed superior WR than microhybrid (1.113×/1017. There was no significant difference in compressive stress among the groups. Conclusion: Silorane exhibited less polymerization shrinkage and shrinkage stress compared to methacrylates. Silorane and nanohybrid showed greater WR compared to microhybrid. CS of all groups was similar.

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

Synthesis and Characterization of Novel Polymethylene-Based 3-Miktoarm Star Copolymers by Combining Polyhomologation with Other Living Polymerizations

KAUST Repository

Altaher, Maryam

2015-01-01

Polyethylene (PE) is produced in a huge scale globally and has plenty of desirable properties. It is used in coating, packaging, and artificial joint replacements. The growing need for high performance polyethylene led to the development of new catalysts, monomers and polymerizations. The synthesis of polymethylene (equivalent to polyethylene) by living polyhomologation opened the way to well-defined polymethylenes-based polymeric materials with controlled structure, molecular weight and narrow polydispersity. Such model polymers are substantial to study the structure-properties relationships. This research presents a new strategy based on the in situ formation of B-thexyl-silaboracyclic serving as initiating sites for the polyhomologation of dimethylsulfoxonium methylide. Combination with metal-free ring-opening polymerization (ROP) of ɛ-caprolactone (CL) and atom transfer radical polymerization (ATRP) of styrene led to three polymethylene-based 3-miktoarm stars copolymers PCL(PM-OH)2, Br-PCL(PM-OH)2 and PS(PM-OH)2.

Synthesis and Characterization of Novel Polymethylene-Based 3-Miktoarm Star Copolymers by Combining Polyhomologation with Other Living Polymerizations

KAUST Repository

Altaher, Maryam

2015-05-01

Polyethylene (PE) is produced in a huge scale globally and has plenty of desirable properties. It is used in coating, packaging, and artificial joint replacements. The growing need for high performance polyethylene led to the development of new catalysts, monomers and polymerizations. The synthesis of polymethylene (equivalent to polyethylene) by living polyhomologation opened the way to well-defined polymethylenes-based polymeric materials with controlled structure, molecular weight and narrow polydispersity. Such model polymers are substantial to study the structure-properties relationships. This research presents a new strategy based on the in situ formation of B-thexyl-silaboracyclic serving as initiating sites for the polyhomologation of dimethylsulfoxonium methylide. Combination with metal-free ring-opening polymerization (ROP) of ɛ-caprolactone (CL) and atom transfer radical polymerization (ATRP) of styrene led to three polymethylene-based 3-miktoarm stars copolymers PCL(PM-OH)2, Br-PCL(PM-OH)2 and PS(PM-OH)2.

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.

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)

Conjugation of diisocyanate side chains to dimethacrylate reduces polymerization shrinkage and increases the hardness of composite resins.

Science.gov (United States)

Jan, Yih-Dean; Lee, Bor-Shiunn; Lin, Chun-Pin; Tseng, Wan-Yu

2014-04-01

Polymerization shrinkage is one of the main causes of dental restoration failure. This study tried to conjugate two diisocyanate side chains to dimethacrylate resins in order to reduce polymerization shrinkage and increase the hardness of composite resins. Diisocyanate, 2-hydroxyethyl methacrylate, and bisphenol A dimethacrylate were reacted in different ratios to form urethane-modified new resin matrices, and then mixed with 50 wt.% silica fillers. The viscosities of matrices, polymerization shrinkage, surface hardness, and degrees of conversion of experimental composite resins were then evaluated and compared with a non-modified control group. The viscosities of resin matrices increased with increasing diisocyanate side chain density. Polymerization shrinkage and degree of conversion, however, decreased with increasing diisocyanate side chain density. The surface hardness of all diisocyanate-modified groups was equal to or significantly higher than that of the control group. Conjugation of diisocyanate side chains to dimethacrylate represents an effective means of reducing polymerization shrinkage and increasing the surface hardness of dental composite resins. Copyright © 2012. Published by Elsevier B.V.

Synthesis of Y2O3: Eu added the group 1 or 2 elements using complex-polymerization and its luminescent properties

International Nuclear Information System (INIS)

Park, Sang Mi; Jang, Ho G.; Kim, Chang Hae; Park, Joung Kyu; Park, Hee Dong

2001-01-01

Europium activated yttrium oxide (Y 2 O 3 :Eu) is extensively applied to red phosphor for Flat Panel Display because of its high efficiency and the thermal and chemical stability. Flat Panel Display screen which have a high resolution and high efficiency needs to the phosphors of ideally small size spherical particle. In this study, we prepared a Y 2 O 3 :Eu phosphor using polymeric precursor methods and investigated the codoping effect by introducing the group 1 or 2 elements to Y 2 O 3 :Eu phosphor in view of improvement of luminance efficiency

Effect of water temperature on the fit of provisional crown margins during polymerization: An in vitro study

Directory of Open Access Journals (Sweden)

Vivekanandan Ramkumar

2012-01-01

Full Text Available Aim: To evaluate the effect of water temperature on the marginal fit of bis-acrylic composite provisional crown during resin polymerization. Materials and Methods: Precisely machined 10 brass master dies were designed to simulate molar teeth. Five brass dies were selected and precisely machined to simulate all ceramic crown preparation. An acrylic jaw replica was made in which brass dies were arranged equidistant from each other. A custom-made metallic tray was fabricated on the acrylic jaw replica to make polyvinyl siloxane impression matrix. Bis-acrylic composite resin provisional crowns were made using polyvinyl siloxane impression matrix. Provisional crowns were polymerized at room temperature (Group I direct technique, on dental stone cast; Group I indirect technique crowns and at different water temperatures (Group II direct technique crowns. The vertical marginal gap between all the provisional crown margins and the finish line of brass dies was measured using a Research Stereomicroscope System. Results: The results were statistically analyzed using one-way analysis of variance (ANOVA test and Newman-Keul′s test. The results showed that crowns polymerized in 20°C and 30°C water had marginal gap approximately three times smaller than those polymerized in 30°C air, due to the reduced polymerization shrinkage. Conclusion: This study shows that crowns polymerized in 20°C and 30°C water had mean vertical marginal gap approximately three times smaller than those polymerized in 30°C air. It was approximately closer to that of crowns fabricated by indirect technique. Warmer water also supposedly hastens polymerization.

Effect of water temperature on the fit of provisional crown margins during polymerization: An in vitro study.

Science.gov (United States)

Ramkumar, Vivekanandan; Sangeetha, Arunachalam; Kumar, Vinaya

2012-08-01

To evaluate the effect of water temperature on the marginal fit of bis-acrylic composite provisional crown during resin polymerization. Precisely machined 10 brass master dies were designed to simulate molar teeth. Five brass dies were selected and precisely machined to simulate all ceramic crown preparation. An acrylic jaw replica was made in which brass dies were arranged equidistant from each other. A custom-made metallic tray was fabricated on the acrylic jaw replica to make polyvinyl siloxane impression matrix. Bis-acrylic composite resin provisional crowns were made using polyvinyl siloxane impression matrix. Provisional crowns were polymerized at room temperature (Group I direct technique, on dental stone cast; Group I indirect technique crowns) and at different water temperatures (Group II direct technique crowns). The vertical marginal gap between all the provisional crown margins and the finish line of brass dies was measured using a Research Stereomicroscope System. The results were statistically analyzed using one-way analysis of variance (ANOVA) test and Newman-Keul's test. The results showed that crowns polymerized in 20°C and 30°C water had marginal gap approximately three times smaller than those polymerized in 30°C air, due to the reduced polymerization shrinkage. This study shows that crowns polymerized in 20°C and 30°C water had mean vertical marginal gap approximately three times smaller than those polymerized in 30°C air. It was approximately closer to that of crowns fabricated by indirect technique. Warmer water also supposedly hastens polymerization.

Synthesis by ATRP of triblock copolymers with densely grafted styrenic end blocks from a polyisobutylene macroinitiator

DEFF Research Database (Denmark)

Truelsen, Jens Høg; Kops, Jørgen; Pedersen, Walther Batsberg

2000-01-01

A macroinitiator was prepared from a triblock copolymer of polyisobutylene (PIB) with end blocks of poly(p-methylstyrene) (P(p-MeS)) by bromination to obtain initiating bromomethyl groups for atom transfer radical polymerization (ATRP). Controlled polymerization of styrene and p-acetoxystyrene yi......A macroinitiator was prepared from a triblock copolymer of polyisobutylene (PIB) with end blocks of poly(p-methylstyrene) (P(p-MeS)) by bromination to obtain initiating bromomethyl groups for atom transfer radical polymerization (ATRP). Controlled polymerization of styrene and p...

Silica-Polystyrene Nanocomposite Particles Synthesized by Nitroxide-Mediated Polymerization and Their Encapsulation through Miniemulsion Polymerization

Directory of Open Access Journals (Sweden)

Bérangère Bailly

2006-01-01

Full Text Available Polystyrene (PS chains with molecular weights comprised between 8000 and 64000 g⋅mol-1 and narrow polydispersities were grown from the surface of silica nanoparticles (Aerosil A200 fumed silica and Stöber silica, resp. through nitroxide-mediated polymerization (NMP. Alkoxyamine initiators based on N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide (DEPN and carrying a terminal functional group have been synthesized in situ and grafted to the silica surface. The resulting grafted alkoxyamines have been employed to initiate the growth of polystyrene chains from the inorganic surface. The maximum grafting density of the surface-tethered PS chains was estimated and seemed to be limited by initiator confinement at the interface. Then, the PS-grafted Stöber silica nanoparticles were entrapped inside latex particles via miniemulsion polymerization. Transmission electron microscopy indicated the successful formation of silica-polystyrene core-shell particles.

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.

Hyper-cross-linked, hybrid membranes via interfacial polymerization

NARCIS (Netherlands)

Raaijmakers, Michiel

2015-01-01

Hyper-cross-linked, hybrid membranes consist of covalent networks of alternating organic and inorganic, or biological groups. This thesis reports on the preparation of such hybrid networks via interfacial polymerization. The structure-property relationships of the hybrid networks depend strongly on

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...

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

Critically evaluated rate coefficients for free-radical polymerization, 5. Propagation rate coefficient for butyl acrylate

NARCIS (Netherlands)

Asua, J.M.; Beuermann, S.; Buback, M.; Castignolles, P.; Charleux, B.; Gilbert, R.G.; Hutchinson, R.A.; Leiza, J.R.; Nikitin, A.N.; Vairon, J.P.; Herk, van A.M.

2004-01-01

Propagation rate coefficients, kp, for free-radical polymerization of butyl acrylate (BA) previously reported by several groups are critically evaluated. All data were determined by the combination of pulsed-laser polymerization (PLP) and subsequent polymer analysis by size exclusion (SEC)

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.

Fluorosilicone multi-block copolymers tethering quaternary ammonium salt groups for antimicrobial purpose

Energy Technology Data Exchange (ETDEWEB)

Zhou, Fang; Qin, Xiaoshuai; Li, Yancai; Ren, Lixia; Zhao, Yunhui, E-mail: zhaoyunhui@tju.edu.cn; Yuan, Xiaoyan

2015-08-30

Highlights: • QAS-containing fluorosilicone multi-block copolymers were synthesized. • The block length of PHFBMA in the copolymers was tailored via RAFT polymerization. • Surface roughness of the copolymers decreased with the increased PHFBMA content. • A certain length of PHFBMA block enhanced C−N{sup +} percentage on the surface. - Abstract: Symmetrically structured fluorosilicone multi-block copolymers containing poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(hexafluorobutyl methacrylate) (PHFBMA) were sequentially synthesized via reversible addition–fragmentation chain transfer polymerization, using a polydimethylsiloxane (PDMS) chain transfer agent with dithiocarbonate groups at both ends. Then, the CBABC-type block copolymers were quaternized with n-octyliodide to tether quaternary ammonium salt (QAS) groups in the PDMAEMA blocks for the antimicrobial use. The obtained fluorosilicone copolymers showed clear variations in the C-N{sup +} composition and surface morphology on their films depending on the content of the PHFBMA blocks, which were characterized by X-ray photoelectron spectroscopy and atomic force microscopy, respectively. The results indicated that the symmetrical CBABC structure favored PDMS and QAS tethered blocks migrating to the film surface. With the mass percentage of the PHFBMA increased from 0 to 32.5%, the surface roughness of the copolymer film decreased gradually with a tendency to form a smooth surface. Owing to the surface properties, fluorosilicone multi-block copolymers containing a certain amount of PHFBMA with higher C-N{sup +} content and relatively smooth morphology demonstrated obvious antimicrobial activity against Gram-positive bacteria, Bacillus subtilis and Gram-negative bacteria, Escherichia coli. The functionalized multi-block copolymers based on fluorosilicone and QAS groups would have potential applications in antimicrobial coatings.

Fluorosilicone multi-block copolymers tethering quaternary ammonium salt groups for antimicrobial purpose

International Nuclear Information System (INIS)

Zhou, Fang; Qin, Xiaoshuai; Li, Yancai; Ren, Lixia; Zhao, Yunhui; Yuan, Xiaoyan

2015-01-01

Highlights: • QAS-containing fluorosilicone multi-block copolymers were synthesized. • The block length of PHFBMA in the copolymers was tailored via RAFT polymerization. • Surface roughness of the copolymers decreased with the increased PHFBMA content. • A certain length of PHFBMA block enhanced C−N + percentage on the surface. - Abstract: Symmetrically structured fluorosilicone multi-block copolymers containing poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(hexafluorobutyl methacrylate) (PHFBMA) were sequentially synthesized via reversible addition–fragmentation chain transfer polymerization, using a polydimethylsiloxane (PDMS) chain transfer agent with dithiocarbonate groups at both ends. Then, the CBABC-type block copolymers were quaternized with n-octyliodide to tether quaternary ammonium salt (QAS) groups in the PDMAEMA blocks for the antimicrobial use. The obtained fluorosilicone copolymers showed clear variations in the C-N + composition and surface morphology on their films depending on the content of the PHFBMA blocks, which were characterized by X-ray photoelectron spectroscopy and atomic force microscopy, respectively. The results indicated that the symmetrical CBABC structure favored PDMS and QAS tethered blocks migrating to the film surface. With the mass percentage of the PHFBMA increased from 0 to 32.5%, the surface roughness of the copolymer film decreased gradually with a tendency to form a smooth surface. Owing to the surface properties, fluorosilicone multi-block copolymers containing a certain amount of PHFBMA with higher C-N + content and relatively smooth morphology demonstrated obvious antimicrobial activity against Gram-positive bacteria, Bacillus subtilis and Gram-negative bacteria, Escherichia coli. The functionalized multi-block copolymers based on fluorosilicone and QAS groups would have potential applications in antimicrobial coatings

Polymerizations of beta-substituted allylic arsonium ylides with catalytic amounts of organoboron compounds

International Nuclear Information System (INIS)

Mondiere, R.

2004-01-01

My Ph.D. work consisted in the generalization and optimization of a new polymerization reaction involving allylic arsonium ylides and catalytic amounts of various boron compounds. Thus, various β-substituted allylic arsonium salts were produced according to synthetic strategies that depended on the nature of the functional group born by the salt. These salts were converted in situ to the corresponding arsonium ylides which were then treated with boron compounds to yield polymers. Our new method of polymerization afforded either non conjugated polyenes that are functionalized every three atoms of carbon, or statistic copolymers, depending on the nature of the group R born on the β position of the ylide. These new polymers cannot be synthesized by usual methods of polymerization. Initial molar ratios of reactants were found to give molar mass control of the synthesized polymers. This controlled polymerization allowed us to produce several bloc copolymers. All the polymers were characterized by NMR techniques, by size exclusion chromatography and, for some of them, by mass spectrometry. Investigation of their physicochemical properties will need additional experiments. (author)

"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...

Chain-growth cycloaddition polymerization via a catalytic alkyne [2 + 2 + 2] cyclotrimerization reaction and its application to one-shot spontaneous block copolymerization.

Science.gov (United States)

Sugiyama, Yu-ki; Kato, Rei; Sakurada, Tetsuya; Okamoto, Sentaro

2011-06-29

A cobalt-catalyzed alkyne [2 + 2 + 2] cycloaddition reaction has been applied to polymerizations yielding linear polymers via selective cross-cyclotrimerization of yne-diyne monomers, which occurs in a chain-growth manner. Additionally, through control of the alkyne reactivity of the two monomers, this method was efficiently applied to the spontaneous block copolymerization of their mixture. Here we present the proposed mechanism of the catalyst transfer process of this cycloaddition polymerization.

Gas-Phase Mass-Transfer Resistances at Polymeric Electrolyte Membrane Fuel Cells Electrodes: Theoretical Analysis on the Effectiveness of Interdigitated and Serpentine Flow Arrangements

Directory of Open Access Journals (Sweden)

Elisabetta Arato

2016-03-01

Full Text Available Mass transfer phenomena in polymeric electrolyte membrane fuel cells (PEMFC electrodes has already been analyzed in terms of the interactions between diffusive and forced flows. It was demonstrated that the whole phenomenon could be summarized by expressing the Sherwood number as a function of the Peclet number. The dependence of Sherwood number on Peclet one Sh(Pe function, which was initially deduced by determining three different flow regimes, has now been given a more accurate description. A comparison between the approximate and the accurate results for a reference condition of diluted reactant and limit current has shown that the former are useful for rapid, preliminary calculations. However, a more precise and reliable estimation of the Sherwood number is worth attention, as it provides a detailed description of the electrochemical kinetics and allows a reliable comparison of the various geometrical arrangements used for the distribution of the reactants.

Electrophoresis- and FRET-Based Measures of Serpin Polymerization.

Science.gov (United States)

Faull, Sarah V; Brown, Anwen E; Haq, Imran; Irving, James A

2017-01-01

Many serpinopathies, including alpha-1 antitrypsin (A1AT) deficiency, are associated with the formation of unbranched polymer chains of mutant serpins. In vivo, this deficiency is the result of mutations that cause kinetic or thermodynamic destabilization of the molecule. However, polymerization can also be induced in vitro from mutant or wild-type serpins under destabilizing conditions. The characteristics of the resulting polymers are dependent upon induction conditions. Due to their relationship to disease, serpin polymers, mainly those formed from A1AT, have been widely studied. Here, we describe Förster resonance energy transfer (FRET) and gel-based approaches for their characterization.

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.

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.

Stress transfer from pile group in saturated and unsaturated soil using theoretical and experimental approaches

Directory of Open Access Journals (Sweden)

al-Omari Raid R.

2017-01-01

Full Text Available Piles are often used in groups, and the behavior of pile groups under the applied loads is generally different from that of single pile due to the interaction of neighboring piles, therefore, one of the main objectives of this paper is to investigate the influence of pile group (bearing capacity, load transfer sharing for pile shaft and tip in comparison to that of single piles. Determination of the influence of load transfer from the pile group to the surrounding soil and the mechanism of this transfer with increasing the load increment on the tip and pile shaft for the soil in saturated and unsaturated state (when there is a negative pore water pressure. Different basic properties are used that is (S = 90%, γd = 15 kN / m3, S = 90%, γd = 17 kN / m3 and S = 60%, γd =15 kN / m3. Seven model piles were tested, these was: single pile (compression and pull out test, 2×1, 3×1, 2×2, 3×2 and 3×3 group. The stress was measured with 5 cm diameter soil pressure transducer positioned at a depth of 5 cm below the pile tip for all pile groups. The measured stresses below the pile tip using a soil pressure transducer positioned at a depth of 0.25L (where L is the pile length below the pile tip are compared with those calculated using theoretical and conventional approaches. These methods are: the conventional 2V:1H method and the method used the theory of elasticity. The results showed that the method of measuring the soil stresses with soil pressure transducer adopted in this study, gives in general, good results of stress transfer compared with the results obtained from the theoretical and conventional approaches.

Hyperbranched polymers from polymerization in solid state

International Nuclear Information System (INIS)

Tomaz, Vivian A.; Silva, Rafael; Muniz, Edvani C.; Rubira, Adley F.

2009-01-01

The macroscopic properties of polymers are directly related to the chemical characteristics of the monomeric units and also with the geometric arrangement of polymer chains. Thus, polymers were synthesized from two well-known chelators EDTA and EDA. We evaluated the conditions for the polymerization of the precursors in the solid state. The polymerization was carried out varying the proportions of reagents, aiming the polymers with different degrees of chain branching and the materials were characterized by FTIR. The materials obtained from the best condition for synthesis were purified by size-exclusion chromatography of and were subjected to characterization by FTIR and NMR of 1 H and 13 C. The content of end groups in these samples was determined by back titration. (author)

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...

Radiation-Induced Graft Polymerization: Gamma Radiation and Electron Beam Technology for Materials Development

International Nuclear Information System (INIS)

Madrid, Jordan F.; Cabalar, Patrick Jay; Lopez, Girlie Eunice; Abad, Lucille V.

2015-01-01

The formation of functional hybrid materials by attaching polymer chains with advantageous tailored properties to the surface of a base polymer with desirable bulk character is an attractive application of graft copolymerization. Radiation-induced graft polymerization (RIGP) has been a popular approach for surface modification of polymers because of its merits over conventional chemical processes. RIGP, which proceeds primarily via free radical polymerization process, has the advantages such as simplicity, low cost, control over process and adjustment of the materials composition and structure. RIGP can be performed using either electron beam or gamma radiation and it can be applied to both synthetic and natural polymers. These merits make RIGP a popular research topic worldwide. Moreover, the materials synthesized and produced via RIGP has found applications, and were proposed to produce continuous impact, in the fields of medicine, agriculture, pollution remediation, rare earth and valuable metals recovery, fuel cell membrane synthesis and catalysis to name a few. From 2012 our group has performed electron beam and gamma radiation-induced graft polymerization of various monomers onto polymers of natural and synthetic origins (e.g. monomers - glycidyl methacrylate, styrene, acrylonitrile, N,N-dimethylaminoethyl methacrylate; base polymers – polyethylene/polypropylene nonwoven fabric, polypropylene nonwoven fabric pineapple fibers, cellulose nonwoven fabric microcrystalline cellulose). We tested these grafted materials for heavy metals (Pb, Ni, Cu) and organic molecule removal from aqueous solutions and E. coli activity (using reversible addition fragmentation chain transfer RAFT mediated grafting). The results clearly showed the success of materials modified via FIGP in these applications. Currently, we are studying the applications of grafted materials on treatment of waste waters from tanning industry, value addition to abaca nonwoven fabrics cell sheet

Thermally conductive, electrically insulating and melt-processable polystyrene/boron nitride nanocomposites prepared by in situ reversible addition fragmentation chain transfer polymerization

International Nuclear Information System (INIS)

Huang, Xingyi; Wang, Shen; Zhu, Ming; Yang, Ke; Jiang, Pingkai; Bando, Yoshio; Golberg, Dmitri; Zhi, Chunyi

2015-01-01

Thermally conductive and electrically insulating polymer/boron nitride (BN) nanocomposites are highly attractive for various applications in many thermal management fields. However, so far most of the preparation methods for polymer/BN nanocomposites have usually caused difficulties in the material post processing. Here, an in situ grafting approach is designed to fabricate thermally conductive, electrically insulating and post-melt processable polystyrene (PS)/BN nanosphere (BNNS) nanocomposites by initiating styrene (St) on the surface functionalized BNNSs via reversible addition fragmentation chain transfer polymerization. The nanocomposites exhibit significantly enhanced thermal conductivity. For example, at a St/BN feeding ratio of 5:1, an enhancement ratio of 1375% is achieved in comparison with pure PS. Moreover, the dielectric properties of the nanocomposites show a desirable weak dependence on frequency, and the dielectric loss tangent of the nanocomposites remains at a very low level. More importantly, the nanocomposites can be subjected to multiple melt processing to form different shapes. Our method can become a universal approach to prepare thermally conductive, electrically insulating and melt-processable polymer nanocomposites with diverse monomers and nanofillers. (paper)

Surface molecular imprinting onto fluorescein-coated magnetic nanoparticlesvia reversible addition fragmentation chain transfer polymerization: A facile three-in-one system for recognition and separation of endocrine disrupting chemicals

Science.gov (United States)

Li, Ying; Dong, Cunku; Chu, Jia; Qi, Jingyao; Li, Xin

2011-01-01

In this study, we present a general protocol for the making of surface-imprinted magnetic fluorescence beads viareversible addition-fragmentation chain transfer polymerization. The resulting composites were characterized by X-ray diffraction analysis, transmission electron microscopy, scanning electron microscopy, fluorescence spectroscopy, Fourier transform infrared spectroscopy, and energy dispersive spectroscopy. The as-synthesized beads exhibited homogeneous polymer films (thickness of about 5.7 nm), spherical shape, high fluorescence intensity and magnetic property (Magnetization (Ms) = 3.67 emu g-1). The hybrids bind the original template 17β-estradiol with an appreciable selectivity over structurally related compounds. In addition, the resulting hybrids performed without obvious deterioration after five repeated cycles. This study therefore demonstrates the potential of molecularly imprinted polymers for the recognition and separation of endocrine disrupting chemicals.In this study, we present a general protocol for the making of surface-imprinted magnetic fluorescence beads viareversible addition-fragmentation chain transfer polymerization. The resulting composites were characterized by X-ray diffraction analysis, transmission electron microscopy, scanning electron microscopy, fluorescence spectroscopy, Fourier transform infrared spectroscopy, and energy dispersive spectroscopy. The as-synthesized beads exhibited homogeneous polymer films (thickness of about 5.7 nm), spherical shape, high fluorescence intensity and magnetic property (Magnetization (Ms) = 3.67 emu g-1). The hybrids bind the original template 17β-estradiol with an appreciable selectivity over structurally related compounds. In addition, the resulting hybrids performed without obvious deterioration after five repeated cycles. This study therefore demonstrates the potential of molecularly imprinted polymers for the recognition and separation of endocrine disrupting chemicals. Electronic

Polymerization reactivity of sulfomethylated alkali lignin modified with horseradish peroxidase.

Science.gov (United States)

Yang, Dongjie; Wu, Xiaolei; Qiu, Xueqing; Chang, Yaqi; Lou, Hongming

2014-03-01

Alkali lignin (AL) was employed as raw materials in the present study. Sulfomethylation was conducted to improve the solubility of AL, while sulfomethylated alkali lignin (SAL) was further polymerized by horseradish peroxidase (HRP). HRP modification caused a significant increase in molecular weight of SAL which was over 20 times. It was also found to increase the amount of sulfonic and carboxyl groups while decrease the amount of phenolic and methoxyl groups in SAL. The adsorption quantity of self-assembled SAL film was improved after HRP modification. Sulfonation and HRP modification were mutually promoted. The polymerization reactivity of SAL in HRP modification was increased with its sulfonation degree. Meanwhile, HRP modification facilitated SAL's radical-sulfonation reaction. Copyright © 2014. Published by Elsevier Ltd.

Direct dry transfer of chemical vapor deposition graphene to polymeric substrates

OpenAIRE

Fechine, Guilhermino J. M.; Martin-Fernandez, Inigo; Yiapanis, George; de Oliveira, Ricardo V. Bof; Hu, Xiao; Yarovsky, Irene; Neto, Antonio H. Castro; Ozyilmaz, Barbaros

2014-01-01

We demonstrate the direct dry transfer of large area Chemical Vapor Deposition graphene to several polymers (low density polyethylene, high density polyethylene, polystyrene, polylactide acid and poly(vinylidenefluoride-co-trifluoroethylene) by means of only moderate heat and pressure, and the later mechanical peeling of the original graphene substrate. Simulations of the graphene-polymer interactions, rheological tests and graphene transfer at various experimental conditions show that contro...

UV-Vis/FT-NIR in situ monitoring of visible-light induced polymerization of PEGDA hydrogels initiated by eosin/triethanolamine/O2.

Science.gov (United States)

Kaastrup, Kaja; Aguirre-Soto, Alan; Wang, Chen; Bowman, Christopher N; Stansbury, Jeffery; Sikes, Hadley D

In conjunction with a tertiary amine coinitiator, eosin, a photoreducible dye, has been shown to successfully circumvent oxygen inhibition in radical photopolymerization reactions. However, the role of O 2 in the initiation and polymerization processes remains inconclusive. Here, we employ a UV-Vis/FT-NIR analytical tool for real-time, simultaneous monitoring of chromophore and monomer reactive group concentrations to investigate the eosin-activated photopolymerization of PEGDA-based hydrogels under ambient conditions. First, we address the challenges associated with spectroscopic monitoring of the polymerization of hydrogels using UV-Vis and FT-NIR, proposing metrics for quantifying the extent of signal loss from reflection and scattering, and showing their relation to microgelation and network formation. Second, having established a method for extracting kinetic information by eliminating the effects of changing refractive index and scattering, the coupled UV-Vis/FT-NIR system is applied to the study of eosin-activated photopolymerization of PEGDA in the presence of O 2 . Analysis of the inhibition time, rate of polymerization, and rate of eosin consumption under ambient and purged conditions indicates that regeneration of eosin in the presence of oxygen and consumption of oxygen occur via a nonchain process. This suggests that the uniquely high O 2 resilience is due to alternative processes such as energy transfer from photo-activated eosin to oxygen. Uncovering the intricacies of the role of O 2 in eosin-mediated initiation aids the design of O 2 resistant free radical polymerization systems relevant to photonics, optoelectronics, biomaterials, and biosensing.

Influences of Electrolytes on Soap-Free P(ST-MMA-AA) Emulsion Polymerization

Institute of Scientific and Technical Information of China (English)

Zeping LI; Ronglong LI; Yi DU; Chengyou KAN; Deshan LIU

2005-01-01

@@ 1Introduction Functional polymer microspheres are kinds of polymer particles with special structures, morphologies or functional groups[1] , and have been gained much attention because of their specific properties and their application since 1980s. Although some researches have investigated that the latex particle size and its distribution,as well as the stability of polymerization and the resultant latex were strongly influenced by introducing electrolyte into the emulsion polymerization system[2] , few of them focused on the systematic study of electrolytes on the soap-free emulsion polymerization, which is considered as a conventional approach to synthesize functional polymer microspheres with clean surfaces[2]. In this presentation, the influences of variety and dosage of electrolytes on soap-free emulsion polymerization of St, MMA and AA were studied, and a series of micron or submicron sized latex particles with narrow distribution were obtained.

Characteristics of polyimide-based composite membranes fabricated by low-temperature plasma polymerization

International Nuclear Information System (INIS)

Dung Thi Tran; Mori, Shinsuke; Suzuki, Masaaki

2008-01-01

Composite membranes were prepared by the deposition of plasma-polymerized allylamine films onto a porous polyimide substrate. The relationship between the plasma conditions and the membrane characteristics was described in terms of monomer flow rate, plasma discharge power, plasma polymerization time, and so on. Scanning electron microscope (SEM) images indicate that the thickness of the plasma polymer layer increased and the membrane skin pore size decreased gradually with the increasing of plasma polymerization time. Fourier transform infrared (FTIR) spectra demonstrate the appearance of amine groups in the plasma deposited polymer and the contact angle measurements indicate that the hydrophilicity of the membrane surfaces increased significantly after plasma polymerization. The composite membranes can reject salt from sodium chloride feed solution, and membrane separation performance depends strongly on the plasma conditions applied during the preparation of the plasma deposited polymer films

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.

SENSITIVITY ANALYSIS OF KINETIC CONSTANTS AS A TOOL FOR ELUCIDATING THE POLYMERIZATION MECHANISM OF ACRYL-FURANIC COMPOUNDS

Directory of Open Access Journals (Sweden)

Jurgen Lange

2013-12-01

Full Text Available By means of the sensitivity analysis of kinetics constants in a proposed mechanism for radical polymerization of acrylfuranic compounds [Furfuryl Acrylate (FA and Methacrylate (FM],it is elucidated which elementary steps are relevant in the phenomenology. In this analysis, the application of Come's methodology allows to classify the elementary steps of a mechanism in three categories: Non-sensible, Non-determinant, Sensible. The results obtained with this tool in modeling of experimental data in free radical polymerization of FA and FM suggest that kinetic mechanism consists mainly on five elementary steps: 1 Primary initiation, 2 propagation, 3 degradative transfers (which include intermolecular and primary, 4 re-initiation and 5 cross-termination. Thus, taking into account these elementary steps in mathematical modeling, the polymerization of FA and FM in different experimental conditions was successfully simulated.

Enhanced electrical properties in solution-processed InGaZnO thin-film transistors by viable hydroxyl group transfer process

Science.gov (United States)

Kim, Do-Kyung; Jeong, Hyeon-Seok; Kwon, Hyeok Bin; Kim, Young-Rae; Kang, Shin-Won; Bae, Jin-Hyuk

2018-05-01

We propose a simple hydroxyl group transfer method to improve the electrical characteristics of solution-processed amorphous InGaZnO (IGZO) thin-film transistors (TFTs). Tuned poly(dimethylsiloxane) elastomer, which has a hydroxyl group as a terminal chemical group, was adhered temporarily to an IGZO thin-film during the solidification step to transfer and supply sufficient hydroxyl groups to the IGZO thin-film. The transferred hydroxyl groups led to efficient hydrolysis and condensation reactions, resulting in a denser metal–oxygen–metal network being achieved in the IGZO thin-film compared to the conventional IGZO thin-film. In addition, it was confirmed that there was no morphological deformation, including to the film thickness and surface roughness. The hydroxyl group transferred IGZO based TFTs exhibited enhanced electrical properties (field-effect mobility of 2.21 cm2 V‑1 s‑1, and on/off current ratio of 106) compared to conventional IGZO TFTs (field-effect mobility of 0.73 cm2 V‑1 s‑1 and on/off current ratio of 105).

Cell-derived matrix coatings for polymeric scaffolds.

Science.gov (United States)

Decaris, Martin L; Binder, Bernard Y; Soicher, Matthew A; Bhat, Archana; Leach, J Kent

2012-10-01

Cells in culture deposit a complex extracellular matrix that remains intact following decellularization and possesses the capacity to modulate cell phenotype. The direct application of such decellularized matrices (DMs) to 3D substrates is problematic, as transport issues influence the homogeneous deposition, decellularization, and modification of DM surface coatings. In an attempt to address this shortcoming, we hypothesized that DMs deposited by human mesenchymal stem cells (MSCs) could be transferred to the surface of polymeric scaffolds while maintaining their capacity to direct cell fate. The ability of the transferred DM (tDM)-coated scaffolds to enhance the osteogenic differentiation of undifferentiated and osteogenically induced MSCs under osteogenic conditions in vitro was confirmed. tDM-coated scaffolds increased MSC expression of osteogenic marker genes (BGLAP, IBSP) and intracellular alkaline phosphatase production. In addition, undifferentiated MSCs deposited significantly more calcium when seeded onto tDM-coated scaffolds compared with control scaffolds. MSC-seeded tDM-coated scaffolds subcutaneously implanted in nude rats displayed significantly higher blood vessel density after 2 weeks compared with cells on uncoated scaffolds, but we did not observe significant differences in mineral deposition after 8 weeks. These data demonstrate that DM-coatings produced in 2D culture can be successfully transferred to 3D substrates and retain their capacity to modulate cell phenotype.

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.

Mussel inspired polymerized P(TA-TETA) for facile functionalization of carbon nanotube

Science.gov (United States)

Si, Shuxian; Gao, Tingting; Wang, Junhao; Liu, Qinze; Zhou, Guowei

2018-03-01

This article describes a novel and effective approach for non-covalent modification of carbon nanotube (CNT) via the mussel inspired polymerization of tannic acid (TA) and triethylenetetramine (TETA) and subsequent surface initiated atom transfer radical polymerization (SI-ATRP). Fourier transform infrared spectroscopy (FT-IR), thermo-gravimetric analysis (TGA), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and photograph were used to study the successful preparation of polymer brush grafted CNT (CNT-P(TA-TETA)-PDMAEMA) composite as well as the pH-responsive behavior of the composite. Furthermore, by amine protonation and in situ reduction, gold nanoparticles were successfully uploaded and the catalytic property of CNT-P(TA-TETA)-PDMAEMA/Au was investigated. We believe that the surface functionalization strategy can be extended to graphene and other substrates, and the surface properties can be regulated by grafting polymer brushes with different functionalities.

Evaluation of the polymerization shrinkage of experimental flowable composite resins through optical coherence tomography

Science.gov (United States)

Carneiro, Vanda S. M.; Mota, Cláudia C. B. O.; Souza, Alex F.; Cajazeira, Marlus R. R.; Gerbi, Marleny E. M. M.; Gomes, Anderson S. L.

2018-02-01

This study evaluated the polymerization shrinkage of two experimental flowable composite resins (CR) with different proportions of Urethane dimethacrylate (UDMA)/triethylene glycol dimethacrylate (TEGDMA) monomers in the organic matrix (50:50 and 60:40, respectively). A commercially available flowable CR, Tetric N-Flow (Ivoclair Vivadent, Liechtenstein, Germany), was employed as the control group. The resins were inserted in a cylindrical teflon mold (7 mm diameter, 0.6 mm height) and scanned with OCT before photoactivation, immediately after and 15 minutes after light-curing (Radii-Cal, SDI, Australia, 1,200 mW/cm2 ) exposure. A Callisto SD-OCT system (Thorlabs Inc, USA), operating at 930 nm central wavelength was employed for imaging acquisition. Cross-sectional OCT images were captured with 8 mm transverse scanning (2000x512 matrix), and processed by the ImageJ software, for comparison between the scanning times and between groups. Pearson correlation showed significant shrinkage for all groups in each time analyzed. Kruskal-Wallis test showed greater polymerization shrinkage for the 50:50 UDMA/TEGDMA group (p=0.001), followed by the control group (p=0.018). TEGDMA concentration was proportionally related to the polymerization shrinkage of the flowable composite resins.

Synthesis, anticancer activity, and inhibition of tubulin polymerization by conformationally restricted analogues of lavendustin A.

Science.gov (United States)

Mu, Fanrong; Hamel, Ernest; Lee, Debbie J; Pryor, Donald E; Cushman, Mark

2003-04-24

Compounds in the lavendustin A series have been shown to inhibit both protein-tyrosine kinases (PTKs) and tubulin polymerization. Since certain lavendustin A derivatives can exist in conformations that resemble both the trans-stilbene structure of the PTK inhibitor piceatannol and the cis-stilbene structure of the tubulin polymerization inhibitor combretastatin A-4, the possibility exists that the ratio of the two types of activities of the lavendustins could be influenced through the synthesis of conformationally restricted analogues. Accordingly, the benzylaniline structure of a series of pharmacologically active lavendustin A fragments was replaced by either their cis- or their trans-stilbene relatives, and effects on both inhibition of tubulin polymerization and cytotoxicity in cancer cell cultures were monitored. Both dihydrostilbene and 1,2-diphenylalkyne congeners were also prepared and evaluated biologically. Surprisingly, conformational restriction of the bridge between the two aromatic rings of the lavendustins had no significant effect on biological activity. On the other hand, conversion of the three phenolic hydroxyl groups of the lavendustin A derivatives to their corresponding methyl ethers consistently abolished their ability to inhibit tubulin polymerization and usually decreased cytotoxicity in cancer cell cultures as well, indicating the importance of at least one of the phenolic hydroxyl groups. Further investigation suggested that the phenolic hydroxyl group in the salicylamide ring was required for activity, while the two phenol moieties in the hydroquinone ring could be methylated with retention of activity. Two of the lavendustin A derivatives displayed IC(50) values of 1.4 microM for inhibition of tubulin polymerization, which ranks them among the most potent of the known tubulin polymerization inhibitors.

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...

A peroxidase mimic with atom transfer radical polymerization activity constructed through the grafting of heme onto metal-organic frameworks.

Science.gov (United States)

Jiang, Wei; Pan, Yue; Yang, Jiebing; Liu, Yong; Yang, Yan; Tang, Jun; Li, Quanshun

2018-07-01

Atom transfer radical polymerization (ATRP) has been considered to be an efficient strategy for constructing functional macromolecules owing to its simple operation and versatile monomers, and thus it is of great significance to develop ideal catalysts with higher activity and perfect reusability. We constructed a peroxidase mimic through the grafting of heme onto metal-organic frameworks UiO-66-NH 2 (ZrMOF), namely Heme-ZrMOF. After the systematic characterization of structure, the composite Heme-ZrMOF was demonstrated to possess high peroxidase activity using 2,2'-azinobis-(3-ethylbenzthiazoline-6-sulphonate) and 3,3',5,5'-tetramethylbenzidine as substrates. The enzyme mimic was then used as catalysts in the ATRP reactions of different monomers, in which favorable monomer conversion (44.6-98.0%) and product molecular weight (8600-25,600 g/mol) could be obtained. Compared to free heme, Heme-ZrMOF could efficiently achieve the easy separation of heme from the catalytic system and facilitate the ATRP reaction in an aqueous environment to avoid the utilization of organic solvents. In conclusion, the enzyme mimic Heme-ZrMOF could be potentially used as an effective catalyst for preparing well-defined polymers with biomedical applications. Copyright © 2018 Elsevier Inc. All rights reserved.

Gamma-radiation induced polymerization of methyl methacrylate in aliphatic hydrocarbons: kinetics and evidence for incorporation of hydrocarbon in the polymer chain

International Nuclear Information System (INIS)

Mohan, H.; Iyer, R.M.

1989-01-01

On γ-radiolysis, the rate of polymerization of methyl methacrylate in hydrocarbon solvents is observed to decrease. It is explained by hydrocarbon entry into the polymer chains. The hydrocarbon entry into the polymer chains is observed to take place at later stages of polymerization and increases with hydrocarbon chain length. The extent of hydrocarbon entry into the polymer chains is estimated by NMR and GLC analysis. It is observed to be equal to ∼ 12% corresponding to ∼ 97 hexadecane molecules in each polymer chain. The IR, DSC, MW determination and radiation effects on the polymer showed evidences for hydrocarbon entry into the polymer. It is explained by chain transfer from the growing polymer radical to the hydrocarbon molecules. The chain transfer constant is determined to be equal to 1 x 10 -2 . (author)

Synthesis of defined polyhedral oligosilsesquioxane-containing diblock and triblock methacrylate copolymers by atom transfer radical polymerization

Czech Academy of Sciences Publication Activity Database

Janata, Miroslav; Sikora, Antonín; Látalová, Petra; Čadová, Eva; Raus, Vladimír; Matějka, Libor; Vlček, Petr

2013-01-01

Roč. 128, č. 6 (2013), s. 4294-4301 ISSN 0021-8995 R&D Projects: GA ČR GAP106/12/0844; GA ČR GAP108/12/1459 Institutional support: RVO:61389013 Keywords : copolymers * nanostructured polymers * radical polymerization Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.640, year: 2013

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.

Living catalyzed-chain-growth polymerization and block copolymerization of isoprene by rare-earth metal allyl precursors bearing a constrained-geometry-conformation ligand.

Science.gov (United States)

Jian, Zhongbao; Cui, Dongmei; Hou, Zhaomin; Li, Xiaofang

2010-05-07

Aminophenyl functionalized cyclopentadienyl ligated rare-earth metal allyl mediated cationic systems display high cis-1,4 selectivity for the polymerization of isoprene, and living reversible and rapid chain transfer to aluminium additives.

(1-Adamantyl)methyl glycidyl ether: a versatile building block for living polymerization.

Science.gov (United States)

Moers, Christian; Wrazidlo, Robert; Natalello, Adrian; Netz, Isabelle; Mondeshki, Mihail; Frey, Holger

2014-06-01

(1-Adamantyl)methyl glycidyl ether (AdaGE) is introduced as a versatile monomer for oxyanionic polymerization, enabling controlled incorporation of adamantyl moieties in aliphatic polyethers. Via copolymerization with ethoxyethyl glycidyl ether (EEGE) and subsequent cleavage of the acetal protection groups of EEGE, hydrophilic linear polyglycerols with an adjustable amount of pendant adamantyl moieties are obtained. The adamantyl unit permits control over thermal properties and solubility profile of these polymers (LCST). Additionally, AdaGE is utilized as a termination agent in carbanionic polymerization, affording adamantyl-terminated polymers. Using these structures as macroinitiators for the polymerization of ethylene oxide affords amphiphilic, in-chain adamantyl-functionalized block copolymers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of repair resin type and surface treatment on the repair strength of heat-polymerized denture base resin.

Science.gov (United States)

Alkurt, Murat; Yeşil Duymuş, Zeynep; Gundogdu, Mustafa

2014-01-01

Acrylic resin denture fracture is common in prosthodontic practice. When fractured denture bases are repaired, recurrent fractures frequently occur at the repair surface interface or adjacent areas. The purpose of this study was to evaluate the effect of different surface treatments on the flexural strength of the acrylic resin denture base repaired with heat-polymerized acrylic resin, autopolymerizing resin, and light-polymerized acrylic resin. Ninety-six specimens of heat-polymerized acrylic resin were prepared according to the American Dental Association Specification No. 12 (65.0 × 10.0 × 2.5 mm) and sectioned into halves to create a repair gap (3.0 × 10 × 2.5 mm). The sectioned specimens were divided into 3 groups according to their repair materials. The specimens from each group were divided into 4 subgroups according to their surface treatments: a control group without any surface treatment; an experimental group treated with methyl methacrylate monomer (MMA group); an experimental group treated with airborne-particle abrasion with aluminum oxide particles of 250-μm particle size (abrasion group); and an experimental group treated with erbium:yttrium-aluminum-garnet laser (laser group). After the surface treatments, the 3 materials were placed into the repair gaps and then polymerized. After all of the specimens had been ground and polished, they were stored in distilled water at 37°C for 1 week and subjected to a 3-point bend test. Data were analyzed with a 2-way analysis of variance, and the Tukey honestly significant difference test was performed to identify significant differences (α=.05). The effects of the surface treatments and repair resins on the surface of the denture base resin were examined with scanning electron microscopy. Significant differences were found among the groups in terms of repair resin type (P<.001). All surface-treated specimens had higher flexural strength than controls, except the surface treated with the methyl

Transference and Countertransference Issues Unique to Long-Term Group Psychotherapy of Adult Women Molested as Children: Trials and Rewards.

Science.gov (United States)

Abney, Veronica D.; And Others

1992-01-01

Discusses transference and countertransference issues associated with long-term psychodynamic group treatment of adult women molested as children. Describes and examines these women's transference reactions toward group members and the therapist. Also explores the specific effects of race and ethnicity, sexual orientation, and gender of the…

Acrylonitrile-Butadiene Rubber (NBR) Prepared via Living/Controlled Radical Polymerization (RAFT).

Science.gov (United States)

Kaiser, Andreas; Brandau, Sven; Klimpel, Michael; Barner-Kowollik, Christopher

2010-09-15

In the current work we present results on the controlled/living radical copolymerization of acrylonitrile (AN) and 1,3-butadiene (BD) via reversible addition fragmentation chain transfer (RAFT) polymerization techniques. For the first time, a solution polymerization process for the synthesis of nitrile butadiene rubber (NBR) via the use of dithioacetate and trithiocarbonate RAFT agents is described. It is demonstrated that the number average molar mass, $\\overline M _{\\rm n} $, of the NBR can be varied between a few thousand and 60 000 g · mol(-1) with polydispersities between 1.2 and 2.0 (depending on the monomer to polymer conversion). Excellent agreement between the experimentally observed and the theoretically expected molar masses is found. Detailed information on the structure of the synthesized polymers is obtained by variable analytical techniques such as infrared spectroscopy (IR), nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry, and electrospray ionization-mass spectrometry (ESI-MS). Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sulfonated amphiphilic block copolymers : synthesis, self-assembly in water, and application as stabilizer in emulsion polymerization

Science.gov (United States)

Jiguang Zhang; Matthew R. Dubay; Carl J. Houtman; Steven J. Severtson

2009-01-01

Described is the synthesis of diblock copolymers generated via sequential atom transfer radical polymerization (ATRP) of poly(n-butyl acrylate) (PnBA) followed by chain augmentation with either sulfonated poly(2-hydroxyethyl methacrylate) (PHEMA) or poly(2-hydroxyethyl acrylate) (PHEA) blocks. ATRP of PHEMA or PHEA from PnBA macroinitiator was conducted in acetone/...

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.

Synthetic approaches towards new polymer systems by the combination of living carbocationic and anionic polymerizations

DEFF Research Database (Denmark)

Feldthusen, Jesper; Ivan, Bela; Muller, Axel. H.E.

1996-01-01

Recent efforts to obtain block copolymers by combination of living carbocationic and anionic polymerizations are presented.When tolyl-ended polyisobutylene was used as macroinitiator of anionic polymerization of methacrylate derivatives mixtures of homopolymers and block copolymers were formed due...... to incomplete lithiation of this chain end.In another approach a new functionalization method was developed by end-quenching living polyisobutylene with 1,1-diphenylethylene. After transformation of the groups into 2,2-diphenylvinyl end groups and lithiation polymers were synthesized from protected acrylate...

Synthesis and characterization of associating polymers which contain siloxanes chains; Synthese et caracterisation de polymeres associatifs porteurs de groupes siloxanes

Energy Technology Data Exchange (ETDEWEB)

Meyer, V

1999-01-11

Polymers that associate via physical interactions in solutions have received much attention as viscosifiers. Such associating polymers are now used in variety of applications due to their unique theological properties coating, food thickeners, paints, enhanced oil recovery, water treatment). They contain a hydrophilic main chain with hydrophobic side chain that is generally constituted of hydrocarbon or fluorocarbon groups. Novel copolymers with sites of association in aqueous solution were prepared by co-polymerizing acrylamide with an hydrophobic monomer containing siloxane parts. Rheological properties were studied as a function of polymer concentration, microstructure, shear rate and frequency in order to show intra intermolecular associations between the hydrophobic parts. The polymer solution viscosity increases as a function of the hydrophobic group content. Tests of adsorption show a high affinity of these copolymers with clay and the amount absorbed increase with the quantity of hydrophobic entities containing in the chain. These properties are enhanced compared to copolymers containing hydrocarbon chains. (authors) 456 refs.

Development of water-borne thermosetting paint by radiation-induced emulsion polymerization

International Nuclear Information System (INIS)

Makuuchi, K.; Katakai, A.; Nakayama, H.

1981-01-01

In previous papers the features of γ-ray induced emulsion polymerization were studied to use the emulsion as vehicles for water-borne paint. In this paper, the physical properties of thermosetting paints made with emulsions containing N-(n-butoxymethyl)acrylamide (NBM) and hydroxyl and carboxyl functionality were investigated. Since NBM moieties can react with amide, hydroxyl, and carboxyl groups, NBM copolymer emulsions prepared in this study have the self-crosslinking capability. As far as it was investigated, it was difficult to prepare a stable emulsion containing 10% of NBM by the conventional emulsion polymerization by using a water soluble radical initiator such as persulfate. In addition to 1-liter reactor, a pilot-scale plant of 70 liters reactor was used for γ-ray induced emulsion polymerization. Experimental details are given, and results are discussed. (author)

Structural and Kinetic Evidence for an Extended Hydrogen-Bonding Network in Catalysis of Methyl Group Transfer

International Nuclear Information System (INIS)

Doukov, T.; Hemmi, H.; Drennan, C.; Ragsdale, S.

2007-01-01

The methyltetrahydrofolate (CH 3 -H 4 folate) corrinoid-ironsulfur protein (CFeSP) methyltransferase (MeTr) catalyzes transfer of the methyl group of CH3-H4folate to cob(I)amide. This key step in anaerobic CO and CO 2 fixation is similar to the first half-reaction in the mechanisms of other cobalamin-dependent methyltransferases. Methyl transfer requires electrophilic activation of the methyl group of CH 3 -H 4 folate, which includes proton transfer to the N5 group of the pterin ring and poises the methyl group for reaction with the Co(I) nucleophile. The structure of the binary CH 3 -H 4 folate/MeTr complex (revealed here) lacks any obvious proton donor near the N5 group. Instead, an Asn residue and water molecules are found within H-bonding distance of N5. Structural and kinetic experiments described here are consistent with the involvement of an extended H-bonding network in proton transfer to N5 of the folate that includes an Asn (Asn-199 in MeTr), a conserved Asp (Asp-160), and a water molecule. This situation is reminiscent of purine nucleoside phosphorylase, which involves protonation of the purine N7 in the transition state and is accomplished by an extended H-bond network that includes water molecules, a Glu residue, and an Asn residue (Kicska, G. A., Tyler, P. C., Evans, G. B., Furneaux, R. H., Shi, W., Fedorov, A., Lewandowicz, A., Cahill, S. M., Almo, S. C., and Schramm, V. L. (2002) Biochemistry 41, 14489-14498). In MeTr, the Asn residue swings from a distant position to within H-bonding distance of the N5 atom upon CH 3 -H 4 folate binding. An N199A variant exhibits only ∼20-fold weakened affinity for CH 3 -H 4 folate but a much more marked 20,000-40,000-fold effect on catalysis, suggesting that Asn-199 plays an important role in stabilizing a transition state or high energy intermediate for methyl transfer

Tailor-made polyfluoroacrylate and its block copolymer by RAFT polymerization in miniemulsion; improved hydrophobicity in the core-shell block copolymer.

Science.gov (United States)

Chakrabarty, Arindam; Singha, Nikhil K

2013-10-15

Controlled/living radical polymerization (CRP) of a fluoroacrylate was successfully carried out in miniemulsion by Reversible Addition Fragmentation chain Transfer (RAFT) process. In this case, 2,2,3,3,4,4,4-heptafluorobutyl acrylate (HFBA) was polymerized using 2-cyanopropyl dodecyl trithiocarbonate (CPDTC) as RAFT agent, Triton X-405 and sodium dodecyl sulfonate (SDS) as surfactant, and potassium persulphate (KPS) or 2,2'-azobis isobutyronitrile (AIBN) as initiator. Being compatible with hydrophobic fluoroacrylate, this RAFT agent offered very high conversion and good control over the molecular weight of the polymer. The miniemulsion was stable without any costabilizer. The long chain dodecyl group (-C12H25) (Z-group in the RAFT agent) had beneficial effect in stabilizing the miniemulsion. When 2-cyano 2-propyl benzodithioate (CPBD) (Z=-C6H5) was used as RAFT agent, the conversion was less and particle size distribution was very broad. Block copolymerization with butyl acrylate (BA) using PHFBA as macro-RAFT agent showed core-shell morphology with the aggregation of PHFBA segment in the shell. GPC as well as DSC analysis confirmed the formation of block copolymer. The core-shell morphology was confirmed by TEM analysis. The block copolymers (PHFBA-b-PBA) showed significantly higher water contact angle (WCA) showing much better hydrophobicity compared to PHFBA alone. Copyright © 2013 Elsevier Inc. All rights reserved.

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)

Activation and deactivation of neutral palladium(II) phosphinesulfonato polymerization catalysts

KAUST Repository

Rünzi, Thomas

2012-12-10

13C-Labeled ethylene polymerization (pre)catalysts [κ2-(anisyl)2P,O]Pd(13CH3)(L) (1-13CH3-L) (L = pyridine, dmso) based on di(2-anisyl)phosphine benzenesulfonate were used to assess the degree of incorporation of 13CH3 groups into the formed polyethylenes. Polymerizations of variable reaction time reveal that ca. 60-85% of the 13C-label is found in the polymer after already 1 min polymerization time, which provides evidence that the pre-equilibration between the catalyst precursor 1-13CH3-L and the active species 1-13CH3-(ethylene) is fast with respect to chain growth. The fraction of 1-13CH3-L that initiates chain growth is likely higher than the 60-85% determined from the 13C-labeled polymer chain ends since (a) chain walking results in in-chain incorporation of the 13C-label, (b) irreversible catalyst deactivation by formation of saturated (and partially volatile) alkanes diminishes the amount of 13CH3 groups incorporated into the polymer, and (c) palladium-bound 13CH3 groups, and more general palladium-bound alkyl(polymeryl) chains, partially transfer to phosphorus by reductive elimination. NMR and ESI-MS analyses of thermolysis reactions of 1-13CH3-L provide evidence that a mixture of phosphonium salts (13CH3)xP+(aryl)4-x (2-7) is formed in the absence of ethylene. In addition, isolation and characterization of the mixed bis(chelate) palladium complex [κ2-(anisyl)2P,O]Pd[κ2-(anisyl) (13CH3)P,O] (11) by NMR and X-ray diffraction analyses from these mixtures indicate that oxidative addition of phosphonium salts to palladium(0) species is also operative. The scrambling of palladium-bound carbyls and phosphorus-bound aryls is also relevant under NMR, as well as preparative reactor polymerization conditions exemplified by the X-ray diffraction analysis of [κ2-(anisyl)2P,O] Pd[κ2-(anisyl)(CH2CH3)P,O] (12) and [κ2-(anisyl)2P,O]Pd[κ2-(anisyl) ((CH2)3CH3)P,O] (13) isolated from pressure reactor polymerization experiments. In addition, ESI-MS analyses of reactor

Elucidation of the Key Role of [Ru(bpy)3 ](2+) in Photocatalyzed RAFT Polymerization.

Science.gov (United States)

Christmann, Julien; Ibrahim, Ahmad; Charlot, Vincent; Croutxé-Barghorn, Céline; Ley, Christian; Allonas, Xavier

2016-08-04

Photocatalysis reactions using [Ru(II) (bpy)3 ](2+) were studied on the example of visible-light-sensitized reversible addition-fragmentation chain transfer (RAFT) polymerization. Although both photoinduced electron- and energy-transfer mechanisms are able to describe this interaction, no definitive experimental proof has been presented so far. This paper investigates the actual mechanism governing this reaction. A set of RAFT agents was selected, their redox potentials measured by cyclic voltammetry, and relaxed triplet energies calculated by quantum mechanics. Gibbs free-energy values were calculated for both electron- and energy-transfer mechanisms. Quenching rate constants were determined by laser flash photolysis. The results undoubtedly evidence the involvement of a photoinduced energy-transfer reaction. Controlled photopolymerization experiments are discussed in the light of the primary photochemical process and photodissociation ability of RAFT agent triplet states. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Chromatographic assessment of two hybrid monoliths prepared via epoxy-amine ring-opening polymerization and methacrylate-based free radical polymerization using methacrylate epoxy cyclosiloxane as functional monomer.

Science.gov (United States)

Wang, Hongwei; Ou, Junjie; Lin, Hui; Liu, Zhongshan; Huang, Guang; Dong, Jing; Zou, Hanfa

2014-11-07

Two kinds of hybrid monolithic columns were prepared by using methacrylate epoxy cyclosiloxane (epoxy-MA) as functional monomer, containing three epoxy moieties and one methacrylate group. One column was in situ fabricated by ring-opening polymerization of epoxy-MA and 1,10-diaminodecane (DAD) using a porogenic system consisting of isopropanol (IPA), H2O and ethanol at 65°C for 12h. The other was prepared by free radical polymerization of epoxy-MA and ethylene dimethacrylate (EDMA) using 1-propanol and 1,4-butanediol as the porogenic solvents at 60°C for 12h. Two hybrid monoliths were investigated on the morphology and chromatographic assessment. Although two kinds of monolithic columns were prepared with epoxy-MA, their morphologies looked rather different. It could be found that the epoxy-MA-DAD monolith possessed higher column efficiencies (25,000-34,000plates/m) for the separation of alkylbenzenes than the epoxy-MA-EDMA monolith (12,000-13,000plates/m) in reversed-phase nano-liquid chromatography (nano-LC). Depending on the remaining epoxy or methacrylate groups on the surface of two pristine monoliths, the epoxy-MA-EDMA monolith could be easily modified with 1-octadecylamine (ODA) via ring-opening reaction, while the epoxy-MA-DAD monolith could be modified with stearyl methacrylate (SMA) via free radical reaction. The chromatographic performance for the separation of alkylbenzenes on SMA-modified epoxy-MA-DAD monolith was remarkably improved (42,000-54,000 plates/m) when compared with that on pristine epoxy-MA-DAD monolith, while it was not obviously enhanced on ODA-modified epoxy-MA-EDMA monolith when compared with that on pristine epoxy-MA-EDMA monolith. The enhancement of the column efficiency of epoxy-MA-DAD monolith after modification might be ascribed to the decreased mass-transfer resistence. The two kinds of hybrid monoliths were also applied for separations of six phenols and seven basic compounds in nano-LC. Copyright © 2014 Elsevier B.V. All

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.

Concentrations and congener profiles of chlorinated paraffins in domestic polymeric products in China.

Science.gov (United States)

Wang, Chu; Gao, Wei; Liang, Yong; Wang, Yawei; Jiang, Guibin

2018-03-21

Chlorinated paraffins (CPs) are widely used in domestic polymeric products as plasticizers and fire retardants. In this study, concentrations and congener profiles of short-chain and medium-chain chlorinated paraffins (SCCPs and MCCPs) were investigated in domestic polymeric products, including plastics, rubber and food packaging in China. The average concentrations of SCCPs in polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE) and food packaging were 234, 3968, 150 and 188 ng/g, respectively and the corresponding average concentrations of MCCPs in these samples were 37.4, 2537, 208 and 644 ng/g, respectively. The concentrations of CPs in rubber and polyvinylchloride (PVC) were significantly higher than in other matrices. The highest concentrations of SCCPs and MCCPs were found in a PVC cable sheath with 191 mg/g and 145 mg/g, respectively. Congener group profiles analysis indicated C 11 - and C 13 -congener groups were predominant in carbon homologues of SCCPs, and C 14 -congener groups were predominant in MCCPs. High levels of SCCPs and MCCPs in domestic polymeric products implied that they might be a significant source to the environment and human exposure. Copyright © 2018. Published by Elsevier Ltd.

Atom transfer radical copolymerization of styrene and butyl acrylate

NARCIS (Netherlands)

Chambard, G.; Klumperman, B.; Matyjaszewski, K.

2000-01-01

Atom transfer radical polymerization of styrene and butyl acrylate has been investigated from a kinetic point of view. Attention is focused on the activation of the dormant species as well as on the termination that plays a role in these reactions. It has been shown that the activation of a styrene

Effect of delayed polymerization time and bracket manipulation on orthodontic bracket bonding

Science.gov (United States)

Ponikvar, Michael J.

This study examined the effect of bracket manipulation in combination with delayed polymerization times on orthodontic bracket shear bond strength and degree of resin composite conversion. Orthodontics brackets were bonded to extracted third molars in a simulated oral environment after a set period of delayed polymerization time and bracket manipulation. After curing the bracket adhesive, each bracket underwent shear bond strength testing followed by micro-Raman spectroscopy analysis to measure the degree of conversion of the resin composite. Results demonstrated the shear bond strength and the degree of conversion of ceramic brackets did not vary over time. However, with stainless steel brackets there was a significant effect (p ≤ 0.05) of delay time on shear bond strength between the 0.5 min and 10 min bracket groups. In addition, stainless steel brackets showed significant differences related to degree of conversion over time between the 0.5 min and 5 min groups, in addition to the 0.5 min and 10 min groups. This investigation suggests that delaying bracket adhesive polymerization up to a period of 10 min then adjusting the orthodontic bracket may increase both shear bond strength and degree of conversion of stainless steel brackets while having no effect on ceramic brackets.

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....

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.

Effect of air bubble localization after transfer on embryo transfer outcomes.

Science.gov (United States)

Tiras, Bulent; Korucuoglu, Umit; Polat, Mehtap; Saltik, Ayse; Zeyneloglu, Hulusi Bulent; Yarali, Hakan

2012-09-01

Our study aimed to provide information about the effects of air bubble localization after transfer on embryo transfer outcomes. Retrospective analysis of 7489 ultrasound-guided embryo transfers. Group 1 included 6631 embryo transfers in which no movement of the air bubbles was observed after transfer. Group 2 consisted of 407 embryo transfers in which the air bubbles moved towards the uterine fundus spontaneously, a little time after transfer. Group 3 included 370 embryo transfers in which the air bubbles moved towards the uterine fundus with ejection, immediately after transfer. Group 4 consisted of 81 embryo transfers in which the air bubbles moved towards the cervical canal. The four patient groups were different from one another with respect to positive pregnancy tests. Post hoc test revealed that this difference was between group 4 and other groups. An initial finding of our study was significantly decreased positive pregnancy test rates and clinical pregnancy rates with air bubbles moving towards the cervical canal after transfer. Although air bubbles moving towards the uterine fundus with ejection were associated with higher pregnancy rates, higher miscarriage rates and similar live birth rates were observed compared to air bubbles remaining stable after transfer. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

Compatibility between dental adhesive systems and dual-polymerizing composite resins.

Science.gov (United States)

Michaud, Pierre-Luc; MacKenzie, Alexandra

2016-10-01

Information is lacking about incompatibilities between certain types of adhesive systems and dual-polymerizing composite resins, and universal adhesives have yet to be tested with these resins. The purpose of this in vitro study was to investigate the bonding outcome of dual-polymerizing foundation composite resins by using different categories of adhesive solutions and to determine whether incompatibilities were present. One hundred and eighty caries-free, extracted third molar teeth were allocated to 9 groups (n=20), in which 3 different bonding agents (Single Bond Plus [SB]), Scotchbond Multi-purpose [MP], and Scotchbond Universal [SU]) were used to bond 3 different composite resins (CompCore AF [CC], Core Paste XP [CP], and Filtek Supreme Ultra [FS]). After restorations had been fabricated using an Ultradent device, the specimens were stored in water at 37°C for 24 hours. The specimens were tested under shear force at a rate of 0.5 mm/min. The data were analyzed with Kruskal-Wallis tests and post hoc pairwise comparisons (α=.05). All 3 composite resins produced comparable shear bond strengths when used with MP (P=.076). However, when either SB or SU was used, the light-polymerized composite resin (FS) and 1 dual-polymerized foundation composite resin (CC) bonded significantly better than the other dual-polymerized foundation composite resin (CP) (Pincompatibilities exist between different products. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Direct transfer of graphene films for polyurethane substrate

Energy Technology Data Exchange (ETDEWEB)

Vilani, C.; Romani, E.C.; Larrudé, D.G. [Departamento de Física, Pontifícia Universidade Católica do Rio de Janeiro, 22451-900 Rio de Janeiro, RJ (Brazil); Barbosa, Gelza M. [Diretoria de Sistemas de Armas da Marinha, Marinha do Brasil, 20010-00 Rio de Janeiro, RJ (Brazil); Freire, F.L., E-mail: lazaro@vdg.fis.puc-rio.br [Departamento de Física, Pontifícia Universidade Católica do Rio de Janeiro, 22451-900 Rio de Janeiro, RJ (Brazil); Centro Brasileiro de Pesquisas Físicas, 22290-180 Rio de Janeiro, RJ (Brazil)

2015-11-30

Highlights: • Graphene was prepared by CVD using copper foils as substrates. • Monolayer, bilayer and multilayer graphene were transferred to PU. • Samples were characterized by Raman and optical spectroscopies. • PU/monolayer graphene has transmittance around 80% in visible range. - Abstract: We have proposed the direct transfer of large-area graphene films grown by chemical vapor deposition to polymeric substrate by evaporating of solvents of polyurethane/tetrahydrofurane solution. The graphene films on polyurethane substrates were characterized by Raman spectroscopy, optical and atomic force microscopies and UV–vis spectroscopy measurements. The Raman spectra revealed that it is possible to transfer in a controlled manner monolayer, bilayer and multilayer graphene films over polyurethane substrate.

Direct transfer of graphene films for polyurethane substrate

International Nuclear Information System (INIS)

Vilani, C.; Romani, E.C.; Larrudé, D.G.; Barbosa, Gelza M.; Freire, F.L.

2015-01-01

Highlights: • Graphene was prepared by CVD using copper foils as substrates. • Monolayer, bilayer and multilayer graphene were transferred to PU. • Samples were characterized by Raman and optical spectroscopies. • PU/monolayer graphene has transmittance around 80% in visible range. - Abstract: We have proposed the direct transfer of large-area graphene films grown by chemical vapor deposition to polymeric substrate by evaporating of solvents of polyurethane/tetrahydrofurane solution. The graphene films on polyurethane substrates were characterized by Raman spectroscopy, optical and atomic force microscopies and UV–vis spectroscopy measurements. The Raman spectra revealed that it is possible to transfer in a controlled manner monolayer, bilayer and multilayer graphene films over polyurethane substrate.

The influence of charge transfers effects in monazite-type LaVO{sub 4} and perovskite-type LaVO{sub 3} prepared by sol-gel acrylamide polymerization

Energy Technology Data Exchange (ETDEWEB)

Herrera-Pérez, G., E-mail: guillermo.herrera@cimav.edu.mx [CONACYT Research Fellow. Centro de Investigación en Materiales Avanzados (CIMAV), Miguel de Cervantes 120, Chihuahua 31136, Chihuahua (Mexico); Jiménez-Mier, J. [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, 04510 Mexico D. F (Mexico); Yang, W.-L. [The Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Reyes-Rojas, A.; Fuentes-Cobas, L.E. [Department of Physics of Materials Department. Centro de Investigación en Materiales Avanzados (CIMAV), Miguel de Cervantes 120, Chihuahua 31136, Chihuahua (Mexico)

2016-08-15

Highlights: • We elucidate the electronic structure through the vanadium L{sub 2,3} edge in LaVO{sub 4} by XAS. • The interpretation of XAS spectrum was performed by the multiplet calculation. • Our results suggest that LaVO{sub 4} can be considered in the charge transfer regime. - Abstract: Core-hole spectroscopy such as X-ray absorption spectroscopy (XAS) is useful to determine the electronic structure of strongly correlated and strongly hybridized compounds such as vanadates. Monazite-type LaVO{sub 4} and perovskite-type LaVO{sub 3} are good candidates to elucidate the electronic structure through the vanadium L{sub 2,3} edge. LaVO{sub 4} was prepared by sol-gel acrylamide polymerization and solid-state reaction. LaVO{sub 3} was obtained by reduction of LaVO{sub 4} using Zr as gatherer. Monoclinic crystal phase for LaVO{sub 4} and orthorhombic crystal phase for LaVO{sub 3} were confirmed by the Rietveld refinement of X-ray diffraction patterns. XAS comparison between Vanadium L{sub 2,3} edge confirms the presence of V{sup 5+} for the monazite and V{sup 3+} for the orthorhombic perovskite. Multiplet calculations including crystal field and charge transfer effects (CTM) were performed in order to elucidate the tetragonal (D{sub 4h} symmetry) parameters Dq, Ds and Dt, the charge transfer energy Δ, and d-d Coulomb repulsion energy U parameters. CTM confirms for LaVO{sub 3} the strong V 3d–O 2p hybridization with a significant contribution of covalent character due to the delocalization of 3d electrons. For LaVO{sub 4} this work suggest the reclassification of this band insulator as charge transfer insulator that shows a significant contribution of ionic character.

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.

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.

Polymerization of Polar Monomers from a Theoretical Perspective

KAUST Repository

Alghamdi, Miasser

2016-10-11

Density functional theory calculations have been used to investigate catalytic mechanism of polymer formation containing polar groups, from the synthesis of the monomer to the synthesis of the macromolecule. In the spirit of a sustainable and green chemistry, we initially focused attention on the coupling of CO2 as economically convenient and recyclable C1 source with C2H4 to form acrylate and/or butirro-lactone, two important polar monomers. In this process formation of a mettallolactone via oxidative coupling of CO2 and C2H4 is an important intermediate. Given this background, we explored in detail (chapter-3) several Ni based catalysts for CO2 coupling with C2H4 to form acrylate. In this thesis we report on the competitive reaction mechanisms (inner vs outer sphere) for the oxidative coupling of CO2 and ethylene for a set of 11 Ni-based complexes containing bisphosphine ligands. In another effort, considering incorporation of a C=C bond into a metal-oxygen-Functional-Group moiety is a challenging step in several polymerization reactions, we explored the details of this reaction (chapter4) using two different catalysts that are capable to perform this reaction in the synthesis of heterocycles. Specifically, the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-Bis-diphenylphosphino-propane), and the [Pd]/BPh3 intramolecular alkoxyfunctionalizations. Rest of the thesis we worked on understanding the details of the polymerization of polar monomers using organocatalysts based on N-heterocyclic carbenes (NHC) or N-heterocyclic olefins (NHO). In particular (chapter-5) we studied the polymerization of N-methyl N-carboxy- anhydrides, towards cyclic poly(N-substituted glycine)s, promoted by NHC catalysts. In good agreement with the experimental findings, we demonstrated that NHC promoted ring opening polymerization of N-Me N-Carboxyanhydrides may proceed via two different catalytic pathways. In a similar effort we studied polymerization of

Synthesis of polyalkylacrylate nanolatexes by microemulsion polymerization method

Directory of Open Access Journals (Sweden)

A.M. Al-Sabagh

2012-12-01

Full Text Available The paper concerns with the radical polymerization of [octadecyl acrylate (ODA, isooctyl acrylate (iso-OA and α-olefins 1-Octene (n-O]. These microemulsions were stabilized by sodium dodecyl sulfate (SDS and initiated by water-soluble initiator potassium persulfate (KPS. The nanolatex particle sizes were determined by transmission electron microscope (TEM. They were situated between 10 and 100 nm. The microstructures were confirmed by FT-IR and molecular weights determined by Gel permeation chromatography (GPC. The obtained M. wt. were (≈70 × 103, 101 × 103 and 153 × 103 g/mol. The polydispersity, molecular weights, and particle sizes were discussed in the light of micelle formation and shape of the alkyl group via emulsion polymerization.

TEGDMA and UDMA monomers released from composite dental material polymerized with diode and halogen lamps.

Science.gov (United States)

Wacławczyk, Agnieszka; Postek-Stefańska, Lidia; Pietraszewska, Daria; Birkner, Ewa; Zalejska-Fiolka, Jolanta; Wysoczańska-Jankowicz, Iwona

2018-03-20

More than 35 substances released from composite fillings have been identified. Among these, basic monomers and the so-called co-monomers are most often reported. The substances released from polymer-based materials demonstrate allergenic, cytotoxic, genotoxic, mutagenic, embryotoxic, teratogenic, and estrogenic properties. The aim of this study was to measure the amounts of triethylene glycol dimethacrylate (TEGDMA) and urethane dimethacrylate (UDMA) monomers released from composite dental fillings to citrate-phosphate buffer with the pH of 4, 6, 8 after 24 h and 6 months from the polymerization. Ten samples for each polymerization method had been made from the composite material (Filtek Supreme XT, 3M ESPE, St. Paul, USA), which underwent polymerization using the following lamps: halogen lamp (Translux CL, Heraeus Kulzer, Hanau, Germany) (sample H) and diode lamp (Elipar Freelight 2, 3M ESPE), with soft start function (group DS) and without that function (group DWS). It has been demonstrated that the type of light-curing units has a significant impact on the amount of TEGDMA and UDMA released. The amount of UDMA and TEGDMA monomers released from composite fillings differed significantly depending on the source of polymerization applied, as well as the pH of the solution and sample storage time. Elution of the monomers from composite material polymerized using halogen lamp was significantly greater as compared to curing with diode lamps.

Polymethyl methacrylate-co-methacrylic acid coatings with controllable concentration of surface carboxyl groups: A novel approach in fabrication of polymeric platforms for potential bio-diagnostic devices

International Nuclear Information System (INIS)

Hosseini, Samira; Ibrahim, Fatimah; Djordjevic, Ivan; Koole, Leo H.

2014-01-01

Highlights: • Synthesis and processing of PMMA-co-MAA spin-coatings on silicon wafers. • Surface chemistry and morphology as a function of tailored co-polymer structure. • Polymer coatings with controlled number of surface carboxyl groups. - Abstract: The generally accepted strategy in development of bio-diagnostic devices is to immobilize proteins on polymeric surfaces as a part of detection process for diseases and viruses through antibody/antigen coupling. In that perspective, polymer surface properties such as concentration of functional groups must be closely controlled in order to preserve the protein activity. In order to improve the surface characteristics of transparent polymethacrylate plastics that are used for diagnostic devices, we have developed an effective fabrication procedure of polymethylmetacrylate-co-metacrylic acid (PMMA-co-MAA) coatings with controlled number of surface carboxyl groups. The polymers were processed effectively with the spin-coating technique and the detailed control over surface properties is here by demonstrated through the variation of a single synthesis reaction parameter. The chemical structure of synthesized and processed co-polymers has been investigated with nuclear magnetic resonance spectroscopy (NMR) and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-ToF-MS). The surface morphology of polymer coatings have been analyzed with atomic force microscopy (AFM) and scanning electron microscopy (SEM). We demonstrate that the surface morphology and the concentration of surface –COOH groups (determined with UV–vis surface titration) on the processed PMMA-co-MAA coatings can be precisely controlled by variation of initial molar ratio of reactants in the free-radical polymerization reaction. The wettability of developed polymer surfaces also varies with macromolecular structure

Polymethyl methacrylate-co-methacrylic acid coatings with controllable concentration of surface carboxyl groups: A novel approach in fabrication of polymeric platforms for potential bio-diagnostic devices

Energy Technology Data Exchange (ETDEWEB)

Hosseini, Samira; Ibrahim, Fatimah [Center for Innovation in Medical Engineering, Department of Biomedical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603 (Malaysia); Djordjevic, Ivan, E-mail: ivan.djordjevic@um.edu.my [Center for Innovation in Medical Engineering, Department of Biomedical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603 (Malaysia); Koole, Leo H. [Center for Innovation in Medical Engineering, Department of Biomedical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603 (Malaysia); Department of Biomedical Engineering, Faculty of Health. Medicine and Life Science, Maastricht University, PO Box 616, NL 6200 MD Maastricht (Netherlands)

2014-05-01

Highlights: • Synthesis and processing of PMMA-co-MAA spin-coatings on silicon wafers. • Surface chemistry and morphology as a function of tailored co-polymer structure. • Polymer coatings with controlled number of surface carboxyl groups. - Abstract: The generally accepted strategy in development of bio-diagnostic devices is to immobilize proteins on polymeric surfaces as a part of detection process for diseases and viruses through antibody/antigen coupling. In that perspective, polymer surface properties such as concentration of functional groups must be closely controlled in order to preserve the protein activity. In order to improve the surface characteristics of transparent polymethacrylate plastics that are used for diagnostic devices, we have developed an effective fabrication procedure of polymethylmetacrylate-co-metacrylic acid (PMMA-co-MAA) coatings with controlled number of surface carboxyl groups. The polymers were processed effectively with the spin-coating technique and the detailed control over surface properties is here by demonstrated through the variation of a single synthesis reaction parameter. The chemical structure of synthesized and processed co-polymers has been investigated with nuclear magnetic resonance spectroscopy (NMR) and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-ToF-MS). The surface morphology of polymer coatings have been analyzed with atomic force microscopy (AFM) and scanning electron microscopy (SEM). We demonstrate that the surface morphology and the concentration of surface –COOH groups (determined with UV–vis surface titration) on the processed PMMA-co-MAA coatings can be precisely controlled by variation of initial molar ratio of reactants in the free-radical polymerization reaction. The wettability of developed polymer surfaces also varies with macromolecular structure.

Living Polycondensation: Synthesis of Well-Defined Aromatic Polyamide-Based Polymeric Materials

KAUST Repository

Alyami, Mram Z.

2016-01-01

Chain growth condensation polymerization is a powerful tool towards the synthesis of well-defined polyamides. This thesis focuses on one hand, on the synthesis of well-defined aromatic polyamides with different aminoalkyl pendant groups with low

Risk transfer formula for individual and small group markets under the Affordable Care Act.

Science.gov (United States)

Pope, Gregory C; Bachofer, Henry; Pearlman, Andrew; Kautter, John; Hunter, Elizabeth; Miller, Daniel; Keenan, Patricia

2014-01-01

The Affordable Care Act provides for a program of risk adjustment in the individual and small group health insurance markets in 2014 as Marketplaces are implemented and new market reforms take effect. The purpose of risk adjustment is to lessen or eliminate the influence of risk selection on the premiums that plans charge. The risk adjustment methodology includes the risk adjustment model and the risk transfer formula. This article is the third of three in this issue of the Medicare & Medicaid Research Review that describe the ACA risk adjustment methodology and focuses on the risk transfer formula. In our first companion article, we discussed the key issues and choices in developing the methodology. In our second companion paper, we described the risk adjustment model that is used to calculate risk scores. In this article we present the risk transfer formula. We first describe how the plan risk score is combined with factors for the plan allowable premium rating, actuarial value, induced demand, geographic cost, and the statewide average premium in a formula that calculates transfers among plans. We then show how each plan factor is determined, as well as how the factors relate to each other in the risk transfer formula. The goal of risk transfers is to offset the effects of risk selection on plan costs while preserving premium differences due to factors such as actuarial value differences. Illustrative numerical simulations show the risk transfer formula operating as anticipated in hypothetical scenarios.

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

Halloysite nanotubes grafted hyperbranched (co)polymers via surface-initiated self-condensing vinyl (co)polymerization

International Nuclear Information System (INIS)

Mu Bin; Zhao Mingfei; Liu Peng

2008-01-01

Halloysite nanotubes (HNTs) grafted hyperbranched polymers were prepared by the self-condensing vinyl polymerization (SCVP) of 2-((bromoacetyl)oxy)ethyl acrylate (BAEA) and the self-condensing vinyl copolymerization of n-butyl acrylate (BA) and BAEA with BAEA as inimer (AB*) respectively, from the surfaces of the 2-bromoisobutyric acid modified halloysite nanotubes (HNTs-Br) via atom transfer radical polymerization (ATRP) technique. The halloysite nanotubes grafted hyperbranched polymer (HNTs-HP) and the halloysite nanotubes grafted hyperbranched copolymer (HNTs-HCP) were characterized by elemental analysis (EA), Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and transmission electron microscope (TEM). The grafted hyperbranched polymers were characterized with Nuclear magnetic resonance (NMR) and the molecular ratio between the inimer AB* and BA in the grafted hyperbranched copolymers was found to be 3:2, calculated from the TGA and EA results

Halloysite nanotubes grafted hyperbranched (co)polymers via surface-initiated self-condensing vinyl (co)polymerization

Energy Technology Data Exchange (ETDEWEB)

Mu Bin; Zhao Mingfei; Liu Peng [Lanzhou University, State Key Laboratory of Applied Organic Chemistry and Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering (China)], E-mail: pliu@lzu.edu.cn

2008-05-15

Halloysite nanotubes (HNTs) grafted hyperbranched polymers were prepared by the self-condensing vinyl polymerization (SCVP) of 2-((bromoacetyl)oxy)ethyl acrylate (BAEA) and the self-condensing vinyl copolymerization of n-butyl acrylate (BA) and BAEA with BAEA as inimer (AB*) respectively, from the surfaces of the 2-bromoisobutyric acid modified halloysite nanotubes (HNTs-Br) via atom transfer radical polymerization (ATRP) technique. The halloysite nanotubes grafted hyperbranched polymer (HNTs-HP) and the halloysite nanotubes grafted hyperbranched copolymer (HNTs-HCP) were characterized by elemental analysis (EA), Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and transmission electron microscope (TEM). The grafted hyperbranched polymers were characterized with Nuclear magnetic resonance (NMR) and the molecular ratio between the inimer AB* and BA in the grafted hyperbranched copolymers was found to be 3:2, calculated from the TGA and EA results.

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.

Absence of first-order unbinding transitions of fluid and polymerized membranes

Science.gov (United States)

Grotehans, Stefan; Lipowsky, Reinhard

1990-01-01

Unbinding transitions of fluid and polymerized membranes are studied by renormalization-group (RG) methods. Two different RG schemes are used and found to give rather consistent results. The fixed-point structure of both RG's exhibits a complex behavior as a function of the decay exponent tau for the fluctuation-induced interaction of the membranes. For tau greater than tau(S2) interacting membranes can undergo first-order transitions even in the strong-fluctuation regime. These estimates for tau(S2) imply, however, that both fluid and polymerized membranes unbind in a continuous way in the absence of lateral tension.

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.

Polydimethylsiloxane-polymethacrylate block copolymers tethering quaternary ammonium salt groups for antimicrobial coating

Energy Technology Data Exchange (ETDEWEB)

Qin, Xiaoshuai; Li, Yancai; Zhou, Fang; Ren, Lixia; Zhao, Yunhui, E-mail: zhaoyunhui@tju.edu.cn; Yuan, Xiaoyan

2015-02-15

Highlights: • A series of PDMS-b-QPDMAEMA block copolymers were synthesized via RAFT polymerization. • The composition and morphology of the copolymer films strongly depended on the content of QPDMAEMA. • Migration of QPDMAEMA blocks toward surface was promoted when contacting with water. • Heterogeneous film surfaces with higher N{sup +} content exhibited more obvious antimicrobial activity. - Abstract: Block copolymers PDMS-b-PDMAEMA were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization involving N,N-dimethylaminoethyl methacrylate (DMAEMA) by using poly(dimethylsiloxane) (PDMS) macro-chain transfer agent. And, the tertiary amino groups in PDMAEMA were quaternized with n-octyliodide to provide quaternary ammonium salts (QPDMAEMA). The well-defined copolymers generated composition variation and morphology evolvement on film surfaces, which were characterized by X-ray photoelectron spectroscopy, atomic force microscopy, and contact angle measurements. The results indicated that the enrichment of QPDMAEMA brought about lower elemental ratios of Si/N on the film surfaces. The surface morphologies evolved with the variations of QPDMAEMA content, and the variation trend of film roughness was exactly opposite to that of water contact angle hysteresis. With regard to structure-antimicrobial relationships, the copolymer films had more evident antimicrobial activity against Gram-positive, Bacillus subtilis, and the surfaces with heterogeneous morphology and higher N{sup +} content presented better antimicrobial activity. The functionalized copolymers based PDMS and quaternary ammonium salts materials have the potential applications as antimicrobial coatings.

Amphiphilic Fluorinated Block Copolymer Synthesized by RAFT Polymerization for Graphene Dispersions

Directory of Open Access Journals (Sweden)

Hyang Moo Lee

2016-03-01

Full Text Available Despite the superior properties of graphene, the strong π–π interactions among pristine graphenes yielding massive aggregation impede industrial applications. For non-covalent functionalization of highly-ordered pyrolytic graphite (HOPG, poly(2,2,2-trifluoroethyl methacrylate-block-poly(4-vinyl pyridine (PTFEMA-b-PVP block copolymers were prepared by reversible addition-fragmentation chain transfer (RAFT polymerization and used as polymeric dispersants in liquid phase exfoliation assisted by ultrasonication. The HOPG graphene concentrations were found to be 0.260–0.385 mg/mL in methanolic graphene dispersions stabilized with 10 wt % (relative to HOPG PTFEMA-b-PVP block copolymers after one week. Raman and atomic force microscopy (AFM analyses revealed that HOPG could not be completely exfoliated during the sonication. However, on-line turbidity results confirmed that the dispersion stability of HOPG in the presence of the block copolymer lasted for one week and that longer PTFEMA and PVP blocks led to better graphene dispersibility. Force–distance (F–d analyses of AFM showed that PVP block is a good graphene-philic block while PTFEMA is methanol-philic.

Dissolved Divalent Metal and pH Effects on Amino Acid Polymerization: A Thermodynamic Evaluation.

Science.gov (United States)

Kitadai, Norio

2017-03-01

Polymerization of amino acids is a fundamentally important step for the chemical evolution of life. Nevertheless, its response to changing environmental conditions has not yet been well understood because of the lack of reliable quantitative information. For thermodynamics, detailed prediction over diverse combinations of temperature and pH has been made only for a few amino acid-peptide systems. This study used recently reported thermodynamic dataset for the polymerization of the simplest amino acid "glycine (Gly)" to its short peptides (di-glycine and tri-glycine) to examine chemical and structural characteristics of amino acids and peptides that control the temperature and pH dependence of polymerization. Results showed that the dependency is strongly controlled by the intramolecular distance between the amino and carboxyl groups in an amino acid structure, although the side-chain group role is minor. The polymerization behavior of Gly reported earlier in the literature is therefore expected to be a typical feature for those of α-amino acids. Equilibrium calculations were conducted to examine effects of dissolved metals as a function of pH on the monomer-polymer equilibria of Gly. Results showed that metals shift the equilibria toward the monomer side, particularly at neutral and alkaline pH. Metals that form weak interaction with Gly (e.g., Mg 2+ ) have no noticeable influence on the polymerization, although strong interaction engenders significant decrease of the equilibrium concentrations of Gly peptides. Considering chemical and structural characteristics of Gly and Gly peptides that control their interactions with metals, it can be expected that similar responses to the addition of metals are applicable in the polymerization of neutral α-amino acids. Neutral and alkaline aqueous environments with dissolved metals having high affinity with neutral α-amino acids (e.g., Cu 2+ ) are therefore not beneficial places for peptide bond formation on the primitive

Temperature rise during adhesive and composite polymerization with different light-curing sources.

Science.gov (United States)

Pereira Da Silva, A; Alves Da Cunha, L; Pagani, C; De Mello Rode, S

2010-05-01

This study evaluated the temperature rise of the adhesive system Single Bond (SB) and the composite resins Filtek Z350 flow (Z) and Filtek Supreme (S), when polymerized by light-emitting diode (LED XL 3000) and quartz-tungsten halogen (QTH Biolux). Class V cavities (3 yen2 mm) were prepared in 80 bovine incisors under standardized conditions. The patients were divided as follows: G1: Control; G2: SB; G3: SB + Z; G4: SB + S. The groups were subdivided into two groups for polymerization (A: QTH, B: LED). Light curing was performed for 40 s and measurement of temperature changes during polymerization was performed with a thermocouple positioned inside the pulp chamber. Data were statistically analyzed using ANOVA and Tukey tests. The factors material (P<0.00001) and curing unit (P<0.00001) had significant influence on temperature rise. The lowest temperature increase (0.15 degrees C) was recorded in G2 B and the highest was induced in G1 A (0.75 degrees C, P<0.05). In all groups, lower pulp chamber temperature measurements were obtained when using LED compared to QTH (P<0.05). QTH caused greater increases in tooth temperature than LED. However, both sources did not increase pulpal temperature above the critical value that may cause pulpal damage.

Inorganic-organic hybrid coatings on stainless steel by layer-by-layer deposition and surface-initiated atom-transfer-radical polymerization for combating biocorrosion.

Science.gov (United States)

Yuan, S J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

2009-03-01

To improve the biocorrosion resistance of stainless steel (SS) and to confer the bactericidal function on its surface for inhibiting bacterial adhesion and biofilm formation, well-defined inorganic-organic hybrid coatings, consisting of the inner compact titanium oxide multilayers and outer dense poly(vinyl-N-hexylpyridinium) brushes, were successfully developed. Nanostructured titanium oxide multilayer coatings were first built up on the SS substrates via the layer-by-layer sol-gel deposition process. The trichlorosilane coupling agent, containing the alkyl halide atom-transfer-radical polymerization (ATRP) initiator, was subsequently immobilized on the titanium oxide coatings for surface-initiated ATRP of 4-vinylpyridine (4VP). The pyridium nitrogen moieties of the covalently immobilized 4VP polymer, or P(4VP), brushes were quaternized with hexyl bromide to produce a high concentration of quaternary ammonium salt on the SS surfaces. The excellent antibacterial efficiency of the grafted polycations, poly(vinyl-N-pyridinium bromide), was revealed by viable cell counts and atomic force microscopy images of the surface. The effectiveness of the hybrid coatings in corrosion protection was verified by the Tafel plot and electrochemical impedance spectroscopy measurements.

Poly(methacrylic) Acid and g-methacryloxypropyltrimethoxy Silane/Clay Nanocomposites Prepared by In-Situ Polymerization

OpenAIRE

GÜLTEK, Ahmet; SEÇKİN, Turgay

2002-01-01

Poly(methacrylic acid) and poly(acrylic acid) nanocomposites were prepared by in-situ polymerization of g-methacryloxypropyltrimethoxysilane (A174)/clay nanocomposites in which the macromonomer was generated by grafting A-174 onto activated clay samples via hydroxyl groups or via intercalation. In- situ polymerization was carried out in the presence of an initiator. It was found that the structural affinity between the methacrylic or acrylic acid monomers and the amount of clay playe...

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.

Poly I-lactide-layered double hydroxide nanocomposites via in situ polymerization of I-lactide

DEFF Research Database (Denmark)

Katiyar, Vimal; Gerds, N.; Koch, C.B.

2010-01-01

The use of clay nanofillers offers a potential route to improved barrier properties in polylactide films. Magnesium–aluminium layered double hydroxides (LDHs) are interesting in this respect and we therefore explored synthesis of PLA-LDH nanocomposites by ring-opening polymerization. This method ...... weight was significantly reduced when in-situ polymerization was conducted in the presence of the LDHs and we suggest that chain termination via LDH surface hydroxyl groups and/or metal-catalyzed degradation could be responsible.......The use of clay nanofillers offers a potential route to improved barrier properties in polylactide films. Magnesium–aluminium layered double hydroxides (LDHs) are interesting in this respect and we therefore explored synthesis of PLA-LDH nanocomposites by ring-opening polymerization. This method...

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)

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 ...

Research in Water Permeability of Poly(ethylene) Terephthalate Track Membranes Modified by Polymerization of Dimethylaniline under the Action of Direct Current Discharge

CERN Document Server

Kravets, L I; Drachev, A I

2004-01-01

The properties of poly(ethylene) terephthalate track membranes modified by polymerization of dimethylaniline in a discharge of direct current are investigated. The influence of conditions of plasma treatment on the basic characteristics of the membranes (pore size, wettability, surface charge, water permeability) is studied. It is shown that under the action of discharge, a polymeric layer is formed on the membrane surface that can swell in solutions with low pH values. It has been found that the degree of the swelling stipulated by the conformation transfer of macromolecules of the deposited polymeric layer depends upon the size of relative magnification of the mass of the membrane during its plasma treatment. It is also shown that the obtained membranes can reversibly react to changing the pH of solution and applied pressure.

Modeling the chemistry of plasma polymerization using mass spectrometry.

Science.gov (United States)

Ihrig, D F; Stockhaus, J; Scheide, F; Winkelhake, Oliver; Streuber, Oliver

2003-04-01

The goal of the project is a solvent free painting shop. The environmental technologies laboratory is developing processes of plasma etching and polymerization. Polymerized thin films are first-order corrosion protection and primer for painting. Using pure acetylene we get very nice thin films which were not bonded very well. By using air as bulk gas it is possible to polymerize, in an acetylene plasma, well bonded thin films which are stable first-order corrosion protections and good primers. UV/Vis spectroscopy shows nitrogen oxide radicals in the emission spectra of pure nitrogen and air. But nitrogen oxide is fully suppressed in the presence of acetylene. IR spectroscopy shows only C=O, CH(2) and CH(3) groups but no nitrogen species. With the aid of UV/Vis spectra and the chemistry of ozone formation it is possible to define reactive traps and steps, molecule depletion and processes of proton scavenging and proton loss. Using a numerical model it is possible to evaluate these processes and to calculate theoretical mass spectra. Adjustment of theoretical mass spectra to real measurements leads to specific channels of polymerization which are driven by radicals especially the acetyl radical. The estimated theoretical mass spectra show the specific channels of these chemical processes. It is possible to quantify these channels. This quantification represents the mass flow through this chemical system. With respect to these chemical processes it is possible to have an idea of pollutant production processes.

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.

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.

Intramolecular electron transfer through a bridging carboxylate group coordinated to two cobalt(III)-ions

International Nuclear Information System (INIS)

Wieghardt, K.

1978-01-01

Reduction of the binuclear μ-p-nitrobenzoato -di-μ-hydroxo -bis[triammine cobalt(III)] cation with (CH 3 ) 2 COH radicals yields a radical cation with the p-nitrobenzoato radical being coordinated to two cobalt(III) ions at the carboxylic group. The unprotonated form of this species undergoes intramolecular electron transfer producing Co(II) (k = (3.3 +- 0.3). x 10 3 s -1 ). The role of the carboxylate group in the intramolecular electron transfer process is tentatively assessed in terms of an intramolecular outer-sphere reaction because of lack of overlap of the donor orbitals (π) and the acceptor orbital (sigma). The protonated form of the radical cation (pKsub(a) = 2.5) disproportionates via a bimolecular process without production of Co(II). The effect of two coordinated Co(III) ions as compared to only one on the properties of the nitrobenzoate radical anion are discussed. (orig.) 891 HK 892 GM [de

Synthesis of gold nanorod-embedded polymeric nanoparticles by a nanoprecipitation method for use as photothermal agents

Energy Technology Data Exchange (ETDEWEB)

Kim, Eunjung; Choi, Jihye; Haam, Seungjoo [Department of Chemical and Biomolecular Engineering, College of Engineering, Yonsei University, Seoul 120-749 (Korea, Republic of); Yang, Jaemoon; Suh, Jin-Suck; Huh, Yong-Min, E-mail: ej.kim@yonsei.ac.k, E-mail: 177hum@yonsei.ac.k, E-mail: jjakji2@yonsei.ac.k, E-mail: jss@yuhs.a, E-mail: ymhuh@yuhs.a, E-mail: haam@yonsei.ac.k [Department of Radiology, College of Medicine, Yonsei University, Seoul 120-752 (Korea, Republic of)

2009-09-09

For the synthesis of biocompatible photothermal agents, gold nanorod-embedded polymeric nanoparticles (GPNs) were synthesized using a nanoprecipitation method. Uniform gold nanorods (GNRs), which are sensitive to a photothermal effect by near-infrared (NIR) light, with an aspect ratio of 4.0 were synthesized by a seed-mediated growth method. The hydroxyl groups of polycaprolactone diol (PCL diOH) were modified by esterification with mercaptopropionic acid to give a dithiol (polycaprolactone dithiol, PCL diSH) as a phase transfer and capping agent. Subsequently, hexadecyltrimethylammonium bromide (CTAB), a stabilizer of GNRs, was exchanged and/or removed by PCL diSH. PCL diSH-coated GNRs were further wrapped in a hydrophilic polymer, Pluronic F127, as a stabilizer. These newly formulated GPNs exhibit excellent stability in water and a maximum absorbance in the NIR region indicating a highly efficient surface plasmon resonance effect, phenomena useful for photothermal agents.

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.

Activation and deactivation of neutral palladium(II) phosphinesulfonato polymerization catalysts

KAUST Repository

Rü nzi, Thomas; Tritschler, Ulrich; Roesle, Philipp; Gö ttker-Schnetmann, Inigo J.; Mö ller, Heiko Maa; Caporaso, Lucia; Poater, Albert; Cavallo, Luigi; Mecking, Stefan

2012-01-01

13C-Labeled ethylene polymerization (pre)catalysts [κ2-(anisyl)2P,O]Pd(13CH3)(L) (1-13CH3-L) (L = pyridine, dmso) based on di(2-anisyl)phosphine benzenesulfonate were used to assess the degree of incorporation of 13CH3 groups into the formed

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.)

Ring Opening Metathesis Polymerization of Cyclopentene Using a Ruthenium Catalyst Confined by a Branched Polymer Architecture

KAUST Repository

Mugemana, Clement; Bukhriakov, Konstantin; Bertrand, Olivier; Vu, Khanh B.; Gohy, Jean-Francois; Hadjichristidis, Nikolaos; Rodionov, Valentin

2016-01-01

Multi-arm polystyrene stars functionalized with Grubbs-type catalysts in their cores were synthesized and used for the ring-opening metathesis polymerization (ROMP) of cyclopentene. The spatial confinement of the catalytic sites and the nanoscale phase separation between polystyrene and the growing polypentenamer chains lead to a dramatic inhibition of the ROMP termination and chain transfer steps. Consequently, cyclopentene polymerizations proceeded fast and with a high degree of conversion even in air. The Grubbs second generation catalyst was oxidatively inactivated under the same conditions. In contrast to conventional small-molecule catalysts, the ultimate degree of conversion of cyclopentene monomer and the polydispersity of the product polypentenamer are not affected by the temperature. This indicates that spatial confinement of the catalyst resulted in a significant change in the activation parameters for the alkene metathesis ring-opening.

Preparation of Paraffin@Poly(styrene-co-acrylic acid) Phase Change Nanocapsules via Combined Miniemulsion/Emulsion Polymerization.

Science.gov (United States)

Zhang, Feng; Liu, Tian-Yu; Hou, Gui-Hua; Guan, Rong-Feng; Zhang, Jun-Hao

2018-06-01

The fast development of solid-liquid phase change materials calls for nanomaterials with large specific surface area for rapid heat transfer and encapsulation of phase change materials to prevent potential leakage. Here we report a combined miniemulsion/emulsion polymerization method to prepare poly(styrene-co-acrylic acid)-encapsulated paraffin (paraffin@P(St-co-AA)) nanocapsules. The method could suppress the shortcomings of common miniemulsion polymerization (such as evaporation of monomer and decomposition of initiator during ultrasonication). The paraffin@P(St-co-AA) nanocapsules are uniform in size and the polymer shell can be controlled by the weight ratio of St to paraffin. The phase change behavior of the nanocapsules is similar to that of pure paraffin. We believe our method can also be utilized to synthesize other core-shell phase change materials.

Ring Opening Metathesis Polymerization of Cyclopentene Using a Ruthenium Catalyst Confined by a Branched Polymer Architecture

KAUST Repository

Mugemana, Clement

2016-03-22

Multi-arm polystyrene stars functionalized with Grubbs-type catalysts in their cores were synthesized and used for the ring-opening metathesis polymerization (ROMP) of cyclopentene. The spatial confinement of the catalytic sites and the nanoscale phase separation between polystyrene and the growing polypentenamer chains lead to a dramatic inhibition of the ROMP termination and chain transfer steps. Consequently, cyclopentene polymerizations proceeded fast and with a high degree of conversion even in air. The Grubbs second generation catalyst was oxidatively inactivated under the same conditions. In contrast to conventional small-molecule catalysts, the ultimate degree of conversion of cyclopentene monomer and the polydispersity of the product polypentenamer are not affected by the temperature. This indicates that spatial confinement of the catalyst resulted in a significant change in the activation parameters for the alkene metathesis ring-opening.

In-Situ Immobilization of Ni Complex on Amine-Grafted SiO₂ for Ethylene Polymerization.

Science.gov (United States)

Lee, Sang Yun; Ko, Young Soo

2018-02-01

The results on the In-Situ synthesis of Ni complex on amine-grafted SiO2 and its ethylene polymerization were explained. SiO2/2NS/(DME)NiBr2 and SiO2/3NS/(DME)NiBr2(Ni(II) bromide ethylene glycol dimethyl ether) catalysts were active for ethylene polymerization. The highest activity was shown at the polymerization temperature of 25 °C, and SiO2/2NS/(DME)NiBr2 exhibited higher activity than SiO2/3NS/(DME)NiBr2. The PDI values of SiO2/2NS/(DME)NiBr2 were in the range of 8~18. The aminosilane compounds and Ni were evenly grafted and distributed in the silica. It was proposed that DME ligand was mostly removed during the supporting process, and only NiBr2 was complexed with the amine group of 2NS based on the results of FT-IR and ethylene polymerization.

Radiation-induced polymerization of unsaturated phospholipid mixtures for the synthesis of artificial red cells

Science.gov (United States)

Hosoi, F.; Omichi, H.; Akama, K.; Awai, K.; Endo, S.; Nakano, Y.

1997-08-01

Radiation induced polymerization of phospholipid containing unsaturated acyl chains was applied to the synthesis of artificial red cells. Vesicles of 1,2-bis-(2,4-octadecadienoyl)-phosphatidylcholine (DODPC) and 1-stearoyl-2-(2,4-octadecadienoyl)-phosphatidylcholine (AODPC) were irradiated by 60Co γ-rays to obtain polymerized bilayer structure of these monomers. It was found that the polymerization of unsaturated groups located at 2-acyl chain of DODPC polymerized faster than those of AODPC. The difference was explained by the packed state of these monomers in the bilayer vesicles. The artificial red cell was obtained by irradiating the mixture of DODPC or AODPC with hemoglobin, cholesterol and palmitic acid sodium salt. The integrity of the irradiated hemoglobin in the vesicle was maintained by keeping the suspended solution at low temperature. On the other hand, oxidation of heme part became remarkable when the vesicle was kept at 37°C. The presence of extra hemoglobin outside the vesicle was found useful to prevent this oxidation.

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

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...

Effects of electric fields in polymerization on enthalpy of PMAA anhydridization

Energy Technology Data Exchange (ETDEWEB)

Chang Zhenqi; Liu Gang; Zhang Zhicheng

2004-02-19

PMAA (polymethacrylic acid) polymerized by {gamma}-irradiation in electric field forms six-membered cyclic anhydride during heating process and the enthalpy of PMAA anhydridization was determined by DSC. Why the endothermic peak of PMAA anhydridization in DSC curve between 200 and 300 deg. C appears is particularly explained by calculation. The relations between applied electric field and the enthalpy of PMAA anhydridization are studied. The results show that, with the increases of the intensity of electric field in polymerization, the enthalpy of PMAA forming anhydrides nonlinearly increase, which might be related to orientation of carboxylic acid groups of the PMAA in an electric field.

Polymers on the crime scene forensic analysis of polymeric trace evidence

CERN Document Server

Causin, Valerio

2015-01-01

This book approaches the analysis of forensic contact traces from a polymer science perspective. The development of characterization methods of new or unusual traces and the improvement of existing protocols is described. The book starts with a general introduction to polymers and the issues related to transfer, persistence and recovery of polymeric traces. The chapters present a distinctive feature of polymers, discussing how it can be measured, what the practical difficulties which can be encountered in the analysis, and how useful that information is for comparison or identification purposes. Practical tips for the realization of the forensic analyses are included.

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

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.

HPMA-based polymeric micelles for curcumin solubilization and inhibition of cancer cell growth.

Science.gov (United States)

Naksuriya, Ornchuma; Shi, Yang; van Nostrum, Cornelus F; Anuchapreeda, Songyot; Hennink, Wim E; Okonogi, Siriporn

2015-08-01

Curcumin (CM) has been reported as a potential anticancer agent. However, its pharmaceutical applications as therapeutic agent are hampered because of its poor aqueous solubility. The present study explores the advantages of polymeric micelles composed of block copolymers of methoxypoly(ethylene glycol) (mPEG) and N-(2-hydroxypropyl) methacrylamide (HPMA) modified with monolactate, dilactate and benzoyl side groups to enhance CM solubility and inhibitory activity against cancer cells. Amphiphilic block copolymers, ω-methoxypoly(ethylene glycol)-b-(N-(2-benzoyloxypropyl) methacrylamide) (PEG-HPMA-Bz) were synthesized and characterized by (1)H NMR and GPC. One polymer with a molecular weight of 28,000Da was used to formulate CM and compared with other aromatic substituted polymers. CM was loaded by a fast heating method (PEG-HPMA-DL and PEG-HPMA-Bz-L) and a nanoprecipitation method (PEG-HPMA-Bz). Physicochemical characteristics and cytotoxicity/cytocompatibility of the CM loaded polymeric micelles were evaluated. It was found that HPMA-based polymeric micelles significantly enhanced the solubility of CM. The PEG-HPMA-Bz micelles showed the best solubilization properties. CM loaded polymeric micelles showed sustained release of the loading CM for more than 20days. All of CM loaded polymeric micelles formulations showed a significantly potent cytotoxic effect against three cancer cell lines. HPMA-based polymeric micelles are therefore promising nanodelivery systems of CM for cancer therapy. Copyright © 2015 Elsevier B.V. All rights reserved.

Water-free transfer method for CVD-grown graphene and its application to flexible air-stable graphene transistors.

Science.gov (United States)

Kim, Hyun Ho; Chung, Yoonyoung; Lee, Eunho; Lee, Seong Kyu; Cho, Kilwon

2014-05-28

Transferring graphene without water enables water-sensitive substrates to be used in graphene electronics. A polymeric bilayer (PMMA/PBU) is coated on graphene as a supporting layer for the water-free transfer process and as an excellent passivation layer that enhances device operation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

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.

Fabrication of Alkoxyamine-Functionalized Magnetic Core-Shell Microspheres via Reflux Precipitation Polymerization for Glycopeptide Enrichment

Directory of Open Access Journals (Sweden)

Meng Yu

2016-03-01

Full Text Available As a facile method to prepare hydrophilic polymeric microspheres, reflux precipitation polymerization has been widely used for preparation of polymer nanogels. In this article, we synthesized a phthalamide-protected N-aminooxy methyl acrylamide (NAMAm-p for preparation of alkoxyamine-functionalized polymer composite microspheres via reflux precipitation polymerization. The particle size and functional group density of the composite microspheres could be adjusted by copolymerization with the second monomers, N-isopropyl acrylamide, acrylic acid or 2-hydroxyethyl methacrylate. The resultant microspheres have been characterized by TEM, FT-IR, TGA and DLS. The experimental results showed that the alkoxyamine group density of the microspheres could reach as high as 1.49 mmol/g, and these groups showed a great reactivity with ketone/aldehyde compounds. With the aid of magnetic core, the hybrid microspheres could capture and magnetically isolate glycopeptides from the digested mixture of glycopeptides and non-glycopeptides at a 1:100 molar ratio. After that, we applied the composite microspheres to profile the glycol-proteome of a normal human serum sample, 95 unique glycopeptides and 64 glycoproteins were identified with these enrichment substrates in a 5 μL of serum sample.

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.

Surface polyPEGylation of Eu3+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

Science.gov (United States)

Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2017-03-01

The Eu3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.

Synthesis of butyl acrylate-styrene block copolymers in emulsion by reversible addition-fragmentation chain transfer : effect of surfactant migration upon film formation

NARCIS (Netherlands)

Monteiro, M.J.; Sjöberg, M.; Göttgens, C.M.; Vlist, van der J.

2000-01-01

The synthesis of block copolymers in an environmentally friendly medium was carried out in emulsion polymerizations through the reversible addition-fragmentation chain transfer process, using a transfer active xanthate (MADIX) agent, under batch and starved-feed conditions. First, ab initio

A Visible Light Initiating System for Free Radical Promoted Cationic Polymerization

Science.gov (United States)

1994-02-02

identify the end groups in the polymer of cyclohexene oxide. N,N-Dimethylnaphthyl amine (DNA), a compound with high fluorescence quantum yield, was used...candidates to be polymerized via a cationic mechanism include cyclic ethers, cyclic formals and acetals, vinyl ethers, and epoxy compounds . Of these...reported sensitizer, bears two dimethylamino groups, is direct evidence that an aromatic amine can be present in a cationically photopolymerizable system

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)

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.

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.

The fabrication of small molecule organic light-emitting diode pixels by laser-induced forward transfer

Science.gov (United States)

Shaw-Stewart, J. R. H.; Mattle, T.; Lippert, T. K.; Nagel, M.; Nüesch, F. A.; Wokaun, A.

2013-01-01

Laser-induced forward transfer (LIFT) is a versatile organic light-emitting diode (OLED) pixel deposition process, but has hitherto been applied exclusively to polymeric materials. Here, a modified LIFT process has been used to fabricate small molecule Alq3 organic light-emitting diodes (SMOLEDs). Small molecule thin films are considerably more mechanically brittle than polymeric thin films, which posed significant challenges for LIFT of these materials. The LIFT process presented here uses a polymeric dynamic release layer, a reduced environmental pressure, and a well-defined receiver-donor gap. The Alq3 pixels demonstrate good morphology and functionality, even when compared to conventionally fabricated OLEDs. The Alq3 SMOLED pixel performances show a significant amount of fluence dependence, not observed with polymerical OLED pixels made in previous studies. A layer of tetrabutyl ammonium hydroxide has been deposited on top of the aluminium cathode, as part of the donor substrate, to improve electron injection to the Alq3, by over 600%. These results demonstrate that this variant of LIFT is applicable for the deposition of functional small molecule OLEDs as well as polymeric OLEDs.

Estimating heat transfer bias of kinetic measurement for polymers by differential scanning calorimetry with isothermal mode; Evaluation de l'erreur due au transfert de chaleur lors des mesures cinetiques dans les polymeres par calorimetrie differentielle a balayage en mode isotherme

Energy Technology Data Exchange (ETDEWEB)

Danes, Florin; Garnier, Bertrand [Laboratoire de Thermocinetique, UMR CNRS 6607, Ecole Polytechnique de l' Universite de Nantes, rue C. Pauc, BP50609, 44306 cedex 3, Nantes (France)

2003-06-01

The non-uniformity of temperatures in the DSC sample, and the subsequent difference between mean sample temperature and measured one (in the support of the crucible) are identified as the main source of bias for the isothermal mode determination of kinetic characteristics by differential scanning calorimetry. Chemical reactions under consideration are these with important heat effects into thermal insulators, as for example the reticulation of polymeric materials.By introducing an analytical model of heat transfer in DSC reactive samples, we have performed an estimation for the upper limit of the maximal size of samples which corresponds to a given relative error of the reaction rate, as measured by isothermal DSC calorimetry. For example, with a 5% error and flat samples, we have found admissible sample thicknesses which decrease with temperature and are between 1.9 and 3.1 mm for the sulphur vulcanization of a natural rubber and between 0.6 and 1.1 mm for the reticulation of a pre-polymerized epoxy resin. (authors)

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.

Reverse atom transfer radical polymerization of methyl methacrylate initiated by AIBN/FeCl3/isophthalic acid system

Institute of Scientific and Technical Information of China (English)

无

2001-01-01

The reverse ATRP of MMA using AIBN/FeCl3/ isophthalic acid as the initiating system was successfully performed. The new initiating system can be used to synthesize PMMA with high molecular weight and narrow polydis- persity index. The polymerization shows 'living'/controlled characteristics. Compared with other initiating system used in reverse ATRP, the easy availability and non-toxicity of isophthalic acid make it very attractive.

Oxygen sensitive polymeric nanocapsules for optical dissolved oxygen sensors

Science.gov (United States)

Sun, Zhijuan; Cai, Chenxin; Guo, Fei; Ye, Changhuai; Luo, Yingwu; Ye, Shuming; Luo, Jianchao; Zhu, Fan; Jiang, Chunyue

2018-04-01

Immobilization of the oxygen-sensitive probes (OSPs) in the host matrix greatly impacts the performance and long-term usage of the optical dissolved oxygen (DO) sensors. In this work, fluorescent dyes, as the OSPs, were encapsulated with a crosslinked fluorinated polymer shell by interfacial confined reversible addition fragmentation chain transfer miniemulsion polymerization to fabricate oxygen sensitive polymeric nanocapsules (NCs). The location of fluorescent dyes and the fluorescent properties of the NCs were fully characterized by fourier transform infrared spectrometer, x-ray photoelectron spectrometer and fluorescent spectrum. Dye-encapsulated capacity can be precisely tuned from 0 to 1.3 wt% without self-quenching of the fluorescent dye. The crosslinked fluorinated polymer shell is not only extremely high gas permeability, but also prevents the fluorescent dyes from leakage in aqueous as well as in various organic solvents, such as ethanol, acetone and tetrahydrofuran (THF). An optical DO sensor based on the oxygen sensitive NCs was fabricated, showing high sensitivity, short response time, full reversibility, and long-term operational stability of online monitoring DO. The sensitivity of the optical DO sensor is 7.02 (the ratio of the response value in fully deoxygenated and saturated oxygenated water) in the range 0.96-14.16 mg l-1 and the response time is about 14.3 s. The sensor’s work curve was fit well using the modified Stern-Volmer equation by two-site model, and its response values are hardly affected by pH ranging from 2 to 12 and keep constant during continuous measurement for 3 months. It is believed that the oxygen sensitive polymeric NCs-based optical DO sensor could be particularly useful in long-term online DO monitoring in both aqueous and organic solvent systems.

Transfer and dissipation of energy during wave group propagation on a gentle beach slope

Science.gov (United States)

Padilla, Enrique M.; Alsina, José M.

2017-08-01

The propagation of bichromatic wave groups over a constant 1:100 beach slope and the influence of the group modulation is presented. The modulation is controlled by varying the group frequency, fg, which is shown to remarkably affect the energy transfer to high and low frequency components. The growth of the high frequency (hf) wave skewness increases when fg decreases. This is explained by nonlinear coupling between the primary frequencies, which results in a larger growth of hf components as fg decreases, causing the hf waves to break earlier. Due to high spatial resolution, wave tracking has provided an accurate measurement of the varying breakpoint. These breaking locations are very well described (R2>0.91) by the wave-height to effective-depth ratio (γ). However, for any given Iribarren number, this γ is shown to increase with fg. Therefore, a modified Iribarren number is proposed to include the grouping structure, leading to a considerable improvement in reproducing the measured γ-values. Within the surf zone, the behavior of the Incident Long Wave also depends on the group modulation. For low fg conditions, the lf wave decays only slightly by transferring energy back to the hf wave components. However, for high fg wave conditions, strong dissipation of low frequency (lf) components occurs close to the shoreline associated with lf wave breaking. This mechanism is explained by the growth of the lf wave height, induced partly by the self-self interaction of fg, and partly by the nonlinear coupling between the primary frequencies and fg.

Escherichia coli Phosphoenolpyruvate-Dependent Phosphotransferase System : Mechanism of Phosphoryl-Group Transfer from Phosphoenolpyruvate to HPr

NARCIS (Netherlands)

Misset, Onno; Robillard, George T.

1982-01-01

The mechanism of phosphoryl-group transfer from phosphoenolpyruvate (PEP) to HPr, catalyzed by enzyme I of the Escherichia coli PEP-dependent phosphotransferase system, has been studied in vitro. Steady-state kinetics and isotope exchange measurements revealed that this reaction cannot be described

RAFT Polymerization of Styrene and Maleimide in the Presence of Fluoroalcohol: Hydrogen Bonding Effects with Classical Alternating Copolymerization as Reference

Directory of Open Access Journals (Sweden)

Fangjun Yao

2017-03-01

Full Text Available The impacts of hydrogen bonding on polymerization behavior has been of interest for a long time; however, universality and in-depth understanding are still lacking. For the first time, the effect of hydrogen bonding on the classical alternating-type copolymerization of styrene and maleimide was explored. N-phenylmaleimide (N-PMI/styrene was chosen as a model monomer pair in the presence of hydrogen bonding donor solvent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP, which interacted with N-PMI via hydrogen bonding. Reversible addition-fragmentation chain transfer polymerization (RAFT technique was used to guarantee the “living” polymerization and thus the homogeneity of chain compositions. In comparison with the polymerization in nonhydrogen bonding donor solvent (toluene, the copolymerization in HFIP exhibited a high rate and a slight deviation from alternating copolymerization tendency. The reactivity ratios of N-PMI and St were revealed to be 0.078 and 0.068, respectively, while the reactivity ratios in toluene were 0.026 and 0.050. These interesting results were reasonably explained by using computer simulations, wherein the steric repulsion and electron induction by the hydrogen bonding between HFIP and NPMI were revealed. This work first elucidated the hydrogen bonding interaction in the classical alternating-type copolymerization, which will enrich the research on hydrogen bonding-induced polymerizations.

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.

Computational study of chain transfer to monomer reactions in high-temperature polymerization of alkyl acrylates.

Science.gov (United States)

Moghadam, Nazanin; Liu, Shi; Srinivasan, Sriraj; Grady, Michael C; Soroush, Masoud; Rappe, Andrew M

2013-03-28

This article presents a computational study of chain transfer to monomer (CTM) reactions in self-initiated high-temperature homopolymerization of alkyl acrylates (methyl, ethyl, and n-butyl acrylate). Several mechanisms of CTM are studied. The effects of the length of live polymer chains and the type of monoradical that initiated the live polymer chains on the energy barriers and rate constants of the involved reaction steps are investigated theoretically. All calculations are carried out using density functional theory. Three types of hybrid functionals (B3LYP, X3LYP, and M06-2X) and four basis sets (6-31G(d), 6-31G(d,p), 6-311G(d), and 6-311G(d,p)) are applied to predict the molecular geometries of the reactants, products and transition sates, and energy barriers. Transition state theory is used to estimate rate constants. The results indicate that abstraction of a hydrogen atom (by live polymer chains) from the methyl group in methyl acrylate, the methylene group in ethyl acrylate, and methylene groups in n-butyl acrylate are the most likely mechanisms of CTM. Also, the rate constants of CTM reactions calculated using M06-2X are in good agreement with those estimated from polymer sample measurements using macroscopic mechanistic models. The rate constant values do not change significantly with the length of live polymer chains. Abstraction of a hydrogen atom by a tertiary radical has a higher energy barrier than abstraction by a secondary radical, which agrees with experimental findings. The calculated and experimental NMR spectra of dead polymer chains produced by CTM reactions are comparable. This theoretical/computational study reveals that CTM occurs most likely via hydrogen abstraction by live polymer chains from the methyl group of methyl acrylate and methylene group(s) of ethyl (n-butyl) acrylate.

Constrained Geometry Organotitanium Catalysts Supported on Nanosized Silica for Ethylene (co)Polymerization.

Science.gov (United States)

Li, Kuo-Tseng; Wu, Ling-Huey

2017-05-05

Supported olefin polymerization catalysts can prevent reactor-fouling problems and produce uniform polymer particles. Constrained geometry complexes (CGCs) have less sterically hindered active sites than bis-cyclopentadienyl metallocene catalysts. In the literature, micrometer-sized silica particles were used for supporting CGC catalysts, which might have strong mass transfer limitations. This study aims to improve the activity of supported CGC catalysts by using nanometer-sized silica. Ti[(C₅Me₄)SiMe₂(N t Bu)]Cl₂, a "constrained-geometry" titanium catalyst, was supported on MAO-treated silicas (nano-sized and micro-sized) by an impregnation method. Ethylene homo-polymerization and co-polymerization with 1-octene were carried out in a temperature range of 80-120 °C using toluene as the solvent. Catalysts prepared and polymers produced were characterized. For both catalysts and for both reactions, the maximum activities occurred at 100 °C, which is significantly higher than that (60 °C) reported before for supported bis-cyclopentadienyl metallocene catalysts containing zirconium, and is lower than that (≥140 °C) used for unsupported Ti[(C₅Me₄)SiMe₂(N t Bu)]Me₂ catalyst. Activities of nano-sized catalyst were 2.6 and 1.6 times those of micro-sized catalyst for homopolymerization and copolymerization, respectively. The former produced polymers with higher crystallinity and melting point than the latter. In addition, copolymer produced with nanosized catalyst contained more 1-octene than that produced with microsized catalyst.

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.

Preparation of Dimethylaminoethylmethacrylate Grafted Polymeric Adsorbent by Using Radiation-Induced Grafting Technique for Removal of Anions

International Nuclear Information System (INIS)

Kavakli, P. A.

2006-01-01

The development of efficient separation and purification techniques is very important from industrial, environmental and economic points of view. Polymeric materials having polyfunctional groups such as carboxylic, amide, nitrile, iminodiacetic acid, amidoxime, and ammonium groups, etc., not only possess good hydrophilic properties, but also have good ion exchange properties which make them suitable for metal recovery from aqueous solutions. Radiation induced grafting is a powerful technique capable of controlling the introduction of various functional groups to the polymeric materials, keeping the original properties and especially the mechanical strength of the base material, and thus, allowing the synthesis of more stable polymeric adsorbents. The main objective of this study was to develop special polymeric adsorbents to remove NOx and PO 4 anions from aqueous systems. For this purpose, a novel nonwoven fabric was prepared by radiation-induced graft polymerization of imethylaminoethylmethacrylate (DMAEMA) onto polypropylene coated polyethylene nonwoven fabric. The trunk polymer was irradiated by electron beam at a voltage of 2 MeV and a current of 3 mA in a nitrogen atmosphere at dry-ice temperature at different doses. The degree of grafting was determined as a function of the total dose, monomer concentration, temperature, and reaction time. It was found that the degree of grafting of grafted polymer was greatly affected by reaction conditions. Grafting conditions were optimized, and about 150 % degree of grafting samples was used for further experiments. DMAEMA grafted polymer was later protonated by using acid solution to prepare adsorbent for the removal of anions. Adsorption experiments were performed in column mode for removal of phosphate. Approximately 2000 bed volumes of phosphate-free water can be produced from 10 ppb phosphate solution at high space velocity

Photo-triggered solvent-free metamorphosis of polymeric materials.

Science.gov (United States)

Honda, Satoshi; Toyota, Taro

2017-09-11

Liquefaction and solidification of materials are the most fundamental changes observed during thermal phase transitions, yet the design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion remains challenging. Here, we demonstrate that solvent-free repeatable molecular architectural transformation between liquid-star and nonliquid-network polymers that relies on cleavage and reformation of a covalent bond in hexaarylbiimidazole. Liquid four-armed star-shaped poly(n-butyl acrylate) and poly(dimethyl siloxane) with 2,4,5-triphenylimidazole end groups were first synthesized. Subsequent oxidation of the 2,4,5-triphenylimidazoles into 2,4,5-triphenylimidazoryl radicals and their coupling with these liquid star polymers to form hexaarylbiimidazoles afforded the corresponding nonliquid network polymers. The resulting nonliquid network polymers liquefied upon UV irradiation and produced liquid star-shaped polymers with 2,4,5-triphenylimidazoryl radical end groups that reverted to nonliquid network polymers again by recoupling of the generated 2,4,5-triphenylimidazoryl radicals immediately after terminating UV irradiation.The design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion is challenging. Here, the authors show solvent-free repeatable molecular architectural transformation between liquid-star and non-liquid-network polymers by the cleavage and reformation of covalent bonds in the polymer chain.

Implications of the fluorescence for the conformational analysis of polymeric profisentinidins and procyanidins

Science.gov (United States)

Carin A. Heifer; Joo-Sang Sun; Mark A. Matties; Wayne L. Mattice; Richard W. Hemingway; Jan P. Steynberg; Lisa A. Kelly

1995-01-01

The common monomeric units in the polymeric procyanidins are catechin and epicatechin, which have a hydroxyl group at C(5). this hydroxyl group is absent in the profisetinidins. The fluorescence properties have been characterized for the profisentinidin monomer and dimers, and compared with previous results for the procyanidins. There is a measurable heterogeneity in...

Implications of the fluorescence for the conformational analysis of polymeric profisetinidins and procyanidins

Science.gov (United States)

Carin A. Helfer; Joo-Sang Sun; Mark A. Matties; Wayne L. Mattice; Richard W. Hemingway; Jan P. Steynberg; Lisa A. Kelly

1995-01-01

The common monomeric units in the polymeric proeyanidins are catechin and epicatechin, which have a hydroxyl group at C(5). This hydroxyl group is absent in the profisetinidins. The fluorescence properties have been characterized for the profisetinidin monomer and dimers, and compared with previous results for the procyanidins. There is a measurable heterogeneity in...

Cross-linking of polymeric materials

International Nuclear Information System (INIS)

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

1991-01-01