WorldWideScience

Sample records for azobenzene methacrylate block

  1. Photoinduced optical anisotropy in azobenzene methacrylate block copolymers: Influence of molecular weight and irradiation conditions

    DEFF Research Database (Denmark)

    Gimeno, Sofia; Forcen, Patricia; Oriol, Luis;

    2009-01-01

    The photoinduced anisotropy in a series of azomethacrylate block copolymers with different Molecular weights and azo contents has been investigated under several irradiation conditions. Depending on molecular weight and composition, different microstructures (disordered, lamellar, spherical) appear...... the copolymers in which azobenzene units segregate to nano spheres and the lowest (and less stable) Delta n(N) values, appear in disordered systems not showing any defined microstructure. Besides, higher Delta n(N) is obtained in the copolymers with larger molecular weight of the poly (methyl......) and light power (from 100 to 500 mW/cm(2)) also influence the photoinduced response. Photoinduced Delta n(N) growth rate is faster when both temperature and irradiation power increase. Furthermore, birefringence is only induced at temperatures up to 90 degrees C, the maximum value being obtained at...

  2. Photoresponsive Block Copolymers Containing Azobenzenes and Other Chromophores

    Directory of Open Access Journals (Sweden)

    Takaomi Kobayashi

    2010-01-01

    Full Text Available Photoresponsive block copolymers (PRBCs containing azobenzenes and other chromophores can be easily prepared by controlled polymerization. Their photoresponsive behaviors are generally based on photoisomerization, photocrosslinking, photoalignment and photoinduced cooperative motions. When the photoactive block forms mesogenic phases upon microphase separation of PRBCs, supramolecular cooperative motion in liquid-crystalline PRBCs enables them to self-organize into hierarchical structures with photoresponsive features. This offers novel opportunities to photocontrol microphase-separated nanostructures of well-defined PRBCs and extends their diverse applications in holograms, nanotemplates, photodeformed devices and microporous films.

  3. Holographic Gratings and Data Storage in Azobenzene-Containing Block Copolymers and Molecular Glasses

    Science.gov (United States)

    Audorff, Hubert; Kreger, Klaus; Walker, Roland; Haarer, Dietrich; Kador, Lothar; Schmidt, Hans-Werner

    This review covers synthesis, materials development, and photophysics of azobenzene-containing block copolymers as potential media for reversible volume holographic data storage. For high-density holographic data storage, volume gratings must be inscribed in millimeter-thick samples to achieve efficient angle multiplexing. It is demonstrated that block copolymers with azobenzene side-groups in the minority block develop no detrimental surface relief structures and exhibit superior performance regarding volume gratings, compared to homopolymers and statistical copolymers. Several material concepts for optimizing the refractive index modulation and the stability of volume gratings are presented. Stabilities of more than 2 years were achieved. Most important is the development of polymer blends comprising the azobenzene-containing block copolymer and an optically transparent homopolymer. This enables the preparation of millimeter-thick samples with the required optical density of ˜ 0. 7 at the writing wavelength by conventional injection molding techniques. The inscription of up to 200 holograms at the same lateral position was demonstrated. In addition, more than 1,000 write/erase cycles can be performed. This is the first time that the inscription and erasure of the long-term stable angle-multiplexed volume gratings in a rewritable polymeric medium have been achieved by purely optical means. A second important application for azobenzene-containing materials is the controlled preparation of surface relief structures. It is demonstrated that azobenzene-containing molecular glasses are an ideal class for efficient formation of surface relief gratings (SRGs) with amplitude heights of more than 600 nm. Clear relationships can be established between the chemical structure of the molecules and the behavior of SRG formation. All results are in agreement with the gradient force model by Kumar et al. The surface patterns are stable enough to be transferred to a polymer

  4. Ligand switch in photoinduced copper-mediated polymerization: synthesis of methacrylate-acrylate block copolymers

    OpenAIRE

    CHUANG, Ya-Mi; Wenn, Benjamin; Gielen, Sam; Ethirajan, Anitha; Junkers, Thomas

    2015-01-01

    The use of photo-induced copper-mediated radical polymerization (photoCMP) to synthesize mixed acrylate/methacrylate (methyl acrylate, MA and methyl methacrylate, MMA) block copolymers is investigated. Reactions in which only one type of ligand (Me6TREN) is used lead to unsuccessful outcomes of polymerization due to a mismatch in reactivity of the two monomers. A ligand exchange to PMDETA for methacrylate is required to obtain good block structures. Due to insufficient re-initiation of polyac...

  5. Photoresponsive Azopolyester–PMMA Block Copolymers Obtained by Combination of ATRP, Polycondensation, and “Click” Chemistry

    DEFF Research Database (Denmark)

    Berges, Cristina; Javakhishvili, Irakli; Hvilsted, Søren; Sánchez, Carlos; Alcalá, Rafael

    2012-01-01

    Novel azobenzene‐containing block copolymers (BCs) with a polyester block bearing azobenzene moieties in the side chain and a poly (methyl methacrylate) (PMMA) block have been synthesized by the combination of atom transfer radical polymerization (ATRP), polycondensation, and “click” chemistry. Two...

  6. An Observation on the Microphase Separation of Poly(methyl methacrylate)-block-Polystyrene Copolymer

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The phase behavior of a well-defined poly(methyl methacrylate)-b-polystyrene block copolymer was studied by transmission electron microscope.The results show that a microphase transition may have occurred in the copolymer film.A kind of lamellae and an ordered bicontinuous double-diamond morphology are observed clearly.The lamellar morphology reveals a larger period of about 400 nm.

  7. Synthesis of tri-block copolymers through reverse atom transfer radical polymerization of methyl methacrylate using polyurethane macroiniferter

    Directory of Open Access Journals (Sweden)

    2008-08-01

    Full Text Available Reverse atom transfer radical polymerization was successfully used for the first time to synthesis tri-block copolymers. Poly (methyl methacrylate-block-polyurethane-block-poly (methyl methacrylate tri-block copolymers were synthesized using tetraphenylethane-based polyurethane as a macroiniferter, copper(II halide as a catalyst and N, N, N′, N″, N″-pentamethyldiethylenetriamine as a ligand. Controlled nature of the polymerization was confirmed by the linear increase of number average molecular weight with increasing conversion. Mole contents of poly (methyl methacrylate present in the tri-block copolymers were calculated using proton nuclear magnetic resonance spectroscopy and the results were comparable with the gel permeation chromatography results. Differential scanning calorimetric results confirmed the presence of two different types of blocks in the tri-block copolymers.

  8. Phase behavior of multi-arm star-shaped polystyrene-block-poly(methyl methacrylate) copolymer

    Science.gov (United States)

    Jang, Sangshin; Moon, Hong Chul; Bae, Dusik; Kwak, Jonghen; Kim, Jin Kon

    2013-03-01

    We synthesized star-shaped polystyrene-block-poly(methyl methacrylate) copolymer (PS- b-PMMA) by utilizing α-cyclodextrin (α-CD) as a core of the star-shaped block copolymer. Eighteen hydroxyl groups on α-CD were transformed to bromine by the reaction with α-bromoisobutyryl bromide. We found that the number of bromine substituted arms per one α-CD was higher than 16, which was determined by nuclear magnetic resonance and Matrix-assisted laser desorption/ionization. We could control molecular weight of block copolymers by changing polymerization times. The block copolymers were characterized by gel permeation chromatography and nuclear magnetic resonance. Phase behaviors of these star-shaped block copolymers were investigated by small angle X-ray scattering and transmission electron microscopy.

  9. Phase Behavior of Star-shaped polystyrene-block-poly(methyl methacrylate) Copolymers

    Science.gov (United States)

    Jang, Sangshin; Moon, Hongchul; Lee, Youngmin; Kim, Jin Kon

    2012-02-01

    Star-shaped polystyrene-block-poly(methyl methacrylate) copolymer (PS-b-PMMA) was synthesized by utilizing α-cyclodextrin (α-CD) as a junction point of the star-shaped block copolymer. Eighteen hydroxyl groups on α-CD were substituted with bromine by the reaction with α-bromoisobutyryl bromide for atom transfer radical polymerization. We found that the number of bromine substituted arms per one α-CD was higher than 16 measured by nuclear magnetic resonance and Matrix-assisted laser desorption/ionization. We could control molecular weight of this unusual kind of block copolymer depending on polymerization times. Those polymers were characterized by gel permeation chromatography and nuclear magnetic resonance. Phase behavior of these star-shaped block copolymers were investigated.

  10. Manipulating Interfaces through Surface Confinement of Poly(glycidyl methacrylate)-block-poly(vinyldimethylazlactone), a Dually Reactive Block Copolymer

    International Nuclear Information System (INIS)

    The assembly of dually reactive, well-defined diblock copolymers incorporating the chemoselective/functional monomer, 4,4-dimethyl-2-vinylazlactone (VDMA) and the surface-reactive monomer glycidyl methacrylate (GMA) is examined to understand how competition between surface attachment and microphase segregation influences interfacial structure. Reaction of the PGMA block with surface hydroxyl groups not only anchors the copolymer to the surface, but limits chain mobility, creating brush-like structures comprising PVDMA blocks, which contain reactive azlactone groups. The block copolymers are spin coated at various solution concentrations and annealed at elevated temperature to optimize film deposition to achieve a molecularly uniform layer. The thickness and structure of the polymer thin films are investigated by ellipsometry, infrared spectroscopy, and neutron reflectometry. The results show that deposition of PGMA-b-PVDMA provides a useful route to control film thickness while preserving azlactone groups that can be further modified with biotin-poly(ethylene glycol)amine to generate designer surfaces. The method described herein offers guidance for creating highly functional surfaces, films, or coatings through the use of dually reactive block copolymers and postpolymerization modification.

  11. Effect of block composition on thermal properties and melt viscosity of poly[2-(dimethylaminoethyl methacrylate], poly(ethylene oxide and poly(propylene oxide block co-polymers

    Directory of Open Access Journals (Sweden)

    2011-09-01

    Full Text Available To modify the rheological properties of certain commercial polymers, a set of block copolymers were synthesized through oxyanionic polymerization of 2-(dimethylaminoethyl methacrylate to the chain ends of commercial prepolymers, namely poly(ethylene oxide (PEO, poly(ethylene oxide-block-poly(propylene oxide-block-poly(ethylene oxide (PEO-PPO-PEO, and poly(propylene oxide (PPO. The formed block copolymers were analysed with size exclusion chromatography and nuclear magnetic resonance spectroscopy in order to confirm block formation. Thermal characterization of the resulting polymers was done with differential scanning calorimetry. Thermal transition points were also confirmed with rotational rheometry, which was primarily used to measure melt strength properties of the resulting block co-polymers. It was observed that the synthesised poly[2-(dimethylaminoethyl methacrylate]-block (PDM affected slightly the thermal transition points of crystalline PEO-block but the influence was stronger on amorphous PPO-blocks. Frequency sweeps measured above the melting temperatures for the materials confirmed that the pre-polymers (PEO and PEO-PPO-PEO behave as Newtonian fluids whereas polymers with a PDM block structure exhibit clear shear thinning behaviour. In addition, the PDM block increased the melt viscosity when compared with that one of the pre-polymer. As a final result, it became obvious that pre-polymers modified with PDM were in entangled form, in the melted state as well in the solidified form.

  12. Effect of hydrostatic pressure on phase behavior of deutrated polystyrene-block-poly(n-alkyl methacrylate) copolymer

    International Nuclear Information System (INIS)

    The effect of hydrostatic pressure on phase behavior of deutrated polystyrene-block-poly(n-alkyl methacrylate) [dPS-PnAMA] copolymers with various alkyl chains was investigated by small angle neutron scattering (SANS). Polystyrene-block-poly(n-alkyl methacrylate) copolymers are strongly dependant on both pressure and alkyl number (n) even though these block copolymers have just weak interaction. dPS-PnAMA with n = 2 ∼ 4 exhibited only Lower Disordered-to-Order Transit ion (LDOT), whereas the Ordered-to-Disorder (ODT) was found for n = 1 and n = 6. Additionally, a closed-loop phase behavior was found for n = 5. The order-to-disorder transition (ODT) is only weakly dependent on pressure, whereas, the Lower Disorder-to-Order Transition (LDOT) is strongly dependent on pressure. However, phase transition for a closed-loop phase behavior showed the largest pressure dependence

  13. Synthesis of poly ( methyl methacrylate ) -poly ( lactic acid) -poly (methyl methacrylate) tri-block copolymer%PMMA-PLA-PMMA三嵌段共聚物的制备

    Institute of Scientific and Technical Information of China (English)

    沈珺; 仲玉; 魏荣卿; 刘迎; 刘晓宁; 江伟; 薛奇

    2012-01-01

    Poly( methyl methacrylate)-poly (lactic acid)-poly ( methyl methacrylate) tri-block copolymer was prepared using bromize poly ( lactic acid) as the initiator via atom transfer radical polymerization (ATRP). The effects of n( MMA)/n( Br-PLA-Br) on molecular weight were investigated. Results showed that the first-order plot and a narrow molecular weight distribution followed the characteristics of the ATRP , indicating a controllable polymerization. The glass transition temperature and initial decomposition temperature of the copolymer were well improved by copolymerization, thus it had a potential application in plastic industry.%以双溴端聚乳酸( Br-PLA-Br)为引发剂,通过原子转移自由基聚合法(ATRP)合成聚甲基丙烯酸甲酯-聚乳酸-聚甲基丙烯酸甲酯( PMMA - PLA - PMMA)三嵌段共聚物.考察不同单体与引发剂比例对共聚产物相对分子质量的影响,结果表明:共聚产物相对分子质量随单体比例的增加呈线性增加及随时间延长而递增,但相对分子质量分布恒定,符合ATRP活性、可控聚合的特点.热分析结果表明:该共聚产物的热分解温度和玻璃化转变温度较之聚乳酸均有明显的提高,说明该嵌段共聚物提高了聚乳酸的热稳定性.

  14. Nanostructured Double Hydrophobic Poly(Styrene-b-Methyl Methacrylate) Block Copolymer Membrane Manufactured Via Phase Inversion Technique

    KAUST Repository

    Karunakaran, Madhavan

    2016-03-11

    In this paper, we demonstrate the formation of nanostructured double hydrophobic poly(styrene-b-methyl methacrylate) (PS-b-PMMA) block copolymer membranes via state-of-the-art phase inversion technique. The nanostructured membrane morphologies are tuned by different solvent and block copolymer compositions. The membrane morphology has been investigated using FESEM, AFM and TEM. Morphological investigation shows the formation of both cylindrical and lamellar structures on the top surface of the block copolymer membranes. The PS-b-PMMA having an equal block length (PS160K-b-PMMA160K) exhibits both cylindrical and lamellar structures on the top layer of the asymmetric membrane. All membranes fabricated from PS160K-b-PMMA160K shows an incomplete pore formation in both cylindrical and lamellar morphologies during the phase inversion process. However, PS-b-PMMA (PS135K-b-PMMA19.5K) block copolymer having a short PMMA block allowed us to produce open pore structures with ordered hexagonal cylindrical pores during the phase inversion process. The resulting PS-b-PMMA nanostructured block copolymer membranes have pure water flux from 105-820 l/m2.h.bar and 95% retention of PEG50K

  15. Azobenzene-functionalized cascade molecules

    DEFF Research Database (Denmark)

    Archut, A.; Vogtle, F.; De Cola, L.;

    1998-01-01

    Cascade molecules bearing up to 32 azobenzene groups in the periphery have been prepared from poly(propylene imine) dendrimers and N-hydroxysuccinimide esters. The dendritic azobenzene species show similar isomerization properties as the corresponding azobenzene monomers. The all-E azobenzene den...

  16. Lectin-functionalized poly(glycidyl methacrylate)-block-poly(vinyldimethyl azlactone) surface supports for high avidity microbial capture

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, Ryan R [ORNL; Hinestrosa Salazar, Juan P [ORNL; Shubert, Katherine R [ORNL; Morrell, Jennifer L. [University of Tennessee, Knoxville (UTK); Pelletier, Dale A [ORNL; Messman, Jamie M [ORNL; Kilbey, II, S Michael [ORNL; Lokitz, Bradley S [ORNL; Retterer, Scott T [ORNL

    2013-01-01

    Microbial exopolysaccharides (EPS) play a critical and dynamic role in shaping the interactions between microbial community members and their local environment. The capture of targeted microbes using surface immobilized lectins that recognize specific extracellular oligosaccharide moieties offers a non-destructive method for functional characterization based on EPS content. In this report, we evaluate the use of the block co-polymer, poly(glycidyl methacrylate)-block-4,4-dimethyl-2-vinylazlactone (PGMA-b-PVDMA), as a surface support for lectin-specific microbial capture. Arrays of circular polymer supports ten micron in diameter were generated on silicon substrates to provide discrete, covalent coupling sites for Triticum vulgare and Lens culinaris lectins. These supports promoted microbe adhesion and colony formation in a lectin-specific manner. Silicon posts with similar topography containing only physisorbed lectins showed significantly less activity. These results demonstrate that micropatterned PGMA-b-PVDMA supports provide a unique platform for microbial capture and screening based on EPS content by combining high avidity lectin surfaces with three-dimensional topography.

  17. Glyco-Nanoparticles Made from Self-Assembly of Maltoheptaose-block-Poly(methyl methacrylate): Micelle, Reverse Micelle, and Encapsulation.

    Science.gov (United States)

    Zepon, Karine M; Otsuka, Issei; Bouilhac, Cécile; Muniz, Edvani C; Soldi, Valdir; Borsali, Redouane

    2015-07-13

    The synthesis and the solution-state self-assembly of the "hybrid" diblock copolymers, maltoheptaose-block-poly(methyl methacrylate) (MH-b-PMMA), into large compound micelles (LCMs) and reverve micelle-type nanoparticles, are reported in this paper. The copolymers were self-assembled in water and acetone by direct dissolution method, and the morphologies of the nanoparticles were investigated by dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), transmission electron microscopy (TEM), atomic force microscopy (AFM), proton nuclear magnetic resonance ((1)H NMR), and fluorescence spectroscopy as a function of the volume fraction of the copolymer hydrophobic block, copolymer concentration, stirring speed, and solvent polarity. The DLS measurements and TEM images showed that the hydrodynamic radius (Rh) of the LCMs obtained in water increases with the copolymer concentration. Apart from that, increasing the stirring speed leads to polydispersed aggregations of the LCMs. On the other hand, in acetone, the copolymers self-assembled into reverse micelle-type nanoparticles having Rh values of about 6 nm and micellar aggregates, as revealed the results obtained from DLS, AFM, and (1)H NMR analyses. The variation in micellar structure, that is, conformational inversion from LCMs to reverse micelle-type structures in response to polarity of the solvent, was investigated by apparent water contact angle (WCA) and (1)H NMR analyses. This conformational inversion of the nanoparticles was further confirmed by encapsulation and release of hydrophobic guest molecule, Nile red, characterized by fluorescence spectroscopy. PMID:25974198

  18. Synthesis of (meth)acrylate block copolymers by ligated anionic polymerization

    Czech Academy of Sciences Publication Activity Database

    Vlček, Petr; Čadová, Eva; Janata, Miroslav; Látalová, Petra; Toman, Luděk; Kříž, Jaroslav; Kurková, Dana

    Goa : International Union of Pure and Applied Chemistry, 2005. s. 20-21. [International Symposium on Ionic Polymerization. 23.10.2005-28.10.2005, Goa ] R&D Projects: GA MŠk 1P05ME753 Institutional research plan: CEZ:AV0Z40500505 Keywords : block copolymers * anionic polymerization * tert-alkoxides Subject RIV: CD - Macromolecular Chemistry

  19. Preparation and self-assembly behavior of polystyrene-block-poly (dimethylaminoethyl methacrylate amphiphilic block copolymer using atom transfer radical polymerization

    Directory of Open Access Journals (Sweden)

    2008-03-01

    Full Text Available Asymmetric and semi-symmetric amphiphilic diblock copolymers polystyrene-block-poly (dimethylaminoethyl methacrylate (PS-b-PDMAEMA with the same PS block length of 62 repeat units and quite short (3 repeat units or equivalent (47 repeat units length of PDMAEMA have been prepared simply by varying the ratio of the bromine-terminated macroinitiator polystyrene (PS-Br to DMAEMA using atom transfer radical polymerization (ATRP. The chemical structures and compositions of the PS-b-PDMAEMA block copolymers are studied by nuclear magnetic resonance (NMR spectroscopy, gel permeation chromatography (GPC, and elementary analysis (EA. The self-assembly behaviors of copolymers in N,N-dimethyl formamide (DMF with different pH and dioxane/water binary solvent mixture by direct dissolution method (DD, are studied by transmission electron microscopy (TEM, electron diffracting analysis (EDA, and energy-dispersive analysis of X-rays (EDAX techniques. Transmission electron microscopy results suggest that asymmetric block copolymer PS62-b-PDMAEMA3 (the numbers in the form of footnotes represent repeated units of each monomer in the copolymer can form spherical core-shell micelles, large compound reverse micelles (LCRMs, hexagonal/rhombic phases, reverse hexagonal/rhombic phases, vesicles, reverse vesicles and necklace-like reverse micelles, controlled by common or selective solvent and pH, while most of the aggregates of semi-symmetric PS62-b-PDMAEMA47 are simply spherical, such as spherical core-shell micelles and reverse spherical core-shell micelles, besides hexagonal/rhombic phases. All above structures are controlled by three components of the free energy of aggregation: core-chain stretching, interfacial energy and intercoronal chain interaction.

  20. Synthesis of (meth)acrylate block copolymers by ligated anionic polymerization

    Czech Academy of Sciences Publication Activity Database

    Vlček, Petr; Čadová, Eva; Janata, Miroslav; Látalová, Petra; Toman, Luděk; Kříž, Jaroslav; Kurková, Dana

    2006-01-01

    Roč. 240, č. 1 (2006), s. 141-150. ISSN 1022-1360. [International Symposium on Ionic Polymerization. Goa, 23.10.2005-28.10.2005] R&D Projects: GA MŠk 1P05ME753 Institutional research plan: CEZ:AV0Z40500505 Keywords : anionic polymerization * block copolymers * ester-enolates Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.913, year: 2005

  1. Novel architecture design of block copolymers of ethylene glycol methyl ether methacrylate and carboxybetaine acrylamide

    Czech Academy of Sciences Publication Activity Database

    Rodriguez-Emmenegger, Cesar; Hasan, E.; Brynda, Eduard; Houska, Milan; Sedláková, Zdeňka; Bologna Alles, A.; Huck, W.

    Praha : Institute of Macromolecular Chemistry, 2009. s. 111. ISBN 978-80-85009-59-0. [Prague Meetings on Macromolecules /73./ New Frontiers in Macromolecular Science: From Macromolecular Concepts of Living Matter to Polymers for Better Quality of Life. 05.07.2009-09.07.2009, Prague] R&D Projects: GA AV ČR KAN200670701 Institutional research plan: CEZ:AV0Z40500505 Keywords : block copolymers Subject RIV: CD - Macromolecular Chemistry

  2. Poly(lactide): from hyperbranched copolyesters to new block copolymers with functional methacrylates

    OpenAIRE

    Wolf, Florian Karsten

    2010-01-01

    The prologue of this thesis (Chapter 1.0) gives a general overview on lactone based poly(ester) chemistry with a focus on advanced synthetic strategies for ring-opening polymerization, including the emerging field of organo catalysis. This section is followed by a presentation of the state-of the art regarding the two central fields of the thesis: (i) polyfunctional and branched poly(ester)s in Chapter 1.1 as well as (ii) the development of new poly(ester) based block copolymers with function...

  3. Double stimuli-responsive ultrafiltration membranes from polystyrene-block-poly(N,N-dimethylaminoethyl methacrylate) diblock copolymers.

    Science.gov (United States)

    Schacher, Felix; Rudolph, Tobias; Wieberger, Florian; Ulbricht, Mathias; Müller, Axel H E

    2009-07-01

    We report on the formation of self-supporting, double stimuli-responsive ultrafiltration membranes via the non-solvent-induced phase separation (NIPS) process. The polymers, polystyrene-block-poly(N,N-dimethylaminoethyl methacrylate) (PS-b-PDMAEMA), were synthesized via living anionic polymerization in THF using sec-butyllithium as initiator. Two amphiphilic diblock copolymers were used, S(81)D(19)(75) and S(68)D(32)(100). The membranes were cast from mixtures of THF and DMF. The influence of the solvent composition, the "open-time" before immersion into the coagulation bath, and the casting film thickness onto the membrane morphology were thoroughly investigated, and flux values obtained for the different membrane systems were compared. The higher content in hydrophilic polymer for S(68)D(32)(100) resulted in a better compatibility with the nonsolvent bath consisting of water, leading to a slower precipitation and thus an improved control of the phase separation occurring. Under certain conditions, ordered microphase-separated porous morphologies were observed in parts of the membrane cross-section. Further, the "smart" properties of those novel materials are shown for two representative systems. It could be demonstrated that both stimuli for PDMAEMA, pH and temperature, can be reversibly and independently applied in order to significantly change the transmembrane water flux. PMID:20355953

  4. Thermal-Initiating Potentialities of Poly(methyl methacrylate) Peroxide: Metamorphosis of Block-into-Block Copolymer and Comparative Studies on Surface Texture and Morphology

    OpenAIRE

    Nanda, Ajaya K; Kishore

    2001-01-01

    This is the first report concerning the use of vinyl polyperoxide, namely, poly(methyl methacrylate) peroxide (PMMAP), as a thermal initiator for the synthesis of active polymer PMMAP-PS-PMMAP by free-radical polymerization with styrene. The polymerizations have been carried out at different concentrations of macroinitiator PMMAP. The active polymers have been characterized by 1HNMR, DSC, thermogravimetric analysis, and gel permeation chromatography. PMMAP-PS-PMMAP is further used as the ther...

  5. Additive Driven Self Assembly and Photo-induced Ordering in Poly(ethylene glycol)monomethyl ether monomethacrylate-block-Poly(ethyl methacrylate) Copolymers

    Science.gov (United States)

    Li, Cheng; Watkins, James

    2013-03-01

    Recent work in our labs has shown that blending of hydrogen-bond donating polymers, small molecules or nanoparticles with a block copolymer that contains poly(ethylene oxide) (PEO) can enhance microphase segregation strength and yield well ordered morphologies. While PEO crystallization in these polymers is suppressed by strong interactions between the additive and the PEO segments at high additive loadings, crystallization of the PEO block in the absence of these interactions or at low additive loadings is highly undesirable for many applications. To remedy this issue, poly[poly(ethylene glycol) monomethyl ether monomethacrylate]-block-poly(ethyl methacrylate) was prepared using reversible addition-fragmentation chain transfer polymerization(RAFT). This block copolymer is a phase mixed, non-crystallizable system at room temperature. We find that incorporation of organic additives with multiple carboxylic acid groups such as mellitic acid induces phase segregation in this system. Furthermore, the use of additives in which the hydrogen bond donating group is protected with an acid labile group in combination with a photo acid generator enables photo-induced microphase segregation of the composite to yield well ordered films.

  6. Poly(Lactic Acid) Hemodialysis Membranes with Poly(Lactic Acid)-block-Poly(2-Hydroxyethyl Methacrylate) Copolymer As Additive: Preparation, Characterization, and Performance.

    Science.gov (United States)

    Zhu, Lijing; Liu, Fu; Yu, Xuemin; Xue, Lixin

    2015-08-19

    Poly(lactic acid) (PLA) hemodialysis membranes with enhanced antifouling capability and hemocompatibility were developed using poly(lactic acid)-block-poly(2-hydroxyethyl methacrylate) (PLA-PHEMA) copolymers as the blending additive. PLA-PHEMA block copolymers were synthesized via reversible addition-fragmentation (RAFT) polymerization from aminolyzed PLA. Gel permeation chromatography (GPC) and (1)H-nuclear magnetic resonance ((1)H NMR) were applied to characterize the synthesized products. By blending PLA with the amphiphilic block copolymer, PLA/PLA-PHEMA membranes were prepared by nonsolvent induced phase separation (NIPS) method. Their chemistry and structure were characterized with X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and atomic force microscopy (AFM). The results revealed that PLA/PLA-PHEMA membranes with high PLA-PHEMA contents exhibited enhanced hydrophilicity, water permeability, antifouling and hemocompatibility. Especially, when the PLA-PHEMA concentration was 15 wt %, the water flux of the modified membrane was about 236 L m(-2) h(-1). Its urea and creatinine clearance was more than 0.70 mL/min, lysozyme clearance was about 0.50 mL/min, BSA clearance was as less as 0.31 mL/min. All the results suggest that PLA-PHEMA copolymers had served as effective agents for optimizing the property of PLA-based membrane for hemodialysis applications. PMID:26222398

  7. Optical Modulation of the Diffraction Efficiency in an Indoline Azobenzene/Amorphous Polycarbonate Film.

    Science.gov (United States)

    Williams, G V M; Do, My T T; Middleton, A; Raymond, S G; Bhuiyan, M D H; Kay, A J

    2016-12-01

    We have made a diffraction grating in an indoline azobenzene/amorphous polycarbonate film by two-beam interference at 532 nm that periodically photodegrades the indoline azobenzene dye. Subsequent illumination of the film with 532-nm light into the trans-isomer band leads to trans-cis isomerization in the indoline azobenzene dye and results in a decrease in the trans-isomer band absorption coefficient. This causes the diffraction efficiency to decrease when probed at 655 nm. The diffraction efficiency returns to its original value when the 532-nm light is blocked by thermal relaxation from the indoline azobenzene cis-isomer to the trans-isomer. Thus, we have been able to optically modulate the diffraction efficiency in a thin film diffraction grating. PMID:27416904

  8. Polyelectrolyte behavior of polystyrene-block-poly(methacrylic acid) micelles in aqueous solutions at low ionic strength

    Czech Academy of Sciences Publication Activity Database

    Matějíček, P.; Podhájecká, K.; Humpolíčková, J.; Uhlík, F.; Jelínek, K.; Limpouchová, Z.; Procházka, K.; Špírková, Milena

    2004-01-01

    Roč. 37, č. 26 (2004), s. 10141-10154. ISSN 0024-9297 R&D Projects: GA ČR GA203/04/0490; GA ČR GA203/03/0262; GA ČR GP203/04/P117 Institutional research plan: CEZ:AV0Z4050913 Keywords : fluorescence correlation spectroscopy * block polyelectrolyte s * micelles Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.898, year: 2004

  9. Phase behavior of polystyrene-block-poly(n-alkyl methacrylate) copolymers investigated by SANS, SAXS, and temperature-dependent FTIR spectroscopy

    International Nuclear Information System (INIS)

    The phase behavior of polystyrene-block -poly(n-alkyl methacrylate) (PS-PnAMA) copolymer were investigated by Small-Angle Neutron Scattering (SANS), Small-Angle X-ray Scattering (SAXS), and temperature-dependent Fourier Transform Infrared (FTIR) spectroscopy. Also, the effect of hydrostatic pressure on the transition temperatures was studied by using SANS with pressure controller. Phase behavior was changed significantly with the change of alkyl number (n). For n = 2∼4, only Lower Disordered-to-Order Tansition (LDOT) was observed, whereas the Ordered-to-Disorder (ODT) was found for n =1 and n =6. Finally, a closed-loop phase behavior was found for n =5. Using incompressible random phase approximation, the segmental interactions (χ) between PS and PnAMA for all n values were obtained. The standard expression of χ = a + b/T (where T is the absolute temperature) was valid only for n =1 and n =6. But, this relationship was not valid any more for n = 2∼4. For n =5, a more complex behavior of χ upon temperature was observed. We investigated, by using temperature-dependent FTIR, the mechanism why as closed loop phase behavior was observed for n =5. Interestingly, the conformation of C-C-O stretching band of the PnPMA chain (n=5) (and thus the directional enthapic gain) was different in the two disordered states, and, therefore, the driving force to induce the disordered state at lower temperatures was different from that at higher temperatures

  10. Gd@C82 metallofullerenes for neutron capture therapy—fullerene solubilization by poly(ethylene glycol-block-poly(2-(N, N-diethylaminoethyl methacrylate and resultant efficacy in vitro

    Directory of Open Access Journals (Sweden)

    Yukichi Horiguchi, Shinpei Kudo and Yukio Nagasaki

    2011-01-01

    Full Text Available Poly(ethylene glycol-block-poly(2-(N,N-diethylaminoethyl methacrylate (PEG-b-PAMA was found to solubilize fullerenes such as C60, and this technique was applied to metallofullerenes. Gd@C82 was easily dissolved in water in the presence of PEG-b-PAMA without any covalent derivatization, forming a transparent complex about 20–30 nm in diameter. Low cytotoxicity was confirmed in vitro. Neutron irradiation of cultured cells (colon-26 adenocarcinoma with Gd@C82-PEG-b-PAMA-complexed nanoparticles showed effective cytotoxicity, indicating the effective emission of gamma rays and internal conversion electrons produced from the neutron capture reaction of Gd. This result suggests a potentially valuable approach to gadolinium-based neutron capture therapy.

  11. Morphological investigation of polydisperse asymmetric block copolymer systems of poly(styrene) and poly(methacrylic acid) in the strong segregation regime

    DEFF Research Database (Denmark)

    Asad Ayoubi, Mehran; Zhu, Kaizheng; Nyström, Bo; Olsson, Ulf; Almdal, Kristoffer; Khokhlov, Alexei R.; Piculell, Lennart

    2013-01-01

    Samples of compositionally (highly) asymmetric diblock copolymers and, also, mixtures of diblock and triblock copolymers (the latter obtained as end-coupling products of two diblock molecules of the mixture), composed of (a) monodisperse majority block(s) of poly(styrene) (PS) and a polydisperse...

  12. MALDI-TOF MS analysis of the self-termination products in the anionic methyl methacrylate/tert-butyl acrylate block copolymerization

    Czech Academy of Sciences Publication Activity Database

    Vlček, Petr; Čadová, Eva; Horský, Jiří; Janata, Miroslav

    2015-01-01

    Roč. 72, č. 9 (2015), s. 2227-2239. ISSN 0170-0839 Institutional support: RVO:61389013 Keywords : anionic polymerization * acrylates * block copolymer Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.438, year: 2014

  13. Unusual photoanisotropic alignment in amorphous azobenzene polymers

    DEFF Research Database (Denmark)

    Ramanujam, P.S.

    2015-01-01

    560 and 630nm, where the absorption is minimal, results in a possible uniaxial hedgehog arrangement of the molecules. Experiments performed with a dye laser, which can be tuned continuously between 560 and 630nm, are described. Not only azobenzene but also another photosensitive molecule...

  14. Photoinduced Deformation of Azobenzene Polyester Films

    DEFF Research Database (Denmark)

    Bublitz, D.; Helgert, M.; Fleck, B.;

    2000-01-01

    We investigate two types of azobenzene side-chain polyesters which have shown opposite behaviour in light-induced surface grating formation experiments. Thin films of these polymers prepared on a water surface undergo opposite changes of shape under the influence of polarized light. We propose this...

  15. Photoresponsive Release from Azobenzene-Modified Single Cubic Crystal NaCl/Silica Particles

    Directory of Open Access Journals (Sweden)

    Xingmao Jiang

    2011-01-01

    Full Text Available Azobenzene ligands were uniformly anchored to the pore surfaces of nanoporous silica particles with single crystal NaCl using 4-(3-triethoxysilylpropylureidoazobenzene (TSUA. The functionalization delayed the release of NaCl significantly. The modified particles demonstrated a photocontrolled release by trans/cis isomerization of azobenzene moieties. The addition of amphiphilic solvents, propylene glycol (PG, propylene glycol propyl ether (PGPE, and dipropylene glycol propyl ether (DPGPE delayed the release in water, although the wetting behavior was improved and the delay is the most for the block molecules with the longest carbon chain. The speedup by UV irradiation suggests a strong dependence of diffusion on the switchable pore size. TGA, XRD, FTIR, and NMR techniques were used to characterize the structures.

  16. Graphene oxide catalyzed cis-trans isomerization of azobenzene

    Directory of Open Access Journals (Sweden)

    Dongha Shin

    2014-09-01

    Full Text Available We report the fast cis-trans isomerization of an amine-substituted azobenzene catalyzed by graphene oxide (GO, where the amine functionality facilitates the charge transfer from azobenzene to graphene oxide in contrast to non-substituted azobenzene. This catalytic effect was not observed in stilbene analogues, which strongly supports the existence of different isomerization pathways between azobenzene and stilbene. The graphene oxide catalyzed isomerization is expected to be useful as a new photoisomerization based sensing platform complementary to GO-based fluorescence quenching methods.

  17. Grafting of poly[(methyl methacrylate)-block-styrene] onto cellulose via nitroxide-mediated polymerization, and its polymer/clay nanocomposite.

    Science.gov (United States)

    Karaj-Abad, Saber Ghasemi; Abbasian, Mojtaba; Jaymand, Mehdi

    2016-11-01

    For the first time, nitroxide-mediated polymerization (NMP) was used for synthesis of graft and block copolymers using cellulose (Cell) as a backbone, and polystyrene (PSt) and poly(methyl metacrylate) (PMMA) as the branches. For this purpose, Cell was acetylated by 2-bromoisobutyryl bromide (BrBiB), and then the bromine group was converted to 4-oxy-2,2,6,6-tetramethylpiperidin-1-oxyl group by a substitution nucleophilic reaction to afford a macroinitiator (Cell-TEMPOL). The macroinitiator obtained was subsequently used in controlled graft and block copolymerizations of St and MMA monomers to yield Cell-g-PSt and Cell-g-(PMMA-b-PSt). The chemical structures of all samples as representatives were characterized by FTIR and (1)H NMR spectroscopies. In addition, Cell-g-(PMMA-b-PSt)/organophilic montmorillonite nanocomposite was prepared through a solution intercalation method. TEM was used to evaluate the morphological behavior of the polymer-clay system. It was demonstrated that the addition of small percent of organophilic montmorillonite (O-MMT; 3wt.%) was enough to improve the thermal stability of the nanocomposite. PMID:27516276

  18. Photochromic liquid crystalline structures containing azobenzene moieties

    Czech Academy of Sciences Publication Activity Database

    Studenovský, Martin; Sedláková, Zdeňka; Wang, Geng; Nešpůrek, Stanislav; Janus, K.; Boiko, O. P.; Kajzar, F.

    2004-01-01

    Roč. 212, č. 1 (2004), s. 399-406. ISSN 1022-1360. [Electrical and Related Properties of Polymers and Other Organic Solids /9./. Prague, 14.07.2002-18.07.2002] R&D Projects: GA MŠk OC D14.30 Institutional research plan: CEZ:AV0Z4050913 Keywords : azobenzene * liquid crystal * photochromism Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.691, year: 2004

  19. DNA compaction by azobenzene-containing surfactant

    International Nuclear Information System (INIS)

    We report on the interaction of cationic azobenzene-containing surfactant with DNA investigated by absorption and fluorescence spectroscopy, dynamic light scattering, and atomic force microscopy. The properties of the surfactant can be controlled with light by reversible switching of the azobenzene unit, incorporated into the surfactant tail, between a hydrophobic trans (visible irradiation) and a hydrophilic cis (UV irradiation) configuration. The influence of the trans-cis isomerization of the azobenzene on the compaction process of DNA molecules and the role of both isomers in the formation and colloidal stability of DNA-surfactant complexes is discussed. It is shown that the trans isomer plays a major role in the DNA compaction process. The influence of the cis isomer on the DNA coil configuration is rather small. The construction of a phase diagram of the DNA concentration versus surfactant/DNA charge ratio allows distancing between three major phases: colloidally stable and unstable compacted globules, and extended coil conformation. There is a critical concentration of DNA above which the compacted globules can be hindered from aggregation and precipitation by adding an appropriate amount of the surfactant in the trans configuration. This is because of the compensation of hydrophobicity of the globules with an increasing amount of the surfactant. Below the critical DNA concentration, the compacted globules are colloidally stable and can be reversibly transferred with light to an extended coil state.

  20. DNA compaction by azobenzene-containing surfactant

    Science.gov (United States)

    Zakrevskyy, Yuriy; Kopyshev, Alexey; Lomadze, Nino; Morozova, Elena; Lysyakova, Ludmila; Kasyanenko, Nina; Santer, Svetlana

    2011-08-01

    We report on the interaction of cationic azobenzene-containing surfactant with DNA investigated by absorption and fluorescence spectroscopy, dynamic light scattering, and atomic force microscopy. The properties of the surfactant can be controlled with light by reversible switching of the azobenzene unit, incorporated into the surfactant tail, between a hydrophobic trans (visible irradiation) and a hydrophilic cis (UV irradiation) configuration. The influence of the trans-cis isomerization of the azobenzene on the compaction process of DNA molecules and the role of both isomers in the formation and colloidal stability of DNA-surfactant complexes is discussed. It is shown that the trans isomer plays a major role in the DNA compaction process. The influence of the cis isomer on the DNA coil configuration is rather small. The construction of a phase diagram of the DNA concentration versus surfactant/DNA charge ratio allows distancing between three major phases: colloidally stable and unstable compacted globules, and extended coil conformation. There is a critical concentration of DNA above which the compacted globules can be hindered from aggregation and precipitation by adding an appropriate amount of the surfactant in the trans configuration. This is because of the compensation of hydrophobicity of the globules with an increasing amount of the surfactant. Below the critical DNA concentration, the compacted globules are colloidally stable and can be reversibly transferred with light to an extended coil state.

  1. Cooperative Switching in Nanofibers of Azobenzene Oligomers.

    Science.gov (United States)

    Weber, Christopher; Liebig, Tobias; Gensler, Manuel; Zykov, Anton; Pithan, Linus; Rabe, Jürgen P; Hecht, Stefan; Bléger, David; Kowarik, Stefan

    2016-01-01

    Next-generation molecular devices and machines demand the integration of molecular switches into hierarchical assemblies to amplify the response of the system from the molecular level to the meso- or macro-scale. Here, we demonstrate that multi-azobenzene oligomers can assemble to form robust supramolecular nanofibers in which they can be switched repeatedly between the E- and Z-configuration. While in isolated oligomers the azobenzene units undergo reversible photoisomerization independently, in the nanofibers they are coupled via intermolecular interactions and switch cooperatively as evidenced by unusual thermal and kinetic behavior. We find that the photoisomerization rate from the Z-isomer to the E-isomer depends on the fraction of Z-azobenzene in the nanofibers, and is increased by more than a factor of 4 in Z-rich fibers when compared to E-rich fibers. This demonstrates the great potential of coupling individual photochromic units for increasing their quantum efficiency in the solid state with potential relevance for actuation and sensing. PMID:27161608

  2. Cooperative Switching in Nanofibers of Azobenzene Oligomers

    Science.gov (United States)

    Weber, Christopher; Liebig, Tobias; Gensler, Manuel; Zykov, Anton; Pithan, Linus; Rabe, Jürgen P.; Hecht, Stefan; Bléger, David; Kowarik, Stefan

    2016-01-01

    Next-generation molecular devices and machines demand the integration of molecular switches into hierarchical assemblies to amplify the response of the system from the molecular level to the meso- or macro-scale. Here, we demonstrate that multi-azobenzene oligomers can assemble to form robust supramolecular nanofibers in which they can be switched repeatedly between the E- and Z-configuration. While in isolated oligomers the azobenzene units undergo reversible photoisomerization independently, in the nanofibers they are coupled via intermolecular interactions and switch cooperatively as evidenced by unusual thermal and kinetic behavior. We find that the photoisomerization rate from the Z-isomer to the E-isomer depends on the fraction of Z-azobenzene in the nanofibers, and is increased by more than a factor of 4 in Z-rich fibers when compared to E-rich fibers. This demonstrates the great potential of coupling individual photochromic units for increasing their quantum efficiency in the solid state with potential relevance for actuation and sensing. PMID:27161608

  3. Surface modification of magnetite nanoparticle with azobenzene-containing water dispersible polymer

    International Nuclear Information System (INIS)

    We here report the synthesis of magnetite nanoparticle (MNP) grafted with poly (ethylene glycol) methyl ether methacrylate (PEGMA)-azobenzene acrylate (ABA) statistical copolymer via atom transfer radical polymerization (ATRP) for drug entrapment and photocontrolled release. MNP was synthesized via thermal decomposition of iron (III) acetylacetonate in benzyl alcohol and surface functionalized to obtain ATRP initiating sites. Molar compositions of the copolymer on MNP surface were systematically varied (100:0, 90:10, 70:30, and 50:50 of PEGMA:ABA, respectively) to obtain water dispersible particles with various amounts of azobenzene. The presence of polymeric shell on MNP core was evidenced by transmission electron microscopy (TEM). Drug loading and entrapment efficiencies as well as drug release behavior of the copolymer–MNP complexes were investigated. It was found that when percent of ABA in the copolymers was increased, entrapment and loading efficiencies of prednisolone model drug were enhanced. Releasing rate and percent of the released prednisolone of the complex exposed in UV light were slightly enhanced as compared to the system without UV irradiation. This copolymer–MNP complex with photocontrollable drug release and magnetic field-directed properties is warranted for further studies for potential uses as a novel drug delivery vehicle.

  4. Photomechanical bending mechanics of polydomain azobenzene liquid crystal polymer network films

    International Nuclear Information System (INIS)

    Glassy, polydomain azobenzene liquid crystal polymer networks (azo-LCNs) have been synthesized, characterized, and modeled to understand composition dependence on large amplitude, bidirectional bending, and twisting deformation upon irradiation with linearly polarized blue-green (440-514 nm) light. These materials exhibit interesting properties for adaptive structure applications in which the shape of the photoresponsive material can be rapidly reconfigured with light. The basis for the photomechanical output observed in these materials is absorption of actinic light by azobenzene, which upon photoisomerization dictates an internal stress within the local polymer network. The photoinduced evolution of the underlying liquid crystal microstructure is manifested as macroscopic deformation of the glassy polymer film. Accordingly, this work examines the polarization-controlled bidirectional bending of highly concentrated azo-LCN materials and correlates the macroscopic output (observed as bending) to measured blocked stresses upon irradiation with blue-green light of varying polarization. The resulting photomechanical output is highly dependent on the concentration of crosslinked azobenzene mesogens employed in the formulation. Experiments that quantify photomechanical bending and photogenerated stress are compared to a large deformation photomechanical shell model to quantify the effect of polarized light interactions with the material during static and dynamic polarized light induced deformation. The model comparisons illustrate differences in internal photostrain and deformation rates as a function of composition and external mechanical constraints.

  5. Rewritable azobenzene polyester for polarization holographic data storage

    DEFF Research Database (Denmark)

    Kerekes, A; Sajti, Sz.; Loerincz, Emoeke;

    2000-01-01

    Optical storage properties of thin azobenzene side-chain polyester films were examined by polarization holographic measurements. The new amorphous polyester film is the candidate material for the purpose of rewritable holographic memory system. Temporal formation of anisotropic and topographic...... erasing was tested. The ability of azobenzene polyester for rewriting was found satisfactory after many writing-erasing cycles....

  6. Optically induced surface relief phenomena in azobenzene polymers

    DEFF Research Database (Denmark)

    Holme, NCR; Nikolova, Ludmila; Hvilsted, Søren;

    1999-01-01

    Azobenzene polymers and oligomers show intriguing surface relief features when irradiated with polarized laser light. We show through atomic force microscopic investigation of side-chain azobenzene polymers after irradiation through an amplitude mask that large peaks or trenches result depending ...

  7. Photochemical properties of multi-azobenzene compounds.

    Science.gov (United States)

    Bahrenburg, Julia; Sievers, Claudia M; Schönborn, Jan Boyke; Hartke, Bernd; Renth, Falk; Temps, Friedrich; Näther, Christian; Sönnichsen, Frank D

    2013-03-01

    A systematic study is reported of the photochemical properties of the multi-azobenzene compounds bis[4-(phenylazo)phenyl]amine (BPAPA) and tris[4-(phenylazo)phenyl]amine (TPAPA) compared to the parent molecule 4-aminoazobenzene (AAB). The bis- and tris-azobenzenes were synthesised by a variant of the Ullmann reaction and exist in their stable all-E forms at room temperature. Striking changes in the spectral positions and intensities of their first ππ* absorption bands compared to AAB reveal strong electronic coupling between the AB units. The nature of the excited states was explored by quantum chemical calculations at the approximate coupled-cluster (CC2) level. Upon UV/VIS irradiation, the molecules isomerise to the Z-isomer (AAB), ZE- and ZZ-isomers (BPAPA), and ZEE-, ZZE- and ZZZ-isomers (TPAPA), respectively. The photoswitching behaviours were investigated by UV/VIS and NMR spectroscopies. All individual isomers were detected by one-dimensional (1D) (1)H NMR spectroscopy (BPAPA) and two-dimensional (2D) HSQC NMR spectroscopy (TPAPA). A kinetic analysis provided the isomer-specific thermal lifetimes. The variance of the thermal lifetimes demonstrates a dependence of the Z-E isomerisation on the chromophore size and number of AB units. PMID:23224342

  8. The azobenzene optical storage puzzle - Demands on the polymer scaffold?

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Ramanujam, P.S.

    2001-01-01

    The basic mechanism of optical information storage utilizing the azobenzene photoaddressable moiety will briefly be introduced. A synthetically flexible polyester matrix covalently integrating cyanoazobenzene in regularly spaced side chains is particularly well suited for holographic storage. Not...

  9. The Azobenzene Optical Storage Puzzle - Demands on the Polymer Scaffold?

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Ramanujam, PS

    2001-01-01

    The basic mechanism of optical information storage utilizing the azobenzene photoaddressable moiety will briefly be introduced. A synthetically flexible polyester matrix covalently integrating cyanoazobenzene in regularly spaced side chains is particularly well suited for holographic storage. Not...

  10. Azobenzene-based Polymers for Solar Thermal Batteries

    Science.gov (United States)

    Venkataraman, Dhandapani

    Azobenzene exists as two isomers, a higher energy cis-isomer and a lower energy trans-isomer. The isomers interconvert under light or heat. Recently, there is a renewed interest in capturing the difference in the energies of the isomers and using azobenzene-based molecules as active layers for solar thermal batteries. My research group has been exploring azobenzene-based polymers as candidates for solar thermal batteries. In this talk, I will show that the azo-benzene moieties can be converted to the cis-form using light and converted back to the trans form using mechanical force. I will provide some of our recent results that indicate that high energy densities can be achieved in these polymers.

  11. MORPHOLOGY STUDY OF A SERIES OF AZOBENZENE-CONTAINING SIDE-ON LIQUID CRYSTALLINE TRIBLOCK COPOLYMERS

    Institute of Scientific and Technical Information of China (English)

    Wei Deng; Annie Br(u)let; Pierre-antoine Albouy; Patrick Keller; Xiao-gong Wang; Min-hui Li

    2012-01-01

    A series of azobenzene containing side-on liquid crystalline ABA triblock copolymers were investigated.This triblock series possesses the same central liquid crystal block B and various lengths of the amorphous block A.Transmission electron microscopy (TEM),small angle X-rays and neutron scattering (SAXS and SANS) were used to study their morphologies.Aider annealing the samples over weeks at a temperature within the nematic temperature range of block B,different morphologies (disordered,lamellar,perforated layer and hexagonal cylinder) were observed by TEM.The alignment behavior of these azo triblock copolymers in the magnetic field for artificial muscle application,as well as the phase period and the order-disorder transition (ODT) were studied in situ by SANS.

  12. Holographic Gratings in Azobenzene Side-Chain Polymethacrylates

    DEFF Research Database (Denmark)

    Andruzzi, Luisa; Altomare, Angelina; Ciardelli, Francesco; Solaro, Roberto; Hvilsted, Søren; Ramanujam, P.S.

    1999-01-01

    Optical storage properties of thin unoriented liquid crystalline and amorphous side-chain azobenzene polymethacrylate films are examined by polarization holographic measurements. The investigated materials are free radical copolymers derived from two photochromic monomers, 6-(4-oxy-4'-cyanoazoben......Optical storage properties of thin unoriented liquid crystalline and amorphous side-chain azobenzene polymethacrylate films are examined by polarization holographic measurements. The investigated materials are free radical copolymers derived from two photochromic monomers, 6-(4-oxy-4...

  13. Physical processes in azobenzene polymers on irradiation with polarized light

    DEFF Research Database (Denmark)

    Holme, N.C.R.; Nikolova, L.; Norris, T.B.;

    1999-01-01

    Azobenzenes can serve as model compounds for the study of trans-cis isomerization in more complex molecules. We have performed time-resolved spectroscopy in solutions containing free azobenzene chromophores and diols with a view to obtaining the energy levels and lifetimes of the excited states. A...... single beam transmission measurements through a mask, followed by atomic force microscope and profiler investigations. It is concluded that none of the prevalent theories can explain all the observed facts....

  14. Ultrasensitive photoreversible molecular sensors of azobenzene-functionalized plasmonic nanoantennas.

    Science.gov (United States)

    Joshi, Gayatri K; Blodgett, Karl N; Muhoberac, Barry B; Johnson, Merrell A; Smith, Kimberly A; Sardar, Rajesh

    2014-02-12

    This Letter describes an unprecedentedly large and photoreversible localized surface plasmon resonance (LSPR) wavelength shift caused by photoisomerization of azobenzenes attached to gold nanoprisms that act as nanoantennas. The blue light-induced cis to trans azobenzene conformational change occurs in the solid state and controls the optical properties of the nanoprisms shifting their LSPR peak up to 21 nm toward longer wavelengths. This shift is consistent with the increase in thickness of the local dielectric environment (0.6 nm) surrounding the nanoprism and perhaps a contribution from plasmonic energy transfer between the nanoprism and azobenzenes. The effects of the azobenzene conformational change and its photoreversibility were also probed through surface-enhanced Raman spectroscopy (SERS) showing that the electronic interaction between the nanoprisms and bound azobenzenes in their cis conformation significantly enhances the intensity of the Raman bands of the azobenzenes. The SERS data suggests that the isomerization is controlled by first-order kinetics with a rate constant of 1.0 × 10(-4) s(-1). Our demonstration of light-induced photoreversibility of this type of molecular machine is the first-step toward removing present limitations on detection of molecular motion in solid-state devices using LSPR spectroscopy with nanoprisms. Modulating the LSPR peak position and controlling energy transfer across the nanostructure-organic molecule interface are very important for the fabrication of plasmonic-based nanoscale devices. PMID:24393014

  15. Nonlinear optical properties of an azobenzene polymer

    International Nuclear Information System (INIS)

    The nonlinear optical properties of an azobenzene polymer azo12—MO were investigated by a Z-scan technique. The polymer was synthesized by assembling the liquid-crystalline polymer azo12 with methyl orange. The nonlinear refractive index (1.39 × 10−15 cm2/W) and the nonlinear absorption coefficient (0.11 cm/GW) of azo12—MO were determined with 532-nm picosecond laser pulses at the irradiance of 92.40 GW/cm2. When compared to the nonlinear properties of azo12 and methyl orange, azo12—MO possesses the advantages of its two constituents and shows larger nonlinear optical properties. (electromagnetism, optics, acoustics, heat transfer, classical mechanics, and fluid dynamics)

  16. Mechanical Properties of Weakly Segregated Block Copolymers. 3. Influence of Strain Rate and Temperature on Tensile Properties of Poly(styrene-b-butyl methacrylate) Diblock Copolymers with Different Morphologies

    NARCIS (Netherlands)

    Weidisch, R.; Stamm, M.; Michler, G.H.; Fischer, H.R.; Jérôme, R.

    1999-01-01

    Poly(styrene-b-butyl methacrylate) diblock copolymers, PS-6-PBMA, with different morphologies are investigated with respect to the influence of strain rate and temperature on tensile properties. In the first part the mechanical properties of bicontinuous and perforated lamellar structure are compare

  17. Photo-induced fluorescence emission enhancement of azobenzene thin films

    OpenAIRE

    Haruta, Osamu; Matsuo, Yasutaka; Ijiro, Kuniharu

    2008-01-01

    UV irradiation-induced fluorescence enhancement of thin films composed of azobenzene amphiphiles, C12AzoC10N+ (AzoN+), was investigated. UV irradiation to Langmuir-Blodgett (LB) monolayers of AzoN+ indicated that the fluorescence emission from an irradiated area was enhanced and the emission was independent of the aggregation structures of an azobenzene moiety. Moreover, UV irradiation to cast films of AzoN+ revealed that the enhancement was increased by increasing the irradiation time. The f...

  18. Preparation of Pickering Double Emulsions Using Block Copolymer Worms

    OpenAIRE

    Thompson, Kate L.; Mable, Charlotte J.; Lane, Jacob A.; Derry, Mathew J.; Fielding, Lee A.; Armes, Steven P.

    2015-01-01

    The rational formulation of Pickering double emulsions is described using a judicious combination of hydrophilic and hydrophobic block copolymer worms as highly anisotropic emulsifiers. More specifically, RAFT dispersion polymerization was utilized to prepare poly(lauryl methacrylate)–poly(benzyl methacrylate) worms at 20% w/w solids in n-dodecane and poly(glycerol monomethacrylate)–poly(2-hydroxypropyl methacrylate)–poly(benzyl methacrylate) worms at 13% w/w solids in water by polymerization...

  19. Colorimetric Sugar Sensing Using Boronic Acid-Substituted Azobenzenes

    Directory of Open Access Journals (Sweden)

    Yuya Egawa

    2014-02-01

    Full Text Available In association with increasing diabetes prevalence, it is desirable to develop new glucose sensing systems with low cost, ease of use, high stability and good portability. Boronic acid is one of the potential candidates for a future alternative to enzyme-based glucose sensors. Boronic acid derivatives have been widely used for the sugar recognition motif, because boronic acids bind adjacent diols to form cyclic boronate esters. In order to develop colorimetric sugar sensors, boronic acid-conjugated azobenzenes have been synthesized. There are several types of boronic acid azobenzenes, and their characteristics tend to rely on the substitute position of the boronic acid moiety. For example, o-substitution of boronic acid to the azo group gives the advantage of a significant color change upon sugar addition. Nitrogen-15 Nuclear Magnetic Resonance (NMR studies clearly show a signaling mechanism based on the formation and cleavage of the B–N dative bond between boronic acid and azo moieties in the dye. Some boronic acid-substituted azobenzenes were attached to a polymer or utilized for supramolecular chemistry to produce glucose-selective binding, in which two boronic acid moieties cooperatively bind one glucose molecule. In addition, boronic acid-substituted azobenzenes have been applied not only for glucose monitoring, but also for the sensing of glycated hemoglobin and dopamine.

  20. The Volume Holographic Optical Storage Potential in Azobenzene Containing Polymers

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Sanchez, Carlos; Alcalá, Rafael

    2009-01-01

    suitable for holographic storage applications. However, they still present several problems, mainly those related with light sensitivity, response time and stability of the stored information. In this article we review the work performed on volume holographic storage using azobenzene containing polymers as...

  1. Pattern Formation and Quasicrystal Structure in Azobenzene Polymer Film

    Institute of Scientific and Technical Information of China (English)

    XU Ze-Da; CAI Zhi-Gang; ZHANG Ling-Zhi; LIU Yan-Fa; YANG Jie; SHE Wei-Long; ZHOU Jian-Ying

    2000-01-01

    Pattern formation in azobenzene polymer film by degenerate four-wave mixing is reported. Island arrays with specific patterns are analyzed with scanning electron microscopy and polarizing optical microscopy. It is demonstrated that the control of photo-induced nanostructure sized micropattern in the nonlinear organic film is possible by using properly polarized writing beams with the total incident power exceeding a certain threshold.

  2. Photoinduced Circular Anisotropy in Side-Chain Azobenzene Polyesters

    DEFF Research Database (Denmark)

    Nikolova, L.; Todorov, T.; Ivanov, M.;

    1997-01-01

    We report for the first time the inducing of large circular anisotropy in previously unoriented films of side-chain azobenzene polyesters on illumination with circularly polarized light at a wavelength of 488 nm. The circular dichroism and optical activity are measured simultaneously in real time...

  3. Polarisation-sensitive optical elements in azobenzene polyesters and peptides

    DEFF Research Database (Denmark)

    Ramanujam, P.S.; Dam-Hansen, Carsten; Berg, Rolf Henrik;

    2006-01-01

    In this article, we describe fabrication of polarisation holographic optical elements in azobenzene polyesters. Both liquid crystalline and amorphous side-chain polyesters have been utilised. Diffractive optical elements such as lenses and gratings that are sensitive to the polarisation of the in...

  4. Photo-orientation in azobenzene containing polybutadiene based polymer

    Czech Academy of Sciences Publication Activity Database

    Rais, David; Nešpůrek, Stanislav; Zakrevskyy, Y.; Stumpe, J.; Sedláková, Zdeňka; Studenovský, Martin

    2005-01-01

    Roč. 7, č. 3 (2005), s. 1371-1375. ISSN 1454-4164 R&D Projects: GA AV ČR IAA4112401 Institutional research plan: CEZ:AV0Z40500505 Keywords : azobenzene * polybutadien * photo-orientation Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.138, year: 2005

  5. Quantum theory and experimental studies of absorption spectra and photoisomerization of azobenzene polymers

    DEFF Research Database (Denmark)

    Pedersen, Thomas Garm; Ramanujam, P.S.; Johansen, P.M.;

    1998-01-01

    The microscopic properties of azobenzene chromophores are important for a correct description of optical storage systems based on photoinduced anisotropy in azobenzene polymers. A quantum model of these properties is presented and verified by comparison to experimental absorption spectra for trans...... and cis isomers of cyano methoxy azobenzene. In addition, the trans --> cis quantum efficiency is measured, and hence the combined experimental and theoretical work allows one to determine the essential molecular properties, including magnitude and anisotropy of the absorption cross section and...

  6. Geometry Control of Photo-induced Microstructures in an Azobenzene Polymer Film

    Institute of Scientific and Technical Information of China (English)

    Xu Ze-Da; LI Zhen; LIANG Li-Zhen; PENG Zhuo-Lun; CAI Zhi-Gang; ZHOU Jian-Ying; NINULESCU Valerica; ZHANG Ling-Zhi

    2001-01-01

    The mechanisms of photo-induced microstructures in an azobenzene polymer film are presented. They are based on the spatial periodic modulation of optical intensity and the photoisomerization of azobenzene molecules with the movement of main chains. Experiment and theory jointly point out the possibility of photo-inducing desired spatial microstructures in an azobenzene organic polymer via adequate optical lattices and adequately polarized ‘writing' beams.

  7. Surface relief measurements in side-chain azobenzene polyesters with different substituents

    DEFF Research Database (Denmark)

    Helgert, M.; Wenke, L.; Hvilsted, Søren;

    2001-01-01

    Light-induced surface modification of a series of liquid-crystalline side-chain azobenzene polyesters which have the same main- and side-chain structure but eleven different substituents on the azobenzene is investigated. Using a transmission mask as well as single focused beams we show that the...... azobenzene polyester was included in the study for comparison. The results point to a mechanism of the surface relief phenomenon, in which the architecture of the polyesters plays a crucial role....

  8. Holographic Gratings in Azobenzene Side-Chain Polymethacrylates

    DEFF Research Database (Denmark)

    Andruzzi, Luisa; Altomare, Angelina; Ciardelli, Francesco;

    1999-01-01

    Optical storage properties of thin unoriented liquid crystalline and amorphous side-chain azobenzene polymethacrylate films are examined by polarization holographic measurements. The investigated materials are free radical copolymers derived from two photochromic monomers, 6-(4-oxy-4'-cyanoazoben......Optical storage properties of thin unoriented liquid crystalline and amorphous side-chain azobenzene polymethacrylate films are examined by polarization holographic measurements. The investigated materials are free radical copolymers derived from two photochromic monomers, 6-(4-oxy-4...... polarizing optical microscopy. Atomic force microscopy investigations have been carried out on the polarization holographic gratings recorded in the polymethacrylate films. A surface relief grating has been found to appear in all films after irradiation. The copolymers with 50-75% dye content exhibit the...

  9. Synthesis and characterization of termini azobenzene-dendrimer

    Directory of Open Access Journals (Sweden)

    Omid Louie

    2013-10-01

    Full Text Available Some of the organic molecules can be isomerized upon photoirradiation and when they are accompanied by a change in the visible absorption spectrum, it can be called photochromism. Azobenzenes which are important parts of molecular machines and nanotechnology can be called photoisomerizationazobenzene (azo chromophores, and have been incorporated into a wide variety of materials and molecular architectures, including polymers, dendrimers, and molecular glasses. We synthesized and characterized the AB2 type polyamidoamine (PAMAM dendrimers by single active site. PAMAM diazobenzenedendrimer was synthesized and characterized by FTIR and NMR (1H, 13C and CHN-O Elementary analysis. A simple method can be used for the synthesis of azobenzene derivative PAMAM dendrimer and other similar compounds.

  10. Preparation and Nonlinear Optical Property of Azobenzene Substituted Polyacetylene

    Institute of Scientific and Technical Information of China (English)

    Shou Chun YIN; Gang LI; Hong Yao XU; Ya Chen GAO; Yin Lin SONG

    2005-01-01

    Two new functional polyacetylenes bearing different azobenzene group, -{ HC=C[azo-N(CH3)CH2CH2OH] } n-, [poly(EHAB); azo = 4,4'-azobenzene] and - { HC=C[azo-N(CH3)CH2CH2OCOC3H7]}n-, [poly(EEAB)]} were prepared by [Rh(nbd)Cl]2-Et3N catalysts. Poly(EHAB) has poor solubility while poly(EEAB) can be dissolved in common solvent. The polymers were characterized by FTIR, 1H NMR, UV and GPC. The nonlinear optical property of the soluble poly(EEAB) was investigated with 8 ns width pulse at 532 nm by Z-scan technique. The results show that poly(EEAB) is endowed with the larger third-order nonlinear optical property.

  11. Polymer scaffolds bearing azobenzene - Potential for optical information storage

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Ramanujam, P.S.

    2001-01-01

    The fundamental optical storage mechanism of the laser light addressable azobenzene moiety is briefly introduced. A modular and flexible synthesis design furnishes polyester matrices covalently integrating cyanoazobenzene in regularly spaced side chains. Thin films of these materials are particul......The fundamental optical storage mechanism of the laser light addressable azobenzene moiety is briefly introduced. A modular and flexible synthesis design furnishes polyester matrices covalently integrating cyanoazobenzene in regularly spaced side chains. Thin films of these materials are...... particularly well suited for holographic storage. Notable figures of merits of liquid crystalline polyesters are response time to blue-green laser light of the order of nanoseconds, storage capacity expressed as 5000 lines/mm, and high, permanent (almost nine years) diffraction efficiency of the order of 50...

  12. Light-controlled anisotropy in dielectrics containing azobenzene

    Czech Academy of Sciences Publication Activity Database

    Rais, David; Nešpůrek, Stanislav; Sedláková, Zdeňka; Zakrevskyy, Y.; Stumpe, J.

    Vol. Nr 982. Lodz : Department of Molecular Physics, Technical University of Lodz, 2006 - (Socha, A.), s. 270-271 ISSN 0458-1555. [Conference International Dielectric Society /4./ and International Conference Dielectric and Related Phenomena /9./. Poznan (PL), 03.09.2006-07.09.2006] R&D Projects: GA AV ČR IAA4112401 Institutional research plan: CEZ:AV0Z40500505 Keywords : azobenzene * light anisotropy * photochromism Subject RIV: CD - Macromolecular Chemistry

  13. Propagation of polarized light through azobenzene polyester films

    DEFF Research Database (Denmark)

    Nedelchev, L; Matharu, A; Nikolova, Ludmila;

    2002-01-01

    When elliptically polarized light of appropriate wavelength Corresponding to trans-cis-trans isomerisation process is incident on thin films of azobenzene polyesters, a helical structure is induced. We investigate the propagation of the exciting light beam (self-induced) as well as a probe light...... beam outside the absorption band through the polyester films. Investigations are carried out in one amorphous and one liquid crystalline polyester. We show that amorphous polyester after irradiation behaves like classical helical material....

  14. Photoinduced orientation in photochromic polybutadiene containing azobenzene side groups

    Czech Academy of Sciences Publication Activity Database

    Rais, David; Nešpůrek, Stanislav; Zakrevskyy, Y.; Stumpe, J.; Sedláková, Zdeňka; Combellas, C.; Kajzar, F.

    Barcelona : COST Chemistry and Institut de Ciencia de Materials de Barcelona, 2005. s. 67. [Final Evaluation Conference of the Chemistry COST Action D14 ‘Functional Molecular Materials’. 9.6.2005-12.6.2005, San Feliu de Guixols] R&D Projects: GA MŠk 1P04OCD14.30; GA AV ČR IAA4112401 Keywords : azobenzene * photochromic Subject RIV: CD - Macromolecular Chemistry

  15. Dicyclopalladated complexes of asymmetrically substituted azobenzenes: synthesis, kinetics and mechanisms.

    Science.gov (United States)

    Juribašić, Marina; Budimir, Ana; Kazazić, Snježana; Curić, Manda

    2013-11-01

    Two series of new dicyclopalladated complexes {(DMF)PdCl(μ-R(1)C6H3N═NC6H3R(2))PdCl(DMF)} of 4,4'-functionalized azobenzenes with substituents of varying electron-donating or electron-withdrawing strength (R(1) = H, NMe2; R(2) = H, Cl, Br, I, OMe, PhNH, CO2H, SO3Na, or NO2) have been synthesized and fully characterized. (1)H NMR spectroscopy along with the ESI mass spectrometry unambiguously identified the new complexes in the solution, and their solid-state structures were determined by X-ray crystallography. The presence of easily exchangeable solvent ligands was confirmed by (1)H NMR spectroscopy, X-ray experiments, and ESI mass spectrometry. The complexes were additionally characterized by UV-vis and fluorescence spectroscopies. The effect of different 4,4'-substituents on the formation rate of mono- and dicyclopalladated azobenzenes was studied by UV-vis spectroscopy. The experimental results are complemented by the quantum-chemical (DFT) calculations in order to rationalize the kinetic results as well as substituent effects on the reaction rates. It was found that the mono- and dicyclopalladation reactions of azobenzenes proceed in two consecutive processes, adduct formation and palladation steps. The rate-determining step in both palladations is the breaking of the ortho C-H bond, which has been confirmed as an electrophilic substitution process by Hammett correlations and DFT calculations. PMID:24116960

  16. Preparation and optical characteristics of layered perovskite-type lead-bromide-incorporated azobenzene chromophores

    Energy Technology Data Exchange (ETDEWEB)

    Sasai, Ryo, E-mail: rsasai@riko.shimane-u.ac.jp [Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, F3-3(250), Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Shinomura, Hisashi [Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, F3-3(250), Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)

    2013-02-15

    Lead bromide-based layered perovskite powders with azobenzene derivatives were prepared by a homogeneous precipitation method. From the diffuse reflectance (DR) and photoluminescence (PL) spectra of the hybrid powder materials, the present hybrids exhibited sharp absorption and PL peaks originating from excitons produced in the PbBr{sub 4}{sup 2-} layer. When the present hybrid powder was irradiated with UV light at 350 nm, the absorption band from the trans-azobenzene chromophore, observed around 350 nm, decreased, while the absorption band from the cis-azobenzene chromophore, observed around 450 nm, increased. These results indicate that azobenzene chromophores in the present hybrid materials exhibit reversible photoisomerization. Moreover, it was found that the PL intensity from the exciton also varied due to photoisomerization of the azobenzene chromophores in the present hybrid. Thus, for the first time we succeeded in preparing the azobenzene derivative lead-bromide-based layered perovskite with photochromism before and after UV light irradiation. - Graphical abstract: For the first time, we succeeded in preparing the azobenzene derivative lead-bromide-based layered perovskite with photochromism before and after UV light irradiation. Highlights: Black-Right-Pointing-Pointer PbBr-based layered perovskite with azobenezene derivatives could be synthesized by a homogeneous precipitation method. Black-Right-Pointing-Pointer Azobenzene derivatives incorporated the present hybrid that exhibited reversible photoisomerization under UV and/or visible light irradiation. Black-Right-Pointing-Pointer PL property of the present hybrid could also be varied by photoisomerization.

  17. Preparation and optical characteristics of layered perovskite-type lead-bromide-incorporated azobenzene chromophores

    International Nuclear Information System (INIS)

    Lead bromide-based layered perovskite powders with azobenzene derivatives were prepared by a homogeneous precipitation method. From the diffuse reflectance (DR) and photoluminescence (PL) spectra of the hybrid powder materials, the present hybrids exhibited sharp absorption and PL peaks originating from excitons produced in the PbBr42− layer. When the present hybrid powder was irradiated with UV light at 350 nm, the absorption band from the trans-azobenzene chromophore, observed around 350 nm, decreased, while the absorption band from the cis-azobenzene chromophore, observed around 450 nm, increased. These results indicate that azobenzene chromophores in the present hybrid materials exhibit reversible photoisomerization. Moreover, it was found that the PL intensity from the exciton also varied due to photoisomerization of the azobenzene chromophores in the present hybrid. Thus, for the first time we succeeded in preparing the azobenzene derivative lead-bromide-based layered perovskite with photochromism before and after UV light irradiation. - Graphical abstract: For the first time, we succeeded in preparing the azobenzene derivative lead-bromide-based layered perovskite with photochromism before and after UV light irradiation. Highlights: ► PbBr-based layered perovskite with azobenezene derivatives could be synthesized by a homogeneous precipitation method. ► Azobenzene derivatives incorporated the present hybrid that exhibited reversible photoisomerization under UV and/or visible light irradiation. ► PL property of the present hybrid could also be varied by photoisomerization.

  18. Kinetic analysis of the thermal isomerisation pathways in an asymmetric double azobenzene switch

    NARCIS (Netherlands)

    Robertus, Jort; Reker, Siebren F.; Pijper, Thomas C.; Deuzeman, Albert; Browne, Wesley R.; Feringa, Ben L.

    2012-01-01

    Here we report a photochemical and kinetic study of the thermal relaxation reaction of a double azobenzene system, in which two azobenzene photochromic units are connected via a phenyl ring. Upon UV irradiation, three thermally unstable isomers are formed. Kinetic studies using arrayed H-1-NMR spect

  19. DESIGN AND STUDY OF NEW AZOBENZENE LIQUID CRYSTAL/POLYMER MATERIALS

    Institute of Scientific and Technical Information of China (English)

    Yue Zhao

    2003-01-01

    Discussion is presented on the use of the photoisomerization of azobenzene chromophore in the design and preparation of novel functional materials. The two systems reviewed are azobenzene polymer-stabilized liquid crystals and azobenzene elastomers. In the first case, a polymer network containing azobenzene moieties is used to optically induce and stabilize a long-range liquid crystal orientation without the need of treating the surfaces of the substrates. This optical and rubbing-free approach was applied to nematic and ferroelectric liquid crystals. In the second case, an azobenzene side-chain liquid crystalline polymer is grafted onto a styrene-butadiene-styrene triblock copolymer to yield a photoactive thermoplastic elastomer. Coupled mechanical and optical effects make possible the formation of diffraction gratings that may be useful for mechanically tunable optical devices.

  20. Tuning the Photoinduced Motion of Glassy Azobenzene Polymers and Networks

    Science.gov (United States)

    Vaia, R. A.

    2013-03-01

    Continual innovation at the forefront of soft-matter, in areas such as liquid crystal networks, nano-composites and bio-molecules, is providing exciting opportunities to create smart materials systems that exhibit a controlled, reproducible and reversible modulation of physical properties. These material systems evoke the adaptivity of natural organisms, and inspire radical aerospace notions. A key example is photo-responsive polymers, which convert a light stimulus input into a mechanical output (work). Photoinduced conformational changes, such as within azobenzene, dictate molecular-level distortions that summate into a macroscopic strain, which often manifests as a shape change or motion. The transduction of the molecular-level response to a macroscale effect is regulated by mesoscopic features, such as chain packing, free volume, and local molecular order - factors which depend on chemical composition as well as the process history of the material. For example, physical aging increases the density of the glass, reduces local free volume, and thus decreases the minima in local conformation space which strongly influences the azobenzene photochemistry (trans-cis-trans isomerization). The subsequent change in the energy landscape of the system reduces the fraction of azobenzene able to undergo reconfiguration as well as increases the probability that those photoinduced conformations will relax back to the initial local environment. The result is a tuning of the magnitude of macroscopic strain and the ability to shift from shape fixing to shape recovery, respectively. Work done in collaboration with H. Koerner, K.M. Lee, M. Smith, D. Wang, L-S. Tan. and T. White, Air Force Research Laboratory.

  1. Intramolecular photoinduced electron-transfer in azobenzene-perylene diimide

    International Nuclear Information System (INIS)

    This paper studies the intramolecular photoinduced electron-transfer (PET) of covalent bonded azobenzene-perylene diimide (AZO-PDI) in solvents by using steady-state and time-resolved fluorescence spectroscopy together with ultrafast transient absorption spectroscopic techniques. Fast fluorescence quenching is observed when AZO-PDI is excited at characteristic wavelengths of AZO and perylene moieties. Reductive electron-transfer with transfer rate faster than 1011 s−1 is found. This PET process is also consolidated by femtosecond transient absorption spectra

  2. Attraction or Repulsion? London Dispersion Forces Control Azobenzene Switches.

    Science.gov (United States)

    Schweighauser, Luca; Strauss, Marcel A; Bellotto, Silvia; Wegner, Hermann A

    2015-11-01

    Large substituents are commonly seen as entirely repulsive through steric hindrance. Such groups have additional attractive effects arising from weak London dispersion forces between the neutral atoms. Steric interactions are recognized to have a strong influence on isomerization processes, such as in azobenzene-based molecular switches. Textbooks indicate that steric hindrance destabilizes the Z isomers. Herein, we demonstrate that increasing the bulkiness of electronically equal substituents in the meta-position decreases the thermal reaction rates from the Z to the E isomers. DFT computations revealed that attractive dispersion forces essentially lower the energy of the Z isomers. PMID:26350759

  3. Layer-by-layer deposited organic/inorganic hybrid multilayer films containing noncentrosymmetrically orientated azobenzene chromophores.

    Science.gov (United States)

    Kang, En-Hua; Bu, Tianjia; Jin, Pengcheng; Sun, Junqi; Yang, Yanqiang; Shen, Jiacong

    2007-07-01

    Organic/inorganic hybrid multilayer films with noncentrosymmetrically orientated azobenzene chromophores were fabricated by the sequential deposition of ZrO2 layers by a surface sol-gel process and subsequent layer-by-layer (LbL) adsorption of the nonlinear optical (NLO)-active azobenzene-containing polyanion PAC-azoBNS and poly(diallyldimethylammonium chloride) (PDDA). Noncentrosymmetric orientation of the NLO-active azobenzene chromophores was achieved because of the strong repulsion between the negatively charged ZrO(2) and the sulfonate groups of the azobenzene chromophore in PAC-azoBNS. Regular deposition of ZrO(2)/PAC-azoBNS/PDDA multilayer films was verified by UV-vis absorption spectroscopy and quartz crystal microbalance measurements. Both UV-vis absorption spectroscopy and transmission second harmonic generation (SHG) measurements confirmed the noncentrosymmetric orientation of the azobenzene chromophores in the as-prepared ZrO2/PAC-azoBNS/PDDA multilayer films. The square root of the SHG signal (I(2omega)(1/2)) increases with the increase of the azobenzene graft ratio in PAC-azoBNS as the number of deposition cycles of the ZrO(2)/PAC-azoBNS/PDDA films remains the same, while the second-order susceptibility chi(zzz)(2) of the film decreases with the increase of the azobenzene graft ratio. Furthermore, the present method was successfully extended to realize the noncentrosymmetric orientation of azobenzene chromophores in multilayer films when small organic azobenzene compounds with carboxylic acid and/or hydroxyl groups at one end and sulfonate groups at the other end were used. The present method was characterized by its simplicity and flexibility in film preparation, and it is anticipated to be a facile way to fabricate second-order nonlinear optical film materials. PMID:17555337

  4. Structure dependence of photochromism and thermochromism of azobenzene-functionalized polythiophenes

    Directory of Open Access Journals (Sweden)

    2007-07-01

    Full Text Available Two novel azobenzene-functionalized polythiophenes, poly[4-((4-(phenylazophenoxybutyl-3-thienylacetate] (P4 and the copolymer of 3-hexylthiophene and 4-((4-(phenylazophenoxybutyl-3-thienylacetate (COP64 have been synthesized. The structure dependence of photoluminescence features and thermochromic behaviors of both azobenzene-functionalized polymers was investigated. The results show that polymer structure has a strong influence on the conformation and optical properties of the resulting polythiophene derivatives. The photochemical control of photoluminescence property was achieved with homopolymer P4 using photoactive azobenzene side chains.

  5. Photoisomerization dynamics of azobenzene materials for solar thermal fuels

    Science.gov (United States)

    Strubbe, David; Grossman, Jeffrey

    2013-03-01

    A solar thermal fuel absorbs sunlight and stores the energy chemically via an induced structural change, which can later be reversed to release the energy as heat. Azobenzene molecules have a cis-trans photoisomerization with these properties, and hydrogen-bonding and packing via attachment to rigid template structures have shown promise in increasing the energy stored and the length of time it can be stored [A Kolpak et al, Nano Lett. 11, 3156-3162 (2011)]. Other important factors in determining the efficiency of a solar thermal fuel are the absorption cross-section and the quantum yield for photoisomerization, which must also be optimized for a successful material. We employ time-dependent density-functional theory (TDDFT) and the GW/Bethe-Salpeter formalism to calculate the optical absorption and dynamics in the excited-state to address these two factors. We use excited-state forces to map out potential-energy surfaces and follow the structural change after absorption for azobenzene-derived materials, to correlate the efficiency of photoisomerization with the functionalization and template.

  6. Self-Assembled Structures of PMAA-PMMA Block Copolymers : Synthesis, Characterization, and Self-Consistent Field Computations

    NARCIS (Netherlands)

    Li, Feng; Schellekens, Mike; de Bont, Jens; Peters, Ron; Overbeek, Ad; Leermakers, Frans A. M.; Tuinier, Remco

    2015-01-01

    Block copolymers composed of methacrylic acid (MAA) and methyl methacrylate (MMA) blocks are interesting candidates for replacing surfactants in emulsion polymerization methods. Here the synthesis and experimental characterization of well-defined PMAA-PMMA block copolymers made via RAFT polymerizati

  7. Synthesis and characterization of magnetic poly(glycidyl methacrylate) microspheres

    Science.gov (United States)

    Horák, Daniel; Petrovský, Eduard; Kapička, Aleš; Frederichs, Theodor

    2007-04-01

    Magnetic nanoparticles encapsulated in poly(glycidyl methacrylate) microspheres were prepared and their detailed structural and magnetic characteristics given. Iron oxide nanoparticles were obtained by chemical coprecipitation of Fe(II) and Fe(III) salts and stabilized with dextran, (carboxymethyl)dextran or tetramethylammonium hydroxide. The microspheres were prepared by emulsion or dispersion polymerization of glycidyl methacrylate in the presence of ferrofluid. The microspheres were uniform both in shape and usually also in size; their size distribution was narrow. All the magnetic parameters confirm superparamagnetic nature of the microspheres. Blocking temperature was not observed, suggesting the absence of magnetic interactions at low temperatures. This is most probably caused by complete encapsulation and the absence of agglomeration. Such microspheres can be used in biomedical applications.

  8. Synthesis and characterization of magnetic poly(glycidyl methacrylate) microspheres

    Energy Technology Data Exchange (ETDEWEB)

    Horak, Daniel [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovskeho Sq. 2, 162 06 Prague 6 (Czech Republic)]. E-mail: horak@imc.cas.cz; Petrovsky, Eduard [Geophysical Institute, Academy of Sciences of the Czech Republic, Bocni II/1401, 141 31 Prague 4 (Czech Republic); Kapicka, Ales [Geophysical Institute, Academy of Sciences of the Czech Republic, Bocni II/1401, 141 31 Prague 4 (Czech Republic); Frederichs, Theodor [University of Bremen, Department of Geosciences, GEO I, Klagenfurter Strasse, 28359 Bremen (Germany)

    2007-04-15

    Magnetic nanoparticles encapsulated in poly(glycidyl methacrylate) microspheres were prepared and their detailed structural and magnetic characteristics given. Iron oxide nanoparticles were obtained by chemical coprecipitation of Fe(II) and Fe(III) salts and stabilized with dextran, (carboxymethyl)dextran or tetramethylammonium hydroxide. The microspheres were prepared by emulsion or dispersion polymerization of glycidyl methacrylate in the presence of ferrofluid. The microspheres were uniform both in shape and usually also in size; their size distribution was narrow. All the magnetic parameters confirm superparamagnetic nature of the microspheres. Blocking temperature was not observed, suggesting the absence of magnetic interactions at low temperatures. This is most probably caused by complete encapsulation and the absence of agglomeration. Such microspheres can be used in biomedical applications.

  9. Synthesis and Properties of 2'-Deoxyuridine Analogues Bearing Various Azobenzene Derivatives at the C5 Position

    Directory of Open Access Journals (Sweden)

    Shohei Mori

    2015-03-01

    Full Text Available Nucleic acids that change their properties upon photo-irradiation could be powerful materials for molecular sensing with high spatiotemporal resolution. Recently, we reported a photo-isomeric nucleoside bearing azobenzene at the C5 position of 2'-deoxyuridine (dUAz, whose hybridization ability could be reversibly controlled by the appropriate wavelength of light. In this paper, we synthesized and evaluated dUAz analogues that have various para-substitutions on the azobenzene moiety. Spectroscopic measurements and HPLC analyses revealed that the para-substitutions of the azobenzene moiety strongly affect the photo-isomerization ability and thermal stability of the cis-form. The results suggest that proper substitution of the azobenzene moiety can improve the properties of dUAz as a light-responsive nucleic acid probe.

  10. Studies of azobenzene-containing triazatriangulenium adlayers on Au(111) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Ulrich; Kuhn, Sonja; Mueller, Mathias; Filinova, Olena; Baisch, Belinda; Magnussen, Olaf [Institut fuer Experimentelle und Angewandte Physik, Christian-Albrechts-Universitaet zu Kiel, Leibnizstrasse 19, 24118 Kiel (Germany); Kubitschke, Jens; Herges, Rainer [Otto-Diels-Institut fuer Organische Chemie, Christian-Albrechts-Universitaet zu Kiel, Otto-Hahn-Platz 3, 24098 Kiel (Germany)

    2010-07-01

    The attachment of molecular functions such as photoswitches to metal surfaces is of major interest in nanotechnology. One of the most frequently studied class of photoswitches are azobenzenes, which exhibit trans-cis isomerism. The typical method to attach azobenzene to surfaces is self-assembly of thiols on Au. However, in such adlayers the photoisomerization is often totally quenched because of steric effects. To overcome the problems of conventional azobenzene adlayers, we were employing a novel approach using customizable triazatriangulenium (TATA) platforms. Here, we present the structure and photoswitching properties of azobenzene-containing TATA adlayers on Au(111), obtained by structure-sensitive, spectroscopic, and electrochemical methods. Functionalized TATA molecules exhibit a strong tendency to form bilayers. We demonstrate, that it is possible to suppress bilayer formation and thus to form highly-ordered functionalized TATA monolayers. Furthermore, the photoswitching processes in these adlayers obey first order kinetics with quantum efficiencies of <10{sup -3}.

  11. Theoretical Investigation of Nonlinear Optical Properties of Organic and Transition Metal Hybrid Azobenzene Dendrimers

    Institute of Scientific and Technical Information of China (English)

    LIU Cai-Ping; LIU Ping; WU Ke-Chen

    2008-01-01

    In this work, we report a theoretical exploration of the responses of organic azo-benzene dendrimers. The polarizabilities, the first and second hyperpolarizabilities of the azobenzene monomers (GO), and the first, second and third generation (G1, G2 and G3, respectively) are investigated by semi-empirical methods. The calculated results show that the nonlinear optical (NLO)properties of these organic dendrimers are mainly determined by the azobenzene chromospheres.Additionally, the values of β and γ increase almost in proportion to the number of chromophores. On the other hand, two types of transition metal hybrid azobenzene dendrimers (core-hybrid and branch-end hybrid according to the sites combined with transition metals) are simulated and discussed in detail in the framework of time-dependent density functional theory (TDDFT). The calculated results reveal that the NLO responses of these metal dendrimers distinctly varied as a result of altering the charge transfer transition scale and the excitation energies.

  12. Induction of molecular chirality by circularly polarized light in cyclic azobenzene with a photoswitchable benzene rotor.

    Science.gov (United States)

    Hashim, P K; Thomas, Reji; Tamaoki, Nobuyuki

    2011-06-20

    New phototriggered molecular machines based on cyclic azobenzene were synthesized in which a 2,5-dimethoxy, 2,5-dimethyl, 2,5-difluorine or unsubstituted-1,4-dioxybenzene rotating unit and a photoisomerizable 3,3'-dioxyazobenzene moiety are bridged together by fixed bismethylene spacers. Depending upon substitution on the benzene moiety and on the E/Z conformation of the azobenzene unit, these molecules suffer various degrees of restriction on the free rotation of the benzene rotor. The rotation of the substituted benzene rotor within the cyclic azobenzene cavity imparts planar chirality to the molecules. Cyclic azobenzene 1, with methoxy groups at both the 2- and 5-positions of the benzene rotor, was so conformationally restricted that free rotation of the rotor was prevented in both the E and Z isomers and the respective planar chiral enantiomers were resolved. In contrast, compound 2, with 2,5-dimethylbenzene as the rotor, demonstrated the property of a light-controlled molecular brake, whereby rotation of the 2,5-dimethylbenzene moiety is completely stopped in the E isomer (brake ON, rotation OFF), while the rotation is allowed in the Z isomer (brake OFF, rotation ON). The cyclic azobenzene 3, with fluorine substitution on the benzene rotor, was in the brake OFF state regardless of E/Z photoisomerization of the azobenzene moiety. More interestingly, for the first time, we demonstrated the induction of molecular chirality in a simple monocyclic azobenzene by circular-polarized light. The key characteristics of cyclic azobenzene 2, that is, stability of the chiral structure in the E isomer, fast racemization in the Z isomer, and the circular dichroism of enantiomers of both E and Z isomers, resulted in a simple reversible enantio-differentiating photoisomerization directly between the E enantiomers. Upon exposure to r- or l-circularly polarized light at 488 nm, partial enrichment of the (S)- or (R)-enantiomers of 2 was observed. PMID:21567494

  13. Self-Driven Bioelectrochemical Mineralization of Azobenzene by Coupling Cathodic Reduction with Anodic Intermediate Oxidation

    International Nuclear Information System (INIS)

    Highlights: • Azobenzene was reduced to aniline at the cathode of an acetate-fueled MFC. • Aniline was degraded at the bioanode of a single-chamber MFC. • Cathodic reduction of azobenzene was coupled with anodic oxidation of aniline. • Self-driven, complete mineralization of azobenzene in an MFC was accomplished. - Abstract: Bioelectrochemical systems have been intensively studied as a promising technology for wastewater treatment and environment remediation. Coupling of the anodic and cathodic electrochemical reactions allows an enhanced degradation of recalcitrant organics, but external power supply is usually needed to overcome the thermodynamic barrier. In this work, we report a self-driven degradation of azobenzene in a microbial fuel cell (MFC), where the cathodic reduction of azobenzene was effectively coupled with the anodic oxidation of its reduction degradation intermediate (i.e., aniline). The anodic degradation rate of aniline, as the sole carbon source, was significantly higher than that under open-circuit conditions, suggesting a considerable bioelectrochemical oxidation of aniline. Output voltages up to 8 mV were obtained in the MFC. However, a shift of cathodic electron acceptor from oxygen to azobenzene resulted in a decreased aniline degradation rate and output voltage. The present work may provide valuable implications for development of sustainable bioelectrochemical technologies for environmental remediation

  14. Light scattering of thin azobenzene side-chain polyester layers

    DEFF Research Database (Denmark)

    Kerekes, Á.; Lörincz, E.; Ramanujam, P.S.;

    2002-01-01

    Light scattering properties of liquid crystalline and amorphous azobenzene side-chain polyester layers used for optical data storage were examined by means of transmissive scatterometry. Comparative experiments show that the amorphous polyester has significantly lower light scattering...... characteristics than the liquid crystalline polyester. The amorphous samples have negligible polarization part orthogonal to the incident beam. the liquid crystalline samples have relative high orthogonal polarization part in light scattering, The light scattering results can be used to give a lower limit for the...... domain size in thin liquid crystalline polyester layers being responsible for the dominant light scattering. The characteristic domain Sizes obtained from the Fourier transformation of polarization microscopic Pictures confirm these values....

  15. Polymer scaffolds bearing azobenzene - Potential for optical information storage

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Ramanujam, P.S.

    2001-01-01

    The fundamental optical storage mechanism of the laser light addressable azobenzene moiety is briefly introduced. A modular and flexible synthesis design furnishes polyester matrices covalently integrating cyanoazobenzene in regularly spaced side chains. Thin films of these materials are...... particularly well suited for holographic storage. Notable figures of merits of liquid crystalline polyesters are response time to blue-green laser light of the order of nanoseconds, storage capacity expressed as 5000 lines/mm, and high, permanent (almost nine years) diffraction efficiency of the order of 50......% or greater, and erasability. The implications of the main chain nature for polyester morphology and for the permanency of the induced anisotropy are discussed. The design and methods of preparation of other significantly different polymer scaffolds supporting cyanoazobenzene are elaborated...

  16. Photomechanical Bending of Azobenzene-Based Photochromic Molecular Fibers

    Directory of Open Access Journals (Sweden)

    Riku Matsui

    2013-03-01

    Full Text Available Microfibers composed of azobenzene-based photochromic amorphous molecular materials, namely low molecular-mass photochromic materials with a glass-forming property, could be fabricated. These fibers were found to exhibit mechanical bending motion upon irradiation with a laser beam. In addition, the bending direction could be controlled by altering the polarization direction of the irradiated light without changing the position of the light source or the wavelength of the light. In-situ fluorescence observation of mass transport induced at the surface of the fiber doped with CdSe quantum dots suggested that the bending motions were related with the photoinduced mass transport taking place near the irradiated surface of the fiber.

  17. Antimicrobial azobenzene compounds and their potential use in biomaterials

    Science.gov (United States)

    Sessa, L.; Concilio, S.; Iannelli, P.; De Santis, F.; Porta, A.; Piotto, S.

    2016-04-01

    We recently synthesized a class of active compounds with azobenzene structure [1] and lowest in silico toxicity values. The antimicrobial activity of these molecules and their thermal stability are very promising and indicate that they may have interesting and therapeutically significant applications. This work aims to develop new materials with antibacterial and antifungal activity inserting different percentages of synthetic antimicrobial azo compounds in commercial polymer matrices. We realized thin films using solvent casting and melt compounding techniques. The obtained materials retained the proprieties of the pure matrices. This means that azo dye dissolved in the matrix does not influence the thermal behavior and the morphology of the material. Tested films exhibited the capability to inhibit biofilms formation of S. aureus and C. albicans. Spectrophotometric investigation of the azo compound released from the polymer matrices confirmed that the realized materials might be interesting for biomedical tools, antibacterial surfaces, and films for active packaging.

  18. Photodissociation UV-Vis Spectra of Cold Protonated Azobenzene and 4-(Dimethylamino)azobenzene and Their Benzenediazonium Cation Fragment.

    Science.gov (United States)

    Féraud, Géraldine; Dedonder-Lardeux, Claude; Jouvet, Christophe; Marceca, Ernesto

    2016-06-01

    Gas phase photodissociation electronic spectra of protonated azobenzene (ABH(+)) and 4-(dimethylamino)azobenzene (dmaABH(+)) were measured in a cryogenically cooled ion trap at temperatures of a few tens of Kelvin. Experimental results were complemented with electronic structure calculations in the ground state at the MP2/cc-pVDZ level of theory, and in the low lying excited states using the RI-CC2 method. Calculated energies revealed that only the trans isomers of the azonium molecular ions (protonation site on the azo group) will likely exist in the trap at the temperatures achieved in the experiment. The first transition of trans-ABH(+) is π* ← π, and the absorption band in the spectrum appears strongly red-shifted from that of the neutral molecule. The calculations showed that upon excitation the quasi-planar ground state (S0) transforms into a chairlike excited state (S1) by twisting the CNNC dihedral angle about 96°. A 41 cm(-1) active vibrational progression found in the ABH(+) spectrum may be associated with the twisting of the azo bond. Conversely, the electronic spectrum of dmaABH(+) exhibits a steep and unstructured S1 ← S0 absorption corresponding to a less distorted S1 state. The next two quasi-degenerate bands in the ABH(+) spectrum evidence sharper onsets and a charge transfer character. Using a second fragmentation laser and an additional He cooling pulse in the trap, it was possible to measure the UV spectrum of cold benzenediazonium fragments. PMID:27216229

  19. Glycol methacrylate in light microscopy: nucleic acid cytochemistry.

    Science.gov (United States)

    Cole, M B; Ellinger, J

    1981-07-01

    Techniques utilizing Feulgen, azure B bromide, methyl green-pyronin, gallocyanin chromalum and cresyl violet stains have been modified and adapted for visualizing nucleic acids in 0.5-2.0 micrometer sections of tissues embedded in glycol methacrylate (GMA). Methods for evaluating the stain specificity for DNA and RNA using deoxyribonuclease and ribonuclease digestions, aldehyde blocking, and acid extractions are also described. The specificity of the stains in GMA embedded tissues is comparable to that reported for paraffin-embedded tissues. PMID:6167720

  20. Acrylates and methacrylates of formal-glycerine

    International Nuclear Information System (INIS)

    Present article is devoted acrylates and methacrylates of formal-glycerine. The formal-glycerine was obtained in the form of mixture of isomers 1.2 and 1.3 from glycerine and paraform with hydrochloric acid. The structure of obtained acrylates and methacrylates is studied by means of molecular refraction, element analysis and infrared spectroscopy.

  1. 10,000 optical write, read, and erase cycles in an azobenzene sidechain liquid-crystalline polyester

    DEFF Research Database (Denmark)

    Holme, NCR; Ramanujam, P.S.; Hvilsted, Søren

    1996-01-01

    light from a krypton laser at 351 nm. The efficiency of the system shows several exponential decays, presumably associated ci with the azobenzene chromophores' aligning out of the plane of the film and the lifetime of the cis state of the azobenzene. A local temperature increase may also play a role...

  2. Synthesis and Morphological Characterization of Block Copolymers for Improved Biomaterials

    OpenAIRE

    Schricker, Scott; Palacio, Manuel; Thirumamagal, B.T.S.; Bhushan, Bharat

    2010-01-01

    Biocompatible polymers are known to act as scaffolds for the regeneration and growth of bone. Block copolymers are of interest as scaffold materials because a number of the blocks are biocompatible, and their nanostructure is easily tunable with synthetic techniques. In this paper, we report the synthesis of a novel class of biomaterials from block copolymers containing a hydrophobic block of methyl methacrylate and a hydrophilic block of either acrylic acid, dimethyl acrylamide, or 2-hydroxy...

  3. pH-sensitive methacrylic copolymer gels and the production thereof

    Science.gov (United States)

    Mallapragada, Surya K.; Anderson, Brian C.

    2007-05-15

    The present invention provides novel gel forming methacrylic blocking copolymers that exhibit cationic pH-sensitive behavior as well as good water solubility. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol)methyl ether polymer. The polymers may be used for drug and gene delivery, protein separation, as structural supplements, and more.

  4. Optically switchable multi-stopband of non-quarter-wavelength dielectric multilayer using azobenzene polymer liquid crystal

    Science.gov (United States)

    Ozaki, Ryotaro; Kadowaki, Kazunori; Hagio, Takashi; Yagi, Ryohei; Kuwahara, Yutaka; Kurihara, Seiji

    2015-09-01

    Non-quarter-wave stacked dielectric multilayers including azobenzene polymer liquid crystal layers are investigated in this study. The azobenzene polymer liquid crystal has a photoinduced reversible refractive index based on photoisomerization. By using the reversible refractive-index change, the reflectance of a stopband can be controlled. In this system, the azobenzene molecules change their conformation when they are irradiated with ultraviolet (UV) or visible light. In general, stacking many layers of different thicknesses can produce broadband or multicolor reflections for a dielectric multilayer. However, in a multilayer having thick azobenzene layers, UV or visible light used for controlling photoisomerization hardly reaches the bottom part of the multilayer because the light is mainly absorbed at its top surface. To solve this problem, the dependence on the thickness ratio of the multilayer is investigated and a non-quarter-wave stacked multilayer having RGB reflections is experimentally demonstrated using thin azobenzene layers.

  5. Local Density Fluctuations Predict Photoisomerization Quantum Yield of Azobenzene-Modified DNA.

    Science.gov (United States)

    Kingsland, Addie; Samai, Soumyadyuti; Yan, Yunqi; Ginger, David S; Maibaum, Lutz

    2016-08-01

    Azobenzene incorporated into DNA has a photoisomerization quantum yield that depends on the DNA sequence near the azobenzene attachment site. We use Molecular Dynamics computer simulations to elucidate which physical properties of the modified DNA determine the quantum yield. We show for a wide range of DNA sequences that the photoisomerization quantum yield is strongly correlated with the variance of the number of atoms in close proximity to the outer phenyl ring of the azobenzene group. We infer that quantum yield is controlled by the availability of fluctuations that enable the conformational change. We demonstrate that these simulations can be used as a qualitative predictive tool by calculating the quantum yield for several novel DNA sequences, and confirming these predictions using UV-vis spectroscopy. Our results will be useful for the development of a wide range of applications of photoresponsive DNA nanotechnology. PMID:27428569

  6. Photoisomerization of azobenzene containing self-assembled monolayers investigated by Kelvin probe work function measurements

    International Nuclear Information System (INIS)

    Photoisomerization of asymmetric azobenzene disulfide self-assembled monolayer (SAM) on gold was characterized by the Kelvin probe work function measurements in ambient atmosphere. The reversible changes in work function between trans and cis azobenzene SAMs are reasonably interpreted by the molecular dipole moments normal to the surface based on the molecular conformational models. The different para-substituents of azobenzene with electron donating and electron-withdrawing properties induce opposite responses in work function against UV-vis photoirradiation, which is a direct evidence of functional SAMs being effective for the energy-level alignment at the organic/electrode interface. The Kelvin probe measurements in atmosphere eventually provide the work function value equivalent to that determined by ultraviolet photoelectron spectroscopy (UPS) in ultrahigh vacuum in our previous study.

  7. Colorimetric response of azobenzene-terminated polydiacetylene vesicles under thermal and photic stimuli

    Science.gov (United States)

    You, Xian; Chen, Xin; Zou, Gang; Su, Wei; Zhang, Qijin; He, Pingsheng

    2009-11-01

    We study the colorimetric reversibility of pure polymerized p-nitro azobenzene moiety-substituted diacetylene (PNADA) and PNADA/polymerized 10,12-pentacosadiynoic acid (PDA) complex vesicles under thermal and photic stimuli. Because of the strong intermolecular interaction among azobenzene mesogens within the vesicles, PNADA vesicles show enhanced stability and completely reversible thermochromic response. Polydiacetylene based complex vesicles with partial reversible chromatic properties under both thermal and photonic stimuli were reported for the first time, which provided a novel model system for the understanding of the chromatic transition mechanism of polydiacetylene materials.

  8. Determination of the Response Time of Photoanisotropy in Azobenzene Side-Chain Polyesters

    DEFF Research Database (Denmark)

    Bublitz, D.; Fleck, B.; Wenke, L.; Ramanujam, P. S.; Ramanujam, P.S.; Hvilsted, Søren

    We present a method which allows the determination of the response time to polarized light of an azobenzene side-chain polyester. This method is based on the measurement of intensities in dependence on the delay time between a pump and a probe pulse. The described method does not need a very...... sophisticated time resolving measuring equipment. The time resolution is in the order 10 ps and is comparable with the laser pulse duration. The response time of the azobenzene side-chain polyester E1aP has determined to be about 40 ps. (C) 2000 Elsevier Science B.V. All rights reserved....

  9. Modulational instability of incoherently coupled beams in azobenzene-containing polymer with photoisomerization nonlinearity

    Institute of Scientific and Technical Information of China (English)

    Zhang Bing-Zhi; Cui Hu; She Wei-Long

    2009-01-01

    The modulational instability of two incoherently coupled beams in azobenzene-containing polymer with photoisomerization nonlinearity is investigated analytically and numerically. Our results show that as a precursor to spatial optical soliton formation, modulational instability can be adjusted and controlled by the wavelength combinations of the signal and background beams. We also discuss the dependences of strength of modulational instability on intensities of two signal beams and background beam. These findings make it possible to predict the formation of incoherently coupled soliton pairs in azobenzene-containing polymer.

  10. Effect of heat and film thickness on a photoinduced phase transition in azobenzene liquid crystalline polyesters

    DEFF Research Database (Denmark)

    Sanchez, C; Alcala, R; Hvilsted, Søren;

    2003-01-01

    The liquid crystal to isotropic phase transition induced with 488 nm light in films of liquid crystalline azobenzene polyesters has been studied as a function of temperature, light intensity, and film thickness. That phase transition is associated with the photoinduced trans-cis-trans isomerizati......The liquid crystal to isotropic phase transition induced with 488 nm light in films of liquid crystalline azobenzene polyesters has been studied as a function of temperature, light intensity, and film thickness. That phase transition is associated with the photoinduced trans...

  11. Modulational instability of incoherently coupled beams in azobenzene-containing polymer with photoisomerization nonlinearity

    International Nuclear Information System (INIS)

    The modulational instability of two incoherently coupled beams in azobenzene-containing polymer with photoisomerization nonlinearity is investigated analytically and numerically. Our results show that as a precursor to spatial optical soliton formation, modulational instability can be adjusted and controlled by the wavelength combinations of the signal and background beams. We also discuss the dependences of strength of modulational instability on intensities of two signal beams and background beam. These findings make it possible to predict the formation of incoherently coupled soliton pairs in azobenzene-containing polymer. (classical areas of phenomenology)

  12. Polymerization of sodium methacrylate induced by irradiation

    International Nuclear Information System (INIS)

    This work has two objectives, first: it is pretended to localize the lines of carbon links in its IR spectra, and second: following the polymerization of sodium methacrylate according to that it is irradiated with gamma rays. (Author)

  13. Triphenyl group containing molecular glasses of azobenzene for photonic applications

    Science.gov (United States)

    Zarins, Elmars; Tokmakovs, Andrejs; Kokars, Valdis; Ozols, Andris; Augustovs, Peteris; Rutkis, Martins

    2016-03-01

    D-π-A type organic molecules have attracted considerable attention of scientists due to their potential applications in nonlinear optics and holographic data storage as light, flexible and low-cost photonic materials. To provide a better understanding on the relation between the compound chemical structure and their physical properties necessary for the mentioned purposes, eight glassy triphenyl group containing derivatives of azobenzene with incorporated 5,5-dimethylcyclohex-2-enylidene or 4H-pyran-4-ylidene structural fragments and dicyanomethylene, indene-1,3-dione and pyrimidine-2,4,6(1H,3H,5H)-trione acceptor groups have been synthesized and investigated. Thermal stability of synthesized glasses is no lower than 250 °C and glass transition in higher than 70 °C which both further increases (up to 120 °C) by additional number of attached triphenyl-moieties and incorporated structural fragments. Almost all of the synthesized azodyes form good optical quality transparent amorphous films from volatile organic solvents with their light absorption in thin solid films in the range of 400-660 nm. Azocompounds with sterically small cyclohex-2-ene-1-ylidene fragment in their molecules proved to be most efficient materials for holographic data storage and nonlinear optics with diffraction efficiency up to 20.40%, self diffraction efficiency up to 12.94% and NLO coefficient d33 up to 125.7 pm/V. Azodyes with no additionally incorporated structural fragments and indene-1,3-dione electron acceptor group were least efficient materials for these purposes, however may show potential as photoactive components in organic solar cells due to their remarkable light absorption properties in the solid state.

  14. Photomechanical actuator device based on disperse red 1 doped poly(methyl methacrylate) optical fiber

    Science.gov (United States)

    Ye, Xianjun

    The photomechanical effect is the phenomenon involving any mechanical property change of a material induced by light exposure. Photomechanical devices can be built with superior performance over traditional devices and offer versatile control tactics. Previous experiments show that disperse red 1 azobenzene (DR1) doped poly(methyl methacrylate) (PMMA) optical fiber has a fast photomechanical response upon asymmetrical 633nm laser irradiation originating in photoisomerization of the dopants between the cis and trans forms, which causes an elongation of the polymer fiber. In this work, laser light of 355nm wavelength is used to investigate the dynamics of the trans to cis photoisomerization process, which should result in length contraction of the DR1 doped PMMA polymer fiber. A three-point-contact optically-actuated beam controlling tilt mount is made and used as the measurement apparatus to study this process. The photomechanical fiber is observed to elongate upon UV irradiation. Numerical simulations, which take into account the coupled effect between the laser-induced temperature increase and population density change of the dye molecules, show that contraction of the fiber due to direct trans-cis photoisomerization is overwhelmed by elongation due to the photo-thermally-stimulated cis-trans isomerization under high intensity. An ink coated entrance face of the fiber is placed in the measurement tilt mount and is found to exhibit contraction in the fast process under low intensity without sacrificing the good signal to noise ratio enjoyed in the high intensity case.

  15. Lamellar Microdomains of Block-Copolymer-Based Ionic Supramolecules Exhibiting a Hierarchical Self-Assembly

    DEFF Research Database (Denmark)

    Ayoubi, Mehran Asad; Almdal, Kristoffer; Zhu, Kaizheng;

    2014-01-01

    Based on a parent diblock copolymer of poly(styrene)-b-poly(methacrylic acid), PS-b-PMAA, linear-b-amphiphilic comb (L-b-AC) ionic supramolecules [Soft Matter 2013, 9, 1540-1555] are synthesized in which the poly(methacrylate) backbone of the ionic supramolecular AC-block is neutralized by alkyl...

  16. Photosensitive response of azobenzene containing films towards pure intensity or polarization interference patterns

    Energy Technology Data Exchange (ETDEWEB)

    Yadavalli, Nataraja Sekhar; Santer, Svetlana, E-mail: santer@uni-potsdam.de [Department of Experimental Physics, Institute of Physics and Astronomy, University of Potsdam, 14476 Potsdam (Germany); Saphiannikova, Marina [Leibniz Institute of Polymer Research Dresden, 01069 Dresden (Germany)

    2014-08-04

    In this paper, we report on differences in the response of photosensitive azobenzene containing films upon irradiation with the intensity or polarization interference patterns. Two materials are studied differing in the molecular weight: an azobenzene-containing polymer and a molecular glass formed from a much smaller molecule consisting of three connected azobenzene units. Topography changes occurring along with the changes in irradiation conditions are recorded using a homemade set-up combining an optical part for generation and shaping of interference patterns and an atomic force microscope for acquiring the kinetics of film deformation. In this way, we could reveal the unique behavior of photosensitive materials during the first few minutes of irradiation: the change in topography is initially driven by an increase in the azobenzene free volume along with the trans-cis isomerization, followed by the mass transport finally resulting in the surface relief grating. This study demonstrates the great potential of our setup to experimentally highlight puzzling processes governing the formation of surface relief gratings.

  17. Determination of the Response Time of Photoanisotropy in Azobenzene Side-Chain Polyesters

    DEFF Research Database (Denmark)

    Bublitz, D.; Fleck, B.; Wenke, L.;

    2000-01-01

    sophisticated time resolving measuring equipment. The time resolution is in the order 10 ps and is comparable with the laser pulse duration. The response time of the azobenzene side-chain polyester E1aP has determined to be about 40 ps. (C) 2000 Elsevier Science B.V. All rights reserved....

  18. Biphotonic holographic gratings in azobenzene polyesters: Surface relief phenomena and polarization effects

    DEFF Research Database (Denmark)

    Sánchez, C.; Alcalá, R.; Hvilsted, Søren;

    2000-01-01

    Biphotonic holographic gratings have been recorded in a side-chain azobenzene liquid crystalline polyester using a blue incoherent source and a He-Ne laser. Intensity gratings and the appearance of surface relief have been observed when two linearly polarized beams from a He-Ne laser are made to...

  19. Theoretical model of photoinduced anisotropy in liquid-crystalline azobenzene side-chain polyesters

    DEFF Research Database (Denmark)

    Pedersen, Thomas Garm; Johansen, Per Michael; Holme, N.C.R.;

    1998-01-01

    A theoretical framework for the temporal behavior of photoinduced anisotropy in liquid-crystalline azobenzene side-chain polyesters is constructed. The domain structure of the material is taken into account and inter molecular interactions are included through a mean-field description. Photoinduced...

  20. Synthesis of azobenzene-containing liquid crystalline gelator for use in liquid crystal gels

    Institute of Scientific and Technical Information of China (English)

    Guang Wang; Xiao Liang Zhao; Yue Zhao

    2008-01-01

    A liquid crystalline gelator containing the azobenzene chromophore was synthesized for the first time; it was used to form self-assembled network in nematic liquid crystals resulting in liquid crystal gels with distinct features.? 2008 Guang Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

  1. Diffraction from polarization holographic gratings with surface relief in side-chain azobenzene polyesters

    DEFF Research Database (Denmark)

    Naydenova, I; Nikolova, L; Todorov, T;

    1998-01-01

    We investigate the polarization properties of holographic gratings in side-chain azobenzene polyesters in which an anisotropic grating that is due to photoinduced linear and circular birefringence is recorded in the volume of the material and a relief grating appears on the surface. A theoretical...

  2. Self-assembled monolayers of azobenzene functionalized 1,3,5-triazine-4,6-dithiols

    International Nuclear Information System (INIS)

    Two novel azobenzene-functionalized 1,3,5-triazine-4,6-dithiols were synthesized and their ultrathin films were prepared by self-assembling (SA) technique. The switching between trans-and cis-forms was observed by measuring the surface potential using the Kelvin probe technique while alternating irradiation the SA monolayer (SAM) with ultraviolet or visible light

  3. High diffraction efficiency polarization gratings recorded by biphotonic holography in an azobenzene liquid crystalline polyester

    DEFF Research Database (Denmark)

    Sánchez, C; Alcalá, R; Hvilsted, Søren;

    2001-01-01

    High diffraction efficiencies have been achieved with polarization gratings recorded in thin films of an azobenzene side-chain liquid crystalline polyester by means of biphotonic processes. Efficiency values up to 30% have been reached after an induction period of 300 s and subsequent evolution...

  4. Photoinduced anisotropy measurements in liquid-crystalline azobenzene side-chain polyesters

    DEFF Research Database (Denmark)

    Holme, NCR; Ramanujam, P.S.; Hvilsted, Søren

    1996-01-01

    Reversible photoinduced anisotropy in a series of Liquid-crystalline azobenzene side-chain polyesters is investigated as a function of intensity of the write beam and the sample temperature. Measurements reveal that the erasing takes place at a temperature much higher than the glass transition...... temperature. induced anisotropy can be erased by heating the polyesters to approximately 80 degrees C....

  5. Synthesis of Novel Amphiphilic Azobenzenes and X-ray Scattering Studies of Their Langmuir Monolayers

    DEFF Research Database (Denmark)

    Sørensen, Thomas Just; Kjær, Kristian; Breiby, Dag Werner;

    2008-01-01

    air-water interface, the amphiphilic azobenzenes form noncrystalline but stable Langmuir films that display an unusual reversible monolayer collapse close to 35 mN/m. The structures and phase transitions were studied by X-ray reflectivity (XR) and grazing-incidence X-ray diffraction, both utilizing...

  6. 40 CFR 721.9492 - Polymers of styrene, cyclohexyl methacrylate and substituted methacrylate.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polymers of styrene, cyclohexyl... Significant New Uses for Specific Chemical Substances § 721.9492 Polymers of styrene, cyclohexyl methacrylate...) The chemical substances identified generically as polymers of styrene, cyclohexyl methacrylate...

  7. Azobenzene mesogen-passivated gold nanoparticles: Controlled preparation, self-organized superstructures, thermal behavior and photoisomerization

    International Nuclear Information System (INIS)

    Liquid crystal nanoscience has aroused intensive interests mainly due to their unique and collective properties and a variety of potential applications. In this paper, gold nanoparticles (GNPs) coated with alkoxy azobenzene mesogenic thiol ligands of different length polymethylene spacer and linear alkyl thiol co-ligands have been prepared. The thermal properties, phase behavior of thus obtained hybrid GNPs and photophysical properties of their solid-state films have been investigated by differential scanning calorimetry (DSC), variable-temperature small and wide angle X-ray scattering (SAXS/WAXS) and UV–vis spectroscopy. The hybrid GNPs exclusively passivated with azobenzene mesogenic ligands showed lamellar structure while those with mixed ligands exhibited hexagonal columnar superstructure, and the latter complex hybrid GNPs exhibited noticeably improved thermolysis resistance. Moreover, it is very interesting that the solid-state films of the hybrid GNPs displayed reversible photoresponse owing to the trans–cis transformation of azobenzene mesogenic ligands, and compared with the hybrid GNPs coated with mesogenic ligands only, those with mixed ligands exhibited faster photoisomerization rate upon alternate UV and visible light irradiation, which may have some promising applications. - Graphical abstract: Gold nanoparticles (GNPs) coated with azobenzene mesogenic thiol ligands and linear alkyl thiol co-ligands have been prepared showing lamellar or hexagonal columnar superstructures. The complex hybrid GNPs with co-ligands exhibit much improved thermolysis resistance and the solid-state films of the hybrid GNPs display interesting reversible photoisomerization. - Highlights: • Gold nanoparticles (GNPs) coated with azobenzene thiol ligands have been prepared. • The hybrid GNPs with alkyl thiol co-ligands show enhanced thermolysis resistance. • The hybrid GNPs exhibit lamellar or hexagonal columnar superstructures. • The solid-state films of the hybrid

  8. Livingness and synthetic potential of ligated (meth)acrylate polymerization stabilized with alkali metal tert-alkoxides

    Czech Academy of Sciences Publication Activity Database

    Vlček, Petr; Otoupalová, Jaroslava; Janata, Miroslav; Látalová, Petra; Kurková, Dana; Masař, Bohumil; Toman, Luděk

    Boston : International Union of Pure and Applied Chemistry, 2003. s. O63. [International Symposium on Ionic Polymerization. 30.06.2003-04.07.2003, Boston] R&D Projects: GA ČR GA203/01/0513 Institutional research plan: CEZ:AV0Z4050913 Keywords : polymerization anionic * methacrylates * block copolymers Subject RIV: CD - Macromolecular Chemistry

  9. Chain extension of nitroxide-terminated polymer macroinitiators with 2-(dimethylamino)ethyl methacrylate

    Czech Academy of Sciences Publication Activity Database

    Lokaj, Jan; Poláková, Lenka; Holler, Petr; Štěpánek, Petr; Diat, O.

    Prague: Institute of Macromolecular Chemistry AS CR, 2006. s. 100. ISBN 80-85009-52-8. [Microsymposium on Structure and Dynamics of Self-organized Macromolecular Systems /45./. 09.07.2006-13.07.2006, Prague] R&D Projects: GA ČR GESON/03/E001 Institutional research plan: CEZ:AV0Z40500505 Keywords : block copolymers * 2-(dimethylamino)ethyl methacrylate Subject RIV: CD - Macromolecular Chemistry

  10. The Synthesis and Application of Fmoc-Lys(5-Fam) Building Blocks

    OpenAIRE

    Tokmina-Roszyk, Michal; Tokmina-Roszyk, Dorota; Fields, Gregg B.

    2013-01-01

    Fluorescence resonance energy transfer (FRET) peptide substrates are often utilized for protease activity assays. This study has examined the preparation of FRET triple-helical peptide (THP) substrates using 5-carboxyfluorescein (5-Fam) as the fluorophore and 4,4-dimethylamino-azobenzene-4′-carboxylic acid (Dabcyl) as the quencher. The Nα-(9-fluorenylmethoxycarbonyl)-Nε-(5-carboxy-fluorescein)-L-lysine [Fmoc-Lys(5-Fam)] building block was synthesized utilizing two distinct synthetic routes. T...

  11. Polymerization of novel methacrylated anthraquinone dyes

    Directory of Open Access Journals (Sweden)

    Christian Dollendorf

    2013-02-01

    Full Text Available A new series of polymerizable methacrylated anthraquinone dyes has been synthesized by nucleophilic aromatic substitution reactions and subsequent methacrylation. Thereby, green 5,8-bis(4-(2-methacryloxyethylphenylamino-1,4-dihydroxyanthraquinone (2, blue 1,4-bis(4-((2-methacryloxyethyloxyphenylaminoanthraquinone (6 and red 1-((2-methacryloxy-1,1-dimethylethylaminoanthraquinone (12, as well as 1-((1,3-dimethacryloxy-2-methylpropan-2-ylaminoanthraquinone (15 were obtained. By mixing of these brilliant dyes in different ratios and concentrations, a broad color spectrum can be generated. After methacrylation, the monomeric dyes can be covalently emplaced into several copolymers. Due to two polymerizable functionalities, they can act as cross-linking agents. Thus, diffusion out of the polymer can be avoided, which increases the physiological compatibility and makes the dyes promising compounds for medical applications, such as iris implants.

  12. Methacrylate hydrogels reinforced with bacterial cellulose

    Czech Academy of Sciences Publication Activity Database

    Hobzová, Radka; Dušková-Smrčková, Miroslava; Michálek, Jiří; Karpushkin, Evgeny; Gatenholm, P.

    2012-01-01

    Roč. 61, č. 7 (2012), s. 1193-1201. ISSN 0959-8103 R&D Projects: GA AV ČR KJB400500902 Institutional research plan: CEZ:AV0Z40500505 Keywords : bacterial cellulose * methacrylate hydrogel * composite Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.125, year: 2012

  13. Methacrylate Polymer Monoliths for Separation Applications

    Directory of Open Access Journals (Sweden)

    Robert J. Groarke

    2016-06-01

    Full Text Available This review summarizes the development of methacrylate-based polymer monoliths for separation science applications. An introduction to monoliths is presented, followed by the preparation methods and characteristics specific to methacrylate monoliths. Both traditional chemical based syntheses and emerging additive manufacturing methods are presented along with an analysis of the different types of functional groups, which have been utilized with methacrylate monoliths. The role of methacrylate based porous materials in separation science in industrially important chemical and biological separations are discussed, with particular attention given to the most recent developments and challenges associated with these materials. While these monoliths have been shown to be useful for a wide variety of applications, there is still scope for exerting better control over the porous architectures and chemistries obtained from the different fabrication routes. Conclusions regarding this previous work are drawn and an outlook towards future challenges and potential developments in this vibrant research area are presented. Discussed in particular are the potential of additive manufacturing for the preparation of monolithic structures with pre-defined multi-scale porous morphologies and for the optimization of surface reactive chemistries.

  14. Photoinduced reversible switching of porosity in molecular crystals based on star-shaped azobenzene tetramers

    Science.gov (United States)

    Baroncini, Massimo; D'Agostino, Simone; Bergamini, Giacomo; Ceroni, Paola; Comotti, Angiolina; Sozzani, Piero; Bassanetti, Irene; Grepioni, Fabrizia; Hernandez, Taylor M.; Silvi, Serena; Venturi, Margherita; Credi, Alberto

    2015-08-01

    The development of solid materials that can be reversibly interconverted by light between forms with different physico-chemical properties is of great interest for separation, catalysis, optoelectronics, holography, mechanical actuation and solar energy conversion. Here, we describe a series of shape-persistent azobenzene tetramers that form porous molecular crystals in their E-configuration, the porosity of which can be tuned by changing the peripheral substituents on the molecule. Efficient E→Z photoisomerization of the azobenzene units takes place in the solid state and converts the crystals into a non-porous amorphous melt phase. Crystallinity and porosity are restored upon Z→E isomerization promoted by visible light irradiation or heating. We demonstrate that the photoisomerization enables reversible on/off switching of optical properties such as birefringence as well as the capture of CO2 from the gas phase. The linear design, structural versatility and synthetic accessibility make this new family of materials potentially interesting for technological applications.

  15. Novel azobenzene-phthalocyanine dyads——design of photo-modulated J-aggregation

    Institute of Scientific and Technical Information of China (English)

    NIU LiHong; ZHONG Cheng; CHEN ZiHui; ZHANG Zhi; LI ZhongYu; ZHANG FuShi; TANG YingWu

    2009-01-01

    Based on the J-aggregation mechanism of α-aryl/alkoxy-subetituted zinc phthalocyanines(Pcs) in non-coordinating solvents, two novel azobenzene-phthalocyanine dyads (3-azo-ZnPc and 4-azo-ZnPc) were synthesized with the aim of developing Pc compounds whose ability to form J-aggregation could be photo-modulated. It was found that 3-azo-ZnPc in chloroform could be effectively photo-controlled in a wide range. This phenomenon could be explained by the changes in the geometry and dipole moment of azobenzene during the photo-isomerization process. 4-azo-ZnPc did not have this ability at all, with or without UV light illumination. The positions of the oxygen atoms to which the aryl/alkoxy substitution was attached relatively were found important in determining the aggregation ability.

  16. Photoresponsive switches at surfaces based on supramolecular functionalization with azobenzene-oligoglycerol conjugates.

    Science.gov (United States)

    Nachtigall, Olaf; Kördel, Christian; Urner, Leonhard H; Haag, Rainer

    2014-09-01

    The synthesis, supramolecular complexation, and switching of new bifunctional azobenzene-oligoglycerol conjugates in different environments is reported. Through the formation of host-guest complexes with surface immobilized β-cyclodextrin receptors, the bifunctional switches were coupled to gold surfaces. The isomerization of the amphiphilic azobenzene derivatives was examined in solution, on gold nanoparticles, and on planar gold surfaces. The wettability of functionalized gold surfaces can be reversibly switched under light-illumination with two different wavelengths. Besides the photoisomerization processes and concomitant effects on functionality, the thermal cis to trans isomerization of the conjugates and their complexes was monitored. Thermal half-lives of the cis isomers were calculated for different environments. Surprisingly, the half-lives on gold nanoparticles were significantly smaller compared to planar gold surfaces. PMID:25044973

  17. Elucidation of Isomerization Pathways of a Single Azobenzene Derivative Using an STM.

    Science.gov (United States)

    Kazuma, Emiko; Han, Mina; Jung, Jaehoon; Oh, Junepyo; Seki, Takahiro; Kim, Yousoo

    2015-11-01

    The predominant pathway for the isomerization between cis- and trans-azobenzenes-either (i) inversion by the bending of an NNC bond or (ii) rotation by the torsion of two phenyl rings-continues to be a controversial topic. To elucidate each isomerization pathway, a strategically designed and synthesized azobenzene derivative was investigated on a Ag(111) surface. This was achieved by exciting the molecule with tunneling electrons from the tip of a scanning tunneling microscope (STM). Structural analyses of the molecularly resolved STM images reveal that both inversion and rotation pathways are available for isomerization on a metal surface and strongly depend on the initial adsorption structures of the molecule. On the basis of the potential energy diagrams for the isomerization, it is concluded that isomerization pathways on a metal surface are not simply related to the excited states. PMID:26722964

  18. Mechanized azobenzene-functionalized zirconium metal-organic framework for on-command cargo release

    Science.gov (United States)

    Meng, Xiangshi; Gui, Bo; Yuan, Daqiang; Zeller, Matthias; Wang, Cheng

    2016-01-01

    Stimuli-responsive metal-organic frameworks (MOFs) have gained increasing attention recently for their potential applications in many areas. We report the design and synthesis of a water-stable zirconium MOF (Zr-MOF) that bears photoresponsive azobenzene groups. This particular MOF can be used as a reservoir for storage of cargo in water, and the cargo-loaded MOF can be further capped to construct a mechanized MOF through the binding of β-cyclodextrin with the azobenzene stalks on the MOF surface. The resulting mechanized MOF has shown on-command cargo release triggered by ultraviolet irradiation or addition of competitive agents without premature release. This study represents a simple approach to the construction of stimuli-responsive mechanized MOFs, and considering mechanized UiO-68-azo made from biocompatible components, this smart system may provide a unique MOF platform for on-command drug delivery in the future. PMID:27493996

  19. Orientation of azobenzene molecules in polymer films induced by all-optical poling

    Institute of Scientific and Technical Information of China (English)

    Xiaoxia Zhong(钟晓霞); Shouyu Luo(罗售余); Xiuqin Yu(虞秀琴); Qu Li(李劬); Yingli Chen(陈英礼); Yu Sui(隋郁); Jie Yin(印杰)

    2003-01-01

    A model of the alignment of azobenzene molecules in polymer film induced by all-optical poling is proposedand verified by experiment. We found that when the writing beams of frequencies ω and 2ω are both linearlypolarized with their polarization directions parallel to each other, azobenzene molecules tend to reorientto the direction perpendicular to the writing beams polarization. At the end of the writing process, moremolecules orient to the direction perpendicular to the writing beams polarization than those which orientto the parallel direction. The alignment of molecules parallel or perpendicular to the polarization of thewriting beams is characteristic of polarity or no polarity, respectively. The alignment of molecules alongthe polarization of writing beams results in the second order nonlinearity in the polymer film. Accordingto the model, a new method to improve the optical poling efficiency is put forward.

  20. Recent advances towards azobenzene-based light-driven real-time information-transmitting materials

    OpenAIRE

    Jaume García-Amorós; Dolores Velasco

    2012-01-01

    Photochromic switches that are able to transmit information in a quick fashion have attracted a growing interest within materials science during the last few decades. Although very fast photochromic switching materials working within hundreds of nanoseconds based on other chromophores, such as spiropyranes, have been successfully achieved, reaching such fast relaxation times for azobenzene-based photochromic molecular switches is still a challenge. This review focuses on the most recent achie...

  1. Kinetics of the photochromic reaction in a polymer containing azobenzene groups

    Czech Academy of Sciences Publication Activity Database

    Mancheva, I.; Zhivkov, I.; Nešpůrek, Stanislav

    2005-01-01

    Roč. 7, č. 1 (2005), s. 253-256. ISSN 1454-4164 R&D Projects: GA MŠk 1P04OCD14.30 Grant ostatní: Bulgarian Ministry of Education and Science(BG) x-1322 Keywords : photochromism * azobenzene * relaxation properties Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 1.138, year: 2005

  2. Self-assembly of azobenzene bilayer membranes in binary ionic liquid-water nanostructured media.

    Science.gov (United States)

    Kang, Tejwant Singh; Ishiba, Keita; Morikawa, Masa-aki; Kimizuka, Nobuo

    2014-03-11

    Anionic azobenzene-containing amphiphile 1 (sodium 4-[4-(N-methyl-N-dodecylamino)phenylazo]benzenesulfonate) forms ordered bilayer membranes in binary ionic liquid (1-ethyl-3-methylimidazolium ethyl sulfate, [C2mim][C2OSO3])-water mixtures. The binary [C2mim][C2OSO3]-water mixture is macroscopically homogeneous at any mixing ratio; however, it possesses fluctuating nanodomains of [C2mim][C2OSO3] molecules as observed by dynamic light scattering (DLS). These nanodomains show reversible heat-induced mixing behavior with water. Although the amphiphile 1 is substantially insoluble in pure water, it is dispersible in the [C2mim][C2OSO3]-water mixtures. The concentration of [C2mim][C2OSO3] and temperature exert significant influences on the self-assembling characteristics of 1 in the binary media, as shown by DLS, transmission electron microscopy (TEM), UV-vis spectroscopy, and zeta-potential measurements. Bilayer membranes with rod- or dotlike nanostructures were formed at a lower content of [C2mim][C2OSO3] (2-30 v/v %), in which azobenzene chromophores adopt parallel molecular orientation regardless of temperature. In contrast, when the content of [C2mim][C2OSO3] is increased above 60 v/v %, azobenzene bilayers showed thermally reversible gel-to-liquid crystalline phase transition. The self-assembly of azobenzene amphiphiles is tunable depending on the volume fraction of [C2mim][C2OSO3] and temperature, which are associated with the solvation by nanoclusters in the binary [C2mim][C2OSO3]-water media. These observations clearly indicate that mixtures of water-soluble ionic liquids and water provide unique and valiant environments for ordered molecular self-assembly. PMID:24528277

  3. Trans-cis photoisomerization of azobenzene by n→π* excitation:A semiclassical dynamics study

    Institute of Scientific and Technical Information of China (English)

    Shuai Yuan; Wei Feng Wu; Yusheng Dou; Jian She Zhao

    2008-01-01

    A realistic dynamics simulation study is reported for the trans-cis photoisomerization of azobenzene triggered by the n→π*excitation and the results show that the formation of cis isomer follows the rotational motion around the N=N bond.The simulation find that the CNN bond angle bending vibrations also play a significant role in the vibronic coupling between the HOMO and LUMO,which essentially leads a nonadiabatic transition of the molecule to the electronic ground state.

  4. Influence of the substituent on azobenzene side-chain polyester optical storage materials

    DEFF Research Database (Denmark)

    Pedersen, M; Hvilsted, Søren; Holme, NCR;

    1999-01-01

    , chloro, and bromo. C-13 NMR spectroscopic and molecular mass investigations substantiate good film forming characteristics. The optical storage performance of thin polyester films are investigated through polarization holography. The resulting diffraction efficiency is mapped and discussed as a function...... of irradiation power and exposure time. Polytetradecanedioates with cyano-, nitro-, methyl-, fluoro-, or trinuoromethyl-azobenzene reach more than 50% diffraction efficiency. Investigations of anisotropy induced at different temperatures reveal that the polyesters are only photosensitive in a narrow...

  5. Development of a Nonionic Azobenzene Amphiphile for Remote Photocontrol of a Model Biomembrane.

    Science.gov (United States)

    Benedini, Luciano A; Sequeira, M Alejandra; Fanani, Maria Laura; Maggio, Bruno; Dodero, Verónica I

    2016-05-01

    We report the synthesis and characterization of a simple nonionic azoamphiphile, C12OazoE3OH, which behaves as an optically controlled molecule alone and in a biomembrane environment. First, Langmuir monolayer and Brewster angle microscopy (BAM) experiments showed that pure C12OazoE3OH enriched in the (E) isomer was able to form solidlike mesophase even at low surface pressure associated with supramolecular organization of the azobenzene derivative at the interface. On the other hand, pure C12OazoE3OH enriched in the (Z) isomer formed a less solidlike monolayer due to the bent geometry around the azobenzene moiety. Second, C12OazoE3OH is well-mixed in a biological membrane model, Lipoid s75 (up to 20%mol), and photoisomerization among the lipids proceeded smoothly depending on light conditions. It is proposed that the cross-sectional area of the hydroxyl triethylenglycol head of C12OazoE3OH inhibits azobenzenes H-aggregation in the model membrane; thus, the tails conformation change due to photoisomerization is transferred efficiently to the lipid membrane. We showed that the lipid membrane effectively senses the azobenzene geometrical change photomodulating some properties, like compressibility modulus, transition temperature, and morphology. In addition, photomodulation proceeds with a color change from yellow to orange, providing the possibility to externally monitor the system. Finally, Gibbs monolayers showed that C12OazoE3OH is able to penetrate the highly packing biomembrane model; thus, C12OazoE3OH might be used as photoswitchable molecular probe in real systems. PMID:27070294

  6. Characterization of azobenzene polymer networks using in situ solid state NMR and temperature dependent photostriction

    International Nuclear Information System (INIS)

    Azobenzene liquid crystal polymer networks (azo-LCNs) undergo a complex light-driven molecular conformation change of the azobenzene chromophore which imparts a macroscopic shape change within a glassy polymer network. To better understand molecular conformational changes which underlie macroscopic polymer deformation, we have collected solid-state nuclear magnetic resonance (NMR) data on 19F fluorinated side-chain azo-LCNs using an in situ visible light (450–458 nm) LED light source. We illustrate measurable changes in 19F NMR lineshapes under light irradiation, indicating that conformational changes can be probed by NMR. The measured effects of light on NMR spectra are also found to be reversible upon removal of the light source. We further show that sample heating does not affect azobenzene isomerization through analysis of temperature-dependent magic-angle-spinning NMR lineshapes. These results illustrate a narrowing of the lineshapes, but no change in the NMR peak positions, indicating that heating from 30 and 60 ° C affects molecular dynamics but does not change the azobenzene conformation. In addition to NMR data, benchtop photomechanical uni-axial measurements are taken over a temperature range from 23 to 60 ° C. Samples with the fluorinated side-chain azo-LCNs are compared to samples composed only of non-fluorinated main-chain azo-LCN composition. Similar stress relaxation was observed in both compositions under high pre-stretch. The amount of stress relaxation was found to depend on the pre-stretch, the ambient temperature, and the polarization of light. (paper)

  7. Light-enhanced liquid-phase exfoliation and current photoswitching in graphene-azobenzene composites

    Science.gov (United States)

    Döbbelin, Markus; Ciesielski, Artur; Haar, Sébastien; Osella, Silvio; Bruna, Matteo; Minoia, Andrea; Grisanti, Luca; Mosciatti, Thomas; Richard, Fanny; Prasetyanto, Eko Adi; de Cola, Luisa; Palermo, Vincenzo; Mazzaro, Raffaello; Morandi, Vittorio; Lazzaroni, Roberto; Ferrari, Andrea C.; Beljonne, David; Samorì, Paolo

    2016-04-01

    Multifunctional materials can be engineered by combining multiple chemical components, each conferring a well-defined function to the ensemble. Graphene is at the centre of an ever-growing research effort due to its combination of unique properties. Here we show that the large conformational change associated with the trans-cis photochemical isomerization of alkyl-substituted azobenzenes can be used to improve the efficiency of liquid-phase exfoliation of graphite, with the photochromic molecules acting as dispersion-stabilizing agents. We also demonstrate reversible photo-modulated current in two-terminal devices based on graphene-azobenzene composites. We assign this tuneable electrical characteristics to the intercalation of the azobenzene between adjacent graphene layers and the resulting increase in the interlayer distance on (photo)switching from the linear trans-form to the bulky cis-form of the photochromes. These findings pave the way to the development of new optically controlled memories for light-assisted programming and high-sensitive photosensors.

  8. Surface hopping dynamics of direct trans --> cis photoswitching of an azobenzene derivative in constrained adsorbate geometries

    Science.gov (United States)

    Floß, Gereon; Granucci, Giovanni; Saalfrank, Peter

    2012-12-01

    With ongoing miniaturization of electronic devices, the need for individually addressable, switchable molecules arises. An example are azobenzenes on surfaces which have been shown to be switchable between trans and cis forms. Here, we examine the "direct" (rather than substrate-mediated) channel of the trans → cis photoisomerization after ππ* excitation of tetra-tert-butyl-azobenzene physisorbed on surfaces mimicking Au(111) and Bi(111), respectively. In spirit of the direct channel, the electronic structure of the surface is neglected, the latter merely acting as a rigid platform which weakly interacts with the molecule via Van-der-Waals forces. Starting from thermal ensembles which represent the trans-form, sudden excitations promote the molecules to ππ*-excited states which are non-adiabatically coupled among themselves and to a nπ*-excited and the ground state, respectively. After excitation, relaxation to the ground state by internal conversion takes place, possibly accompanied by isomerization. The process is described here by "on the fly" semiclassical surface hopping dynamics in conjunction with a semiempirical Hamiltonian (AM1) and configuration-interaction type methods. It is found that steric constraints imposed by the substrate lead to reduced but non-vanishing, trans → cis reaction yields and longer internal conversion times than for the isolated molecule. Implications for recent experiments for azobenzenes on surfaces are discussed.

  9. Nonadiabatic simulation study of photoisomerization of azobenzene: Detailed mechanism and load-resisting capacity

    CERN Document Server

    Shao, Junfeng; Wen, Zhenyi; Dou, Yusheng; Wang, Zhisong

    2009-01-01

    Nonadiabatic dynamical simulations were carried out to study cis-to-trans isomerization of azobenzene under laser irradiation and/or external mechanical loads. We used a semiclassical electron-radiation-ion dynamics method that is able to describe the coevolution of the structural dynamics and the underlying electronic dynamics in a real-time manner. It is found that azobenzene photoisomerization occurs predominantly by an out-of-plane rotation mechanism even under a nontrivial resisting force of several tens of piconewtons. We have repeated the simulations systematically for a broad range of parameters for laser pulses, but could not find any photoisomerization event by a previously suggested in-plane inversion mechanism. The simulations found that the photoisomerization process can be held back by an external resisting force of 90 - 200 pN depending on the frequency and intensity of the lasers. This study also found that a pure mechanical isomerization is possible from the cis state if the azobenzene molecu...

  10. Optical Input/Electrical Output Memory Elements based on a Liquid Crystalline Azobenzene Polymer.

    Science.gov (United States)

    Mosciatti, Thomas; Bonacchi, Sara; Gobbi, Marco; Ferlauto, Laura; Liscio, Fabiola; Giorgini, Loris; Orgiu, Emanuele; Samorì, Paolo

    2016-03-01

    Responsive polymer materials can change their properties when subjected to external stimuli. In this work, thin films of thermotropic poly(metha)acrylate/azobenzene polymers are explored as active layer in light-programmable, electrically readable memories. The memory effect is based on the reversible modifications of the film morphology induced by the photoisomerization of azobenzene mesogenic groups. When the film is in the liquid crystalline phase, the trans → cis isomerization induces a major surface reorganization on the mesoscopic scale that is characterized by a reduction in the effective thickness of the film. The film conductivity is measured in vertical two-terminal devices in which the polymer is sandwiched between a Au contact and a liquid compliant E-GaIn drop. We demonstrate that the trans → cis isomerization is accompanied by a reversible 100-fold change in the film conductance. In this way, the device can be set in a high- or low-resistance state by light irradiation at different wavelengths. This result paves the way toward the potential use of poly(metha)acrylate/azobenzene polymer films as active layer for optical input/electrical output memory elements. PMID:26890532

  11. Light-enhanced liquid-phase exfoliation and current photoswitching in graphene–azobenzene composites

    Science.gov (United States)

    Döbbelin, Markus; Ciesielski, Artur; Haar, Sébastien; Osella, Silvio; Bruna, Matteo; Minoia, Andrea; Grisanti, Luca; Mosciatti, Thomas; Richard, Fanny; Prasetyanto, Eko Adi; De Cola, Luisa; Palermo, Vincenzo; Mazzaro, Raffaello; Morandi, Vittorio; Lazzaroni, Roberto; Ferrari, Andrea C.; Beljonne, David; Samorì, Paolo

    2016-01-01

    Multifunctional materials can be engineered by combining multiple chemical components, each conferring a well-defined function to the ensemble. Graphene is at the centre of an ever-growing research effort due to its combination of unique properties. Here we show that the large conformational change associated with the trans–cis photochemical isomerization of alkyl-substituted azobenzenes can be used to improve the efficiency of liquid-phase exfoliation of graphite, with the photochromic molecules acting as dispersion-stabilizing agents. We also demonstrate reversible photo-modulated current in two-terminal devices based on graphene–azobenzene composites. We assign this tuneable electrical characteristics to the intercalation of the azobenzene between adjacent graphene layers and the resulting increase in the interlayer distance on (photo)switching from the linear trans-form to the bulky cis-form of the photochromes. These findings pave the way to the development of new optically controlled memories for light-assisted programming and high-sensitive photosensors. PMID:27052205

  12. Photo-induced and thermal reactions in thin films of an azobenzene derivative on Bi(111)

    International Nuclear Information System (INIS)

    Azobenzene is a prototypical molecular switch which can be interconverted with UV and visible light between a trans and a cis isomer in solution. While the ability to control their conformation with light is lost for many molecular photoswitches in the adsorbed state, there are some examples for successful photoisomerization in direct contact with a surface. However, there the process is often driven by a different mechanism than in solution. For instance, photoisomerization of a cyano-substituted azobenzene directly adsorbed on Bi(111) occurs via electronic excitations in the substrate and subsequent charge transfer. In the present study we observe two substrate-mediated trans–cis photoisomerization reactions of the same azobenzene derivative in two different environments within a multilayer thin film on Bi(111). Both processes are associated with photoisomerization and one is around two orders of magnitude more efficient than the other. Furthermore, the cis isomers perform a thermally induced reaction which may be ascribed to a back-isomerization in the electronic ground state or to a phenyl ring rotation of the cis isomer

  13. Tuning the optical emission of MoS2 nanosheets using proximal photoswitchable azobenzene molecules

    International Nuclear Information System (INIS)

    We report photoluminescence measurements performed on monolayer- and two-layer-MoS2 placed on two types of mixed self-assembled monolayers (mSAMs) of photoswitchable azobenzene molecules. The two mSAMs differ via the electronegative character of the azobenzene derivatives. Thin layers of a transition metal dichalcogenide—MoS2—were mechanically exfoliated on mSAM to allow for direct interaction between the molecules and the MoS2 layers. When the MoS2 nanosheet is in contact with the electropositive azobenzene molecules in trans configuration, an emission side band at lower energies and at low excitation powers suggest n-type doping. The photoisomerization of the molecules from trans to cis configuration lowers the doping, quenching the side band and enhancing the overall PL efficiency by a factor of ∼3. Opposite results were observed with the chlorinated, more electronegative molecules, exhibiting a reversed trend in the PL efficiency between trans and cis, but with an overall larger intensity. The type of doping induced by the two types of mSAMs was determined by Kelvin probe force microscopy technique

  14. Synthesis and morphological characterization of block copolymers for improved biomaterials

    International Nuclear Information System (INIS)

    Biocompatible polymers are known to act as scaffolds for the regeneration and growth of bone. Block copolymers are of interest as scaffold materials because a number of the blocks are biocompatible, and their nanostructure is easily tunable with synthetic techniques. In this paper, we report the synthesis of a novel class of biomaterials from block copolymers containing a hydrophobic block of methyl methacrylate and a hydrophilic block of either acrylic acid, dimethyl acrylamide, or 2-hydroxyethyl methacrylate. The block copolymers were synthesized using a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and click chemistry. Since the surface morphology is critical for successful cell growth, atomic force microscopy (AFM) studies were conducted for selected block copolymers. The topography, phase angle and friction maps were obtained in dry and physiological buffer environments to study the morphology. Results of AFM imaging identified the presence of polymer domains corresponding to the copolymer components. The distribution of nanoscale features in these block copolymers is comparable to those found on other surfaces that exhibit favorable cell adhesion and growth. In physiological buffer medium, the hydrophilic component of the block copolymer (acrylic acid or hydroxyethyl methacrylate) appears to be present in greater amounts on the surface as a consequence of water absorption and swelling.

  15. Synthesis and morphological characterization of block copolymers for improved biomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Schricker, Scott, E-mail: Schricker.1@osu.edu [Restorative and Prosthetic Dentistry Section, College of Dentistry, The Ohio State University, Columbus, OH 43210 (United States); Palacio, Manuel [Nanoprobe Laboratory for Bio- and Nanotechnology and Biomimetics, The Ohio State University, Columbus, OH 43210 (United States); Thirumamagal, B.T.S. [Restorative and Prosthetic Dentistry Section, College of Dentistry, The Ohio State University, Columbus, OH 43210 (United States); Bhushan, Bharat [Nanoprobe Laboratory for Bio- and Nanotechnology and Biomimetics, The Ohio State University, Columbus, OH 43210 (United States)

    2010-05-15

    Biocompatible polymers are known to act as scaffolds for the regeneration and growth of bone. Block copolymers are of interest as scaffold materials because a number of the blocks are biocompatible, and their nanostructure is easily tunable with synthetic techniques. In this paper, we report the synthesis of a novel class of biomaterials from block copolymers containing a hydrophobic block of methyl methacrylate and a hydrophilic block of either acrylic acid, dimethyl acrylamide, or 2-hydroxyethyl methacrylate. The block copolymers were synthesized using a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and click chemistry. Since the surface morphology is critical for successful cell growth, atomic force microscopy (AFM) studies were conducted for selected block copolymers. The topography, phase angle and friction maps were obtained in dry and physiological buffer environments to study the morphology. Results of AFM imaging identified the presence of polymer domains corresponding to the copolymer components. The distribution of nanoscale features in these block copolymers is comparable to those found on other surfaces that exhibit favorable cell adhesion and growth. In physiological buffer medium, the hydrophilic component of the block copolymer (acrylic acid or hydroxyethyl methacrylate) appears to be present in greater amounts on the surface as a consequence of water absorption and swelling.

  16. METHACRYLATE AND ACRYLATE ALLERGY IN DENTAL STUDENTS.

    Directory of Open Access Journals (Sweden)

    Maya Lyapina

    2013-09-01

    Full Text Available A multitude of acrylic monomers is used in dentistry, and when dental personnel, patients or students of dental medicine become sensitized, it is of great importance to identify the dental ;acrylic preparations to which the sensitized individual can be exposed. Numerous studies confirm high incidence of sensitization to (meth acrylates in dentatal professionals, as well as in patients undergoing dental treatment and exposed to resin-based materials. Quite a few studies are available aiming to evaluate the incidence of sensitization in students of dental medicineThe purpose of the study is to evaluate the incidence of contact sensitization to some (meth acrylates in students of dental medicine at the time of their education, in dental professionals (dentists, nurses and attendants and in patients, the manifestation of co-reactivity.A total of 139 participants were included in the study, divided into four groups: occupationally exposed to (methacrylates and acrylic monomers dental professionals, 3-4 year-of-education students of dental medicine, 6th year–of-education students of dental medicine and patients with suspected or established sensitization to acrylates, without occupational exposure. All of them were patch-tested with methyl methacrylate (MMA, triethyleneglycol dimethacrylate (TREGDMA, ethyleneglycol dimethacrylate (EGDMA, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy phenyl]propane (bis-GMA, 2-hydroxyethyl methacrylate (2-HEMA, and tetrahidrofurfuril metacrylate. The overall sensitization rates to methacrylates in the studied population are comparative high – from 25.9% for MMA to 31.7% for TREGDMA. Significantly higher incidence of sensitization in the group of 3-4 course students compared to the one in the group of dental professionals for MMA and TREGDMA was observed. Highest was the incidence of sensitization to ethyleneglycol dimethacrylate, BIS-GMA, 2-HEMA and tetrahydrofurfuryl methacrylate in the group of patients, with

  17. Synthesis and Characterization of Polyphosphazenes Modified with Hydroxyethyl Methacrylate and Lactic Acid

    Directory of Open Access Journals (Sweden)

    Evelyn Carolina Martínez Ceballos

    2013-01-01

    Full Text Available Poly(dichlorophosphazene was prepared by melt ring-opening polymerization of the hexachlorocyclotriphosphazene. Poly[bis(2-hydroxyethyl-methacrylate-phosphazene] and poly[(2-hydroxyethyl-methacrylate-graft-poly(lactic-acid-phosphazene] were obtained by nucleophilic condensation reactions at different concentrations of the substituents. The properties of the synthesized copolymers were assessed by FTIR, 1H-NMR and 31P-NMR, thermal analysis (DSC-TGA, and electron microscopy (SEM. The copolymers have a block structure and show two Tg's below room temperature. They are stable up to a temperature of 100°C. The type of the substituents attached to the PZ backbone determines the morphology of the polymers.

  18. The cis-state of an azobenzene photoswitch is stabilized through specific interactions with a protein surface.

    Science.gov (United States)

    Korbus, Michael; Backé, Sarah; Meyer-Almes, Franz-Josef

    2015-03-01

    The photocontrol of protein function like enzyme activity has been the subject of many investigations to enable reversible and spatiotemporally defined cascading biochemical reactions without the need for separation in miniaturized and parallelized assay setups for academic and industrial applications. A photoswitchable amidohydrolase variant from Bordetella/Alcaligenes with the longest reported half-life (approximately 30 h) for the cis-state of the attached azobenzene group was chosen as a model system to dissect the underlying mechanism and molecular interactions that caused the enormous deceleration of the thermal cis-to-trans relaxation of the azobenzene photoswitch. A systematic site-directed mutagenesis study on the basis of molecular dynamics simulation data was employed to investigate enzyme and thermal cis-to-trans relaxation kinetics in dependence on selected amino acid substitution, which revealed a prominent histidine and a hydrophobic cluster as molecular determinants for the stabilization of the cis-isomer of the attached azobenzene moiety on the protein surface. The nature of the involved interactions consists of polar, hydrophobic, and possibly aromatic Π-Π contributions. The elucidated principles behind the stabilization of the cis-state of azobenzene derivatives on a protein surface can be exploited to design improved biologically inspired photoswitches. Moreover, the findings open the door to highly long-lived cis-states of azobenzene groups yielding improved bistable photoswitches that can be controlled by single light-pulses rather than continuous irradiation with UV light that causes potential photodamage to the employed biomolecules. PMID:25664524

  19. NANOSTRUCTURES OF FUNCTIONAL BLOCK COPOLYMERS

    Institute of Scientific and Technical Information of China (English)

    Guojun Liu

    2000-01-01

    Nanostructure fabrication from block copolymers in my group normally involves polymer design, synthesis, selfassembly, selective domain crosslinking, and sometimes selective domain removal. Preparation of thin films with nanochannels was used to illustrate the strategy we took. In this particular case, a linear triblock copolymer polyisopreneblock-poly(2-cinnamoylethyl methacrylate)-block-poly(t-butyl acrylate), PI-b-PCEMA-b-PtBA, was used. Films, 25 to50μm thick, were prepared from casting on glass slides a toluene solution of PI-b-PCEMA-b-PtBA and PtBA homopolymer,hPtBA, where hPtBA is shorter than the PtBA block. At the hPtBA mass fraction of 20% relative to the triblock or the total PtBA (hPtBA and PtBA block) volume fraction of 0.44, hPtBA and PtBA formed a seemingly continuous phase in the matrix of PCEMA and PI. Such a block segregation pattern was locked in by photocrosslinking the PCEMA domain. Nanochannels were formed by extracting out hPtBA with solvent. Alternatively, larger channels were obtained from extracting out hPtBA and hydrolyzing the t-butyl groups of the PtBA block. Such membranes were not liquid permeable but had gas permeability constants ~6 orders of magnitude higher than that of low-density polyethylene films.

  20. The immobilization of enzymes onto poly(ethylene)-g.co-methacrylic acid, [poly(ethylene)-g.co-hydroxyethyl methacrylate]-g.co-methacrylic acid and [poly(ethylene)-g.co-methacrylic acid]-g.co-hydroxyethyl methacrylate

    International Nuclear Information System (INIS)

    A series of graft copolymers has been prepared on the poly(ethylene) backbone. These carry functional groups which are effective in coupling and provide a level of hydrophilicity which is thought to be consistent with generating a suitable micro-environment for enzyme immobilization and subsequent enhanced biocatalyst stability. Four enzymes have been immobilized. These are papain, trypsin, glucose oxidase and α-chymotrypsin. The parent copolymers were assembled via radiation-induced grafting. Secondary grafting was achieved in two ways. The first involved grafting methacrylic acid onto poly(ethylene)-g.co-hydroxyethyl methacrylate, while the second involved grafting hydroxyethyl methacrylate onto poly(ethylene)-g.co-methacrylic acid. The results suggest that a high degree of specificity arises in the systems examined with regard to the enzymes, the type of copolymers and the coupling procedures. Generally, relatively large amounts of enzyme become covalently attached to the copolymers, though the overall level of activity is low. In this work it has been observed that the most satisfactory results were obtained when the partly hydrolyzed poly(ethylene)-g.co-hydroxyethyl methacrylate was used in the immobilization of the biocatalysts. (author)

  1. Heart Block

    Science.gov (United States)

    ... the signal causes the heart to contract and pump blood. Heart block occurs if the electrical signal is ... degree heart block limits the heart's ability to pump blood to the rest of the body. This type ...

  2. Low Molecular Weight pDMAEMA-block-pHEMA Block-Copolymers Synthesized via RAFT-Polymerization: Potential Non-Viral Gene Delivery Agents?

    OpenAIRE

    Thomas Kissel; Christian Pfeiffer; Olga Samsonova; Markus Hellmund; Merkel, Olivia M.

    2011-01-01

    The aim of this study was to investigate non-viral pDNA carriers based on diblock-copolymers consisting of poly(2-(dimethyl amino)ethyl methacrylate) (pDMAEMA) and poly(2-hydroxyethyl methacrylate) (pHEMA). Specifically the block-lengths and molecular weights were varied to determine the minimal requirements for transfection. Such vectors should allow better transfection at acceptable toxicity levels and the entire diblock-copolymer should be suitable for renal clearance. For this purpose, a ...

  3. Photo-induced morphological winding and unwinding motion of nanoscrolls composed of niobate nanosheets with a polyfluoroalkyl azobenzene derivative

    Science.gov (United States)

    Nabetani, Yu; Takamura, Hazuki; Uchikoshi, Akino; Hassan, Syed Zahid; Shimada, Tetsuya; Takagi, Shinsuke; Tachibana, Hiroshi; Masui, Dai; Tong, Zhiwei; Inoue, Haruo

    2016-06-01

    Photo-responsive nanoscrolls can be successfully fabricated by mixing a polyfluoroalkyl azobenzene derivative and a niobate nanosheet, which is exfoliated from potassium hexaniobate. In this study, we have found that the photo-responsive nanoscroll shows a morphological motion of winding and unwinding, which is basically due to the nanosheet sliding within the nanoscroll, by efficient photo-isomerization reactions of the intercalated azobenzene in addition to the interlayer distance change of the nanoscrolls. The relative nanosheet sliding of the nanoscroll is estimated to be ca. 280 nm from the AFM morphology analysis. The distance of the sliding motion is over 20 times that of the averaged nanosheet sliding in the azobenzene/niobate hybrid film reported previously. Photo-responsive nanoscrolls can be expected to be novel photo-activated actuators and artificial muscle model materials.Photo-responsive nanoscrolls can be successfully fabricated by mixing a polyfluoroalkyl azobenzene derivative and a niobate nanosheet, which is exfoliated from potassium hexaniobate. In this study, we have found that the photo-responsive nanoscroll shows a morphological motion of winding and unwinding, which is basically due to the nanosheet sliding within the nanoscroll, by efficient photo-isomerization reactions of the intercalated azobenzene in addition to the interlayer distance change of the nanoscrolls. The relative nanosheet sliding of the nanoscroll is estimated to be ca. 280 nm from the AFM morphology analysis. The distance of the sliding motion is over 20 times that of the averaged nanosheet sliding in the azobenzene/niobate hybrid film reported previously. Photo-responsive nanoscrolls can be expected to be novel photo-activated actuators and artificial muscle model materials. Electronic supplementary information (ESI) available: Fig. S1. Photo-isomerization reaction of nanoscrolls. See DOI: 10.1039/c6nr02177h

  4. Population Blocks.

    Science.gov (United States)

    Smith, Martin H.

    1992-01-01

    Describes an educational game called "Population Blocks" that is designed to illustrate the concept of exponential growth of the human population and some potential effects of overpopulation. The game material consists of wooden blocks; 18 blocks are painted green (representing land), 7 are painted blue (representing water); and the remaining…

  5. Fabrication of narrow surface relief features in a side-chain azobenzene polyester with a scanning near-field microscope

    DEFF Research Database (Denmark)

    Ramanujam, P.S.; Holme, N. C. R.; Pedersen, M.;

    2001-01-01

    We show that it is possible to fabricate topographic submicron features in a side-chain azobenzene polyester with a scanning near-field optical microscope, Through irradiation at a wavelength of 488 run at intensity levels of 12 W/cm(2), topographic features as narrow as 240 nm and as high as 6 nm...... have been reproducibly recorded in a thin film of the polyester. These observations are consistent with the fact that at low intensities peaks are produced evolving into formation of trenches at high intensities in the case of amorphous side-chain azobenzene polyesters. This may find applications in...

  6. Multifunctional poly(alkyl methacrylate) films for dental care

    Energy Technology Data Exchange (ETDEWEB)

    Nielsen, Birthe V; Nevell, Thomas G; Barbu, Eugen; Smith, James R; Tsibouklis, John [School of Pharmacy and Biomedical Sciences, University of Portsmouth, Portsmouth, Hampshire, PO1 2DT (United Kingdom); Rees, Gareth D [GlaxoSmithKline R and D, St George' s Avenue, Weybridge, Surrey, KT13 0DE (United Kingdom)

    2011-02-15

    Towards the evaluation of non-permanent dental coatings for their capacity to impart dental-care benefits, thin films of a homologous series of comb-like poly(alkyl methacrylate)s (ethyl to octadecyl) have been deposited, from aqueous latex formulations, onto dentally relevant substrates. AFM studies have shown that the thickness (40-300 nm) and surface roughness (8-12 nm) of coherent polymer films are influenced by the degree of polymerization and by the length of the pendant chain. Of the polymers under consideration, poly(butyl methacrylate) formed a close-packed film that conferred to dental substrates a high degree of inhibition to acid-mediated erosion (about 27%), as evaluated by released-phosphate determinations. The potential utility of the coatings to act as anti-sensitivity barriers has been evaluated by determining the hydraulic conductance of coated bovine-dentine substrates; single treatments of dentine discs with poly(butyl methacrylate) or with poly(ethyl methacrylate) effected mean respective reductions in fluid flow of about 23% with respect to water-treated controls; repeated applications of the poly(butyl methacrylate) latex led to mean reductions in fluid flow of about 80%. Chromometric measurements have shown that pellicle-coated hydroxyapatite discs treated with poly(butyl methacrylate), poly(hexyl methacrylate) or poly(lauryl methacrylate) exhibit significant resistance to staining by food chromogens.

  7. Vibrational spectra study of phosphorus dendrimer containing azobenzene, ammonium and carbamate groups

    Science.gov (United States)

    Furer, V. L.; Vandyukov, A. E.; Majoral, J. P.; Caminade, A. M.; Kovalenko, V. I.

    2013-06-01

    The FTIR and FT Raman spectra of the first generation dendrimers, possessing carbamate (G1) or ammonium (G2) terminal groups were studied. The structural optimization and normal mode analysis were performed for dendrimers on the basis of the density functional theory (DFT). These calculations of G2 gave the frequencies of vibrations, infrared intensities and Raman scattering activities for the E- and Z-forms of azobenzene unit. The energy difference between the E- and Z-forms of G2 is 27.36 kcal/mol. The calculated geometrical parameters and harmonic vibrational frequencies are predicted in a good agreement with the experimental data. It was found that dendrimers molecules have a concave lens structure with planar -O-C6H4-CHdbnd N-N(CH3)Pdbnd S, and -O-C6H4-Ndbnd N-C6H4-CHdbnd N-NH-Cdbnd O-CH2-N fragments and slightly non-planar cyclotriphosphazene core. The experimental IR and Raman spectra of dendrimers G1 and G2 were interpreted by means of potential energy distributions. Relying on DFT calculations a complete vibrational assignment is proposed. The strong band 1605 cm-1 in the IR spectra show marked changes of the optical density in dependence of substituents in the aromatic ring. The differences in the IR and Raman spectra of G2 for the E- and Z-forms of azobenzene units were cleared up. During structural isomerization of azobenzene units, redistribution of band intensities appears to a much higher extent than frequency shifts.

  8. Study on the prediction of visible absorption maxima of azobenzene compounds

    OpenAIRE

    Liu, Jun-Na; Chen, Zhi-Rong; Yuan, Shen-feng

    2005-01-01

    The geometries of azobenzene compounds are optimized with B3LYP/6-311G* method, and analyzed with nature bond orbital, then their visible absorption maxima are calculated with TD-DFT method and ZINDO/S method respectively. The results agree well with the observed values. It was found that for the calculation of visible absorption using ZINDO/S method could rapidly yield better results by adjusting OWFπ-π (the relationship between π-π overlap weighting factor) value than by the TD-DFT method. ...

  9. Influence of the substituent on azobenzene side-chain polyester optical storage materials

    DEFF Research Database (Denmark)

    Pedersen, M; Hvilsted, Søren; Holme, NCR; Berg, RH

    1999-01-01

    A number of poly(1,3-propylenetetradecanedioates) or poly(1,3-propyleneadipates) with pendant p-substitued azobenzenes linked through a hexylene spacer in the 2-position are prepared. The substituents comprise: cyano, nitro, methoxy, hydrogen, methyl, n-butyl, phenyl, fluoro, trifluoromethyl......, chloro, and bromo. C-13 NMR spectroscopic and molecular mass investigations substantiate good film forming characteristics. The optical storage performance of thin polyester films are investigated through polarization holography. The resulting diffraction efficiency is mapped and discussed as a function...

  10. C5-Azobenzene-substituted 2'-Deoxyuridine-containing Oligodeoxynucleotides for Photo-Switching Hybridization

    Directory of Open Access Journals (Sweden)

    Shohei Mori

    2014-04-01

    Full Text Available A new photoisomeric nucleoside dUAz bearing an azobenzene group at the C5-position of 2'-deoxyuridine was designed and synthesized. Photoisomerization of dUAz in oligodeoxynucleotides can be achieved rapidly and selectively with 365 nm (forward and 450 nm (backward irradiation. Thermal denaturation experiments revealed that dUAz stabilized the duplex in the cis-form and destabilized it in the trans-form with mismatch discrimination ability comparable to thymidine. These results indicate that dUAz could be a powerful material for reversibly manipulating nucleic acid hybridization with spatiotemporal control.

  11. Photomechanical Response of Composite Structures Built from Azobenzene Liquid Crystal Polymer Networks

    Directory of Open Access Journals (Sweden)

    Kyung Min Lee

    2011-09-01

    Full Text Available Optically directed shape adaptive responses have been sought after for many decades in photoresponsive polymeric materials. A number of recent examinations have elucidated elucidated the unique opportunities of photomechanical responses realized in azobenzene-functionalized liquid crystalline polymer networks (both elastomers and glasses. This work summarizes and contrasts the photomechanical response of glassy polydomain, monodomain, and twisted nematic azo-LCN materials to blue-green irradiation. Building from this summary, the combinatorial photomechanical response observed upon irradiation of composite cantilevers is examined. Large scale shape adaptations are realized, with novel responses that may be of potential use in future employment of these materials in actuation.

  12. Azobenzene Modified Imidacloprid Derivatives as Photoswitchable Insecticides: Steering Molecular Activity in a Controllable Manner

    Science.gov (United States)

    Xu, Zhiping; Shi, Lina; Jiang, Danping; Cheng, Jiagao; Shao, Xusheng; Li, Zhong

    2015-10-01

    Incorporating the photoisomerizable azobenzene into imidacloprid produced a photoswitchable insecticidal molecule as the first neonicotinoid example of remote control insecticide performance with spatiotemporal resolution. The designed photoswitchable insecticides showed distinguishable activity against Musca both in vivo and in vitro upon irradiation. Molecular docking study further suggested the binding difference of the two photoisomers. The generation of these photomediated insecticides provides novel insight into the insecticidal activity facilitating further investigation on the functions of insect nicotinic acetylcholine receptors and opens a novel way to control and study insect behavior on insecticide poisoning using light.

  13. Photoresponsive Toroidal Nanostructure Formed by Self-Assembly of Azobenzene-Functionalized Tris(phenylisoxazolyl)benzene.

    Science.gov (United States)

    Adachi, Hiroaki; Hirai, Yuko; Ikeda, Toshiaki; Maeda, Makoto; Hori, Ryo; Kutsumizu, Shoichi; Haino, Takeharu

    2016-03-01

    The self-assembly of tris(phenylisoxazolyl)benzene 1b with photochemically addressable azobenzene moieties produced toroidal nanostructures, the formation and dissociation of which were reversibly regulated upon photoirradiation. 1b displayed a mesogenic behavior. In the solution, the stacked assemblies along with their C3 axes were formed. In the mesophase, two molecules of 1b most likely adopted the antiparallel arrangement to stabilize the columnar organization. This assembling behavior most likely triggered the development of the supramolecular toroidal nanostructures. PMID:26910789

  14. Continuously tunable laser based on polarization gratings in azobenzene-containing material

    International Nuclear Information System (INIS)

    Two simple procedures to manufacture continuously tunable miniature lasers in azobenzene-containing material were developed. Both types of lasers rely on the distributed feedback provided by polarization gratings. In a first approach tuning is achieved by changing the thickness of the active wave guiding layer by means of a wedge layer and in a second approach by gradually changing the spatial frequency of the refractive index grating obtained by modification of the Lloyd interferometer set-up used for holographic inscription of the gratings. A continuous tuning range of up to 35 nm has been demonstrated. (paper)

  15. Optical and Physical Applications of Photocontrollable Materials: Azobenzene-Containing and Liquid Crystalline Polymers

    Directory of Open Access Journals (Sweden)

    Takashi Fukuda

    2012-01-01

    Full Text Available Photocontrol of molecular alignment is an exceptionally-intelligent and useful strategy. It enables us to control optical coefficients, peripheral molecular alignments, surface relief structure, and actuation of substances by means of photoirradiation. Azobenzene-containing polymers and functionalized liquid crystalline polymers are well-known photocontrollable materials. In this paper, we introduce recent applications of these materials in the fields of mechanics, self-organized structuring, mass transport, optics, and photonics. The concepts in each application are explained based on the mechanisms of photocontrol. The interesting natures of the photocontrollable materials and the conceptual applications will stimulate novel ideas for future research and development in this field.

  16. Kinetics of reactions of amines with statistical and block copolymers of glycidyl methacrylate (GMA) and butyl methacrylate (BMA)

    Czech Academy of Sciences Publication Activity Database

    Špaček, V.; Zelenka, J.; Dušek, Karel

    Aghia Pelaghia : Ellenie Polymer Society, 1996. s. -. [European Polymer Federation Symposium on Polymeric Materials /6./. 07.10.1996-11.10.1996, Aghia Pelaghia] Grant ostatní: DuPont Automotive (US) -

  17. Spectroluminescent properties of irradiated polymethyl methacrylate

    International Nuclear Information System (INIS)

    Electron spin resonance spectroscopy (ESR), optical absorption spectroscopy at 77 K and room temperature, fluorescence spectroscopy, and Raman spectroscopy (RS) are used to show a correlation between processes leading to formation of macroradicals in irradiated polymethyl methacrylate (PMMA) and changes in spectroluminescent properties of the polymer. An analysis of the ESR and fluorescence spectra of PMMA irradiated with doses ranging from 5 to 500 kGy shows that the maxima in the fluorescence spectra at 500, 490, and 540-560 nm are due to alkyl, allyl, and polyene end groups, respectively. The fluorescence bands with maxima between 440 and 460 nm may be associated with nonradical pyrolysis products in the polymer

  18. Radiation copolymerization of tributyltin methacrylate and methylmathacrylate

    International Nuclear Information System (INIS)

    The copolymer of tributytin methacrylate and methylmethacrylate is a useful self-polishing antifouling paints materials. It was synthesized by radiation polymerization using 60Co γ ray at room temperature. The copolymerization kinetics of the pair of monomers was studied. The relationship between the reaction rate and the dose rate was found to be Rp = Kp·I-053 and the reactivity ratios were measured to be less than 1. The overall activition energy was 1.29 x 104 J/mol. It was supposed that the copolymerization was of radical machanism

  19. Novel multiarm star block copolymer ionomers as proton conductive membranes

    OpenAIRE

    Demirel, Adem Levent; Erdoğan, Tuba; Bilir, Çiğdem; Ünveren, Elif; Tunca, Ümit

    2014-01-01

    A series of well-defined novel multiarm star block copolymer ionomers with an average of 6, 11 and 15 arms, sulfonated polystyrene-block-poly(2,2,3,3,3-pentafluoropropyl methacrylate) (SPS-b-PFPMA), were prepared via a combination of atom transfer radical polymerization (ATRP), Diels–Alder click reaction and postsulfonation reaction. First, multiarm star polymer with anthracene functionality as reactive periphery groups was prepared by a cross-linking reaction of divinyl benzene using ?-anthr...

  20. trans-cis photoisomerization of azobenzene-conjugated dithiolato-bipyridine platinum(II) complexes: extension of photoresponse to longer wavelengths and photocontrollable tristability.

    Science.gov (United States)

    Sakamoto, Ryota; Kume, Shoko; Sugimoto, Manabu; Nishihara, Hiroshi

    2009-01-01

    Azobenzene derivatives modified with dithiolato-bipyridine platinum(II) complexes were synthesized, revealing their highly extended photoresponses to the long wavelength region as well as unique photocontrollable tristability. The absorptions of trans-1 and trans-2 with one azobenzene group on the dithiolene and bipyridine ligands, respectively, cover the range from 300 to 700 nm. These absorptions are ascribed, by means of time-dependent (TD)DFT calculations, to transitions from dithiolene(pi) to bipyridine(pi*), namely, interligand charge transfer (CT), pi-pi*, and n-pi* transitions of the azobenzene unit, and pi-pi* transitions of the bipyridine ligand. In addition, only trans-1 shows distinctive electronic bands, assignable to transitions from the dithiolene(pi) to azobenzene(pi*), defined as intraligand CT. Complex 1 shows photoisomerization behavior opposite to that of azobenzene: trans-to-cis and cis-to-trans conversions proceed with 405 and 312 nm irradiation, which correspond to excitation with the intraligand CT, and pi-pi* bands of the azobenzene and bipyridine units, respectively. In contrast, complex 2 shows photoisomerization similar to that of azobenzene: trans-to-cis and cis-to-trans transformations occur with 365 and 405 nm irradiation, respectively. Irradiation at 578 nm, corresponding to excitation of the interligand CT transitions, results in cis-to-trans conversion of both 1 and 2, which is the longest wavelength ever reported to effect the photoisomerization of the azobenzene group. The absorption and photochromism of 4, which has azobenzene groups on both the dithiolato and bipyridine ligands, have characteristics quite similar to those of 1 and 2, which furnishes 4 with photocontrollable tristability in a single molecule using light at 365, 405, and 578 nm. We also clarified that 1 and 2 have high photoisomerization efficiencies, and good thermal stability of the cis forms. Complexes 3 and 5 have almost the identical photoresponse to those

  1. Hydrogen-bonded multilayers of micelles of a dually responsive dicationic block copolymer

    OpenAIRE

    Erel, İrem; Karahan, H. Enis; Demirel, A. Levent; Tuncer, Cansel; Bütün, Vural

    2012-01-01

    We report the fabrication of hydrogen-bonded multilayers of micelles of a dually responsive, dicationic block copolymer, poly[2-(N-morpholino)ethyl methacrylate-block-2-(diisopropylamino)ethyl methacrylate] (PMEMA-b-PDPA). By taking advantage of the difference in the hydrophilicity of PMEMA and PDPA blocks, micelles with a PMEMA-corona and a PDPA-core were obtained above pH 6.5 and were assembled layer-by-layer at the surface with tannic acid (TA) at pH 7.4 through hydrogen bonding interactio...

  2. Thermoresponsive and Redox Behaviors of Poly(N-isopropylacrylamide)-Based Block Copolymers Having TEMPO Groups as Their Side Chains

    OpenAIRE

    Toru Uemukai; Tomoya Hioki; Manabu Ishifune

    2013-01-01

    Thermoresponsive and redox-active block copolymers having 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) moieties have been synthesized by using the reversible addition-fragmentation chain transfer (RAFT) polymerization technique. N-Isopropylacrylamide (NIPAAm) and 2,2,6,6-tetramethylpiperidyl methacrylate (TEMPMA) monomers were copolymerized stepwise under RAFT polymerization conditions to afford the thermoresponsive block copolymers, PNIPAAm-block-PTEMPMA and PNIPAAm-block-PTEMPMA-block-PNIPA...

  3. Ab initio calculation of the electronic spectrum of azobenzene dyes and its impact on the design of optical data storage materials

    DEFF Research Database (Denmark)

    Åstrand, Per-Olof; Ramanujam, P.S.; Hvilsted, Søren; Bak, K.L.; Sauer, S.P.A.

    2000-01-01

    Electronic excitation energies of 16 azobenzene dyes have been calculated by ab initio methods within the second-order polarization propagator approximation (SOPPA). Good agreement with expriment is found for the lowest singlet and triplet states for both the trans- and cis-azobenzene molecules......V. Furthermore, the experimental singlet π → π* transitions are reproduced for a set of azobenzene dyes with different electron donor and acceptor groups and the correct shifts in excitation energy are obtained for the different substituents. It has also been demonstrated that ab initio methods can be used to...... determine suitable candidates for azo components used in materials for data storage....

  4. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  5. 21 CFR 172.775 - Methacrylic acid-divinylbenzene copolymer.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Methacrylic acid-divinylbenzene copolymer. 172.775 Section 172.775 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES... HUMAN CONSUMPTION Other Specific Usage Additives § 172.775 Methacrylic acid-divinylbenzene...

  6. Gating the photochromism of an azobenzene by strong host-guest interactions in a divalent pseudo[2]rotaxane.

    Science.gov (United States)

    Lohse, Mirko; Nowosinski, Karol; Traulsen, Nora L; Achazi, Andreas J; von Krbek, Larissa K S; Paulus, Beate; Schalley, Christoph A; Hecht, Stefan

    2015-06-18

    The ability of an E-configured azobenzene guest to undergo photoisomerisation is controlled by the presence of a complementary host. Addition of base/acid allowed for a weakening/strengthening of the interactions in the divalent pseudo[2]rotaxane complex and hence could switch on/off photochromic activity. PMID:25929291

  7. Temperature- and Photocontrolled Unfolding/Folding of a Triple-Helical Azobenzene-Stapled Collagen Peptide Monitored by Infrared Spectroscopy.

    Science.gov (United States)

    Lorenz, Lisa; Kusebauch, Ulrike; Moroder, Luis; Wachtveitl, Josef

    2016-05-01

    The triple-helical structure of a model collagen peptide possessing azobenzene-derived clamps integrated in all three strands as side-chain-to-side-chain crosslinks is analyzed by IR spectroscopy in comparative thermal excursion experiments with the triple helix of a typical reference collagen peptide consisting of only glycine-proline-hydroxyproline repeats. By exploiting the known stabilizing effects of aqueous alcoholic solvents on the unique collagen fold, deuterated ethylene glycol/water (1:1) is used as a solvent to investigate the effect of the light-switchable trans/cis-azobenzene clamp on the stability of the triple helix in terms of H/D exchange rates and thermal unfolding. Results of this comparative analysis clearly reveal only a minor destabilization of the triple helix by the hydrophobic azobenzene moieties compared to the reference collagen peptide as reflected by a lower midpoint of the thermal unfolding and higher rates of H/D exchange. However, it also reveals that the driving force exerted by the trans-to-cis photoisomerization of the azobenzene moieties is insufficient for unfolding of the compact triple-helical collagen fold. Only temperature-dependent untightening of this fold with heating results in a reversible photomodulated unfolding and refolding of the azo-collagen peptide into the original triple helix. PMID:26918674

  8. Synthesis of poly glycidylmethacrylate grafted azobenzene copolymer: Photosensitivity and nonlinear optical properties

    Science.gov (United States)

    Sousani, Abbas; Moghadam, Peyman Najafi; Hasanzadeh, Reza; Motiei, Hamideh; Bagheri, Massoumeh

    2016-01-01

    In this work poly glycidylmethacrylate grafted 4-hydroxy-4‧-methoxy-azobenzene (Azo-PGMA) was synthesized. For this propose firstly 4-hydroxy-4‧-methoxy-azobenzene (AZO) was prepared, then poly glycidylmethacrylate was prepared by free radical polymerization of glycidylmethacrylate in the presence of benzoyl peroxide as initiator under inert atmosphere in dry THF. Finally the homopolymer was functionalized by AZO moieties. The characterization of the synthesized copolymer was carried out by 1H NMR, FT-IR, thermal gravimetric analyze (TGA), differential scanning calorimetry (DSC) and optical polarizing microscope (POM) analysis. The UV-vis studies were carried out on Azo-PGMA copolymer and the results showed that the synthesized Azo-PGMA copolymer has ultra-fast response to UV light and has slow relaxation time. Also the third-order nonlinear optical properties of the Azo-PGMA copolymer and AZO were studied by using Z-scan technique. Nonlinear refraction and absorption coefficients of the above mentioned materials were measured by the closed and open aperture Z-scan method using a continuous wave Nd-YAG laser at 532 nm. The positive nonlinear absorption in Azo-PGMA and AZO was investigated at the wavelength of λ = 532 nm, respectively and the measured values of nonlinear refraction in both of the samples were from the order of 10-8 cm2/W.

  9. Photomodulation of fluoride ion binding through anion-π interactions using a photoswitchable azobenzene system

    Science.gov (United States)

    Rananaware, Anushri; Samanta, Mousumi; Bhosale, Rajesh S.; Kobaisi, Mohammad Al; Roy, Biswajit; Bheemireddy, Varun; Bhosale, Sidhanath V.; Bandyopadhyay, Subhajit; Bhosale, Sheshanath V.

    2016-03-01

    The discovery of photoswitchable azobenzene-systems that undergo trans-to-cis photoisomerisation was a milestone in supramolecular chemistry. Such photoswitches have possible applications in data storage, stimuli responsive delivery systems, and molecular machines due to fast and selective switching. However, the light induced cis isomer of azobenzene is rather unstable and reverts thermally and photochemically to the thermodynamically stable trans configuration. We report, for the first time, controlled photoswitching of an azo-naphthalenediimide (azo-NDI) which can be achieved upon binding of fluoride ions through anion-π interaction. This NDI-F–NDI “sandwich” stabilises the cis configuration through the generation of an NDI•‑ radical anion, and a dianionic, NDI2‑ species that becomes unusually stable in the cis form. The sandwiched cis form reverts to the trans form only upon decomplexation of F‑. A model pollutant was successfully degraded using the photogenerated NDI-F–NDI sandwich. This opens a wide range of applications in molecular and supramolecular nanotechnology.

  10. Nonadiabatic hybrid quantum and molecular mechanic simulations of azobenzene photoswitching in bulk liquid environment.

    Science.gov (United States)

    Böckmann, Marcus; Doltsinis, Nikos L; Marx, Dominik

    2010-01-21

    A nonadiabatic hybrid quantum and molecular mechanical (na-QM/MM) molecular dynamics scheme has been implemented recently combining the nonadiabatic Car-Parrinello molecular dynamics method by Doltsinis and Marx [Phys. Rev. Lett. 2002, 88, 166402] with the QM/MM coupling approach by Laio et al. [J. Chem. Phys. 2002, 116, 6941]. Here an extensive validation of the underlying, density functional theory based, electronic structure methods by comparison to CASPT2 ab initio data is presented for the case of azobenzene. The "on the fly" na-QM/MM method is then applied to study Z-->E and E-->Z photoisomerization of azobenzene in a bulk liquid environment. The isomerization mechanism is found to be a pedal motion of the central CN horizontal lineNC group in both cases. While the Z-->E reaction is barely affected by the environment, E-->Z photoisomerization is slowed down considerably in the liquid compared to the gas phase. This effect is due to the fact that reorientation of the phenyl rings is significantly hindered in the liquid by steric nearest neighbor interactions. Nonradiative decay is found to be substantially faster for Z-AB (subpicosecond regime) than for E-AB (picosecond regime). The main molecular motions responsible for nonadiabatic coupling have been identified as the oscillations in the NN and CN bond lengths, the CNN bond angles, and the CNNC dihedral angle. PMID:19928885

  11. Synthesis of Poly(methacrylic acid)-functionalized SBA-15 and its Adsorption of Phenol in Aqueous Media

    International Nuclear Information System (INIS)

    Poly(methacrylic acid)-functionalized SBA-15 silicas (denoted as P-x-PMA/SBA-15 where x is molar ratio of TSPM/(TEOS+TSPM) in percentage in the initial mixture) were synthesized by co-condensation of tetraethoxysilane and varying contents of 3-(trimethoxysilyl)propyl methacrylate in acidic medium with the block copolymer Pluronic 123 as a structure directing agent and then polymerization by methacrylic acid in the presence of ammonium persulfate as an initiator. The functionalized materials were characterized by PXRD, TEM, SEM, IR, and N2 adsorption-desorption at 77 K. The investigation of phenol adsorption in aqueous solution on the materials showed that the poly(methacrylic acid)-functionalized mesoporous silicas possess strong adsorption ability for phenol with interaction of various kinds of hydrogen bonds. The adsorption data were fitted to Langmuir isotherms and the maximum adsorption capacity of the three functionalized materials P-5-PMA/SBA-15, P-10-PMA/SBA-15, and P-15-PMA/SBA-15 to be 129.37 mg/g, 187.97 mg/g, and 78.43 mg/g, respectively, were obtained. The effect of the pH on phenol adsorption was studied

  12. Methacrylic Zwitterionic, Thermoresponsive, and Hydrophilic (Co)Polymers via Cu(0)-Polymerization: The Importance of Halide Salt Additives.

    Science.gov (United States)

    Simula, Alexandre; Anastasaki, Athina; Haddleton, David M

    2016-02-01

    The synthesis of hydrophilic, thermoresponsive, and zwitterionic polymethacrylates is reported by Cu(0)-mediated reversible deactivation radical polymerization in water and/or water/alcohol mixtures. The predisproportionation of [Cu(I) (PMDETA)Cl] in water prior to initiator and monomer addition is exploited to yield well-defined polymethacrylates with full monomer conversions in 30 min. The addition of supplementary halide salts (NaCl) enables the synthesis of various molecular weight poly[poly(ethylene glycol) methyl ether methacrylate] (PEGMA475 ) (DPn = 10-80, Mn ≈ 10 000-40 000 g mol(-1) ) with full monomer conversion and narrow molecular weight distributions attained in all cases (Đ ≈ 1.20-1.30). A bifunctional PEG initiator (average Mn ≈ 1000 g mol(-1) ) is utilized for the polymerization of a wide range of methacrylates including 2-dimethylaminoethyl methacrylate, 2-morpholinoethyl methacrylate, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, and 2-methacryloyloxyethyl phosphorylcholine. Despite the high water content, high end group fidelity is demonstrated by in situ chain extensions and block copolymerizations with PEGMA475 yielding well-defined functional telechelic pentablock copolymers within 2.5 h. PMID:26691684

  13. Synthesis of Poly(methacrylic acid)-functionalized SBA-15 and its Adsorption of Phenol in Aqueous Media

    Energy Technology Data Exchange (ETDEWEB)

    Vo, Vien; Kim, Heejun; Kim, Hayeong; Kim, Youngmee; Kim, Sung Jin [Ewha Womans Univ., Seoul (Korea, Republic of)

    2013-12-15

    Poly(methacrylic acid)-functionalized SBA-15 silicas (denoted as P-x-PMA/SBA-15 where x is molar ratio of TSPM/(TEOS+TSPM) in percentage in the initial mixture) were synthesized by co-condensation of tetraethoxysilane and varying contents of 3-(trimethoxysilyl)propyl methacrylate in acidic medium with the block copolymer Pluronic 123 as a structure directing agent and then polymerization by methacrylic acid in the presence of ammonium persulfate as an initiator. The functionalized materials were characterized by PXRD, TEM, SEM, IR, and N{sub 2} adsorption-desorption at 77 K. The investigation of phenol adsorption in aqueous solution on the materials showed that the poly(methacrylic acid)-functionalized mesoporous silicas possess strong adsorption ability for phenol with interaction of various kinds of hydrogen bonds. The adsorption data were fitted to Langmuir isotherms and the maximum adsorption capacity of the three functionalized materials P-5-PMA/SBA-15, P-10-PMA/SBA-15, and P-15-PMA/SBA-15 to be 129.37 mg/g, 187.97 mg/g, and 78.43 mg/g, respectively, were obtained. The effect of the pH on phenol adsorption was studied.

  14. Study of the molecular mobility of methyl-methacrylate and methacrylic acid copolymers by solid state NMR

    International Nuclear Information System (INIS)

    Several methyl-methacrylate/methacrylic acid copolymers were prepared in the presence of concentrated nitric acid. The obtained copolymers were characterized by molecular weigh determination and hydrolization degree. The molecular mobility of these copolymers was studied by solid state nuclear magnetic resonance. Results are presented

  15. Predicting the chromatographic retention of polymers: poly(methyl methacrylate)s and polyacryate blends.

    Science.gov (United States)

    Bashir, Mubasher A; Radke, Wolfgang

    2007-09-01

    The suitability of a retention model especially designed for polymers is investigated to describe and predict the chromatographic retention behavior of poly(methyl methacrylate)s as a function of mobile phase composition and gradient steepness. It is found that three simple yet rationally chosen chromatographic experiments suffice to extract the analyte specific model parameters necessary to calculate the retention volumes. This allows predicting accurate retention volumes based on a minimum number of initial experiments. Therefore, methods for polymer separations can be developed in relatively short time. The suitability of the virtual chromatography approach to predict the separation of polymer blend is demonstrated for the first time using a blend of different polyacrylates. PMID:17586517

  16. Preparation of ultrafine poly(methyl methacrylate-co-methacrylic acid) biodegradable nanoparticles loaded with ibuprofen.

    Science.gov (United States)

    Saade, Hened; Diaz de León-Gómez, Ramón; Enríquez-Medrano, Francisco Javier; López, Raúl Guillermo

    2016-08-01

    Ibuprofen-loaded polymeric particles with around 9.2 nm in mean diameter, as determined by electron microscopy, dispersed in an aqueous media containing up to 12.8% solids were prepared by semicontinuous heterophase polymerization. The polymeric material is a (2/1 mol/mol) methyl methacrylate-co-methacrylic acid copolymer similar to Eudragit S100, deemed safe for human consumption and used in the manufacturing of drug-loaded pills as well as micro- and nanoparticles. The loading efficiency was 100%, attaining around 10-12% in drug content. Release studies showed that the drug is released from the nanoparticles at a slower rate than that in the case of free IB. Given their size as well as the pH values required for their dissolution, it is believed that this type of particles could be used as a basis for preparing nanosystems loaded with a variety of drugs. PMID:27126476

  17. RAFT Copolymerization of Glycidyl Methacrylate and N,N-Dimethylaminoethyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    曹俊; 张丽芬; 潘向强; 程振平; 朱秀林

    2012-01-01

    In this work, copolymerization of two functional monomers, glycidyl methacrylate (GMA) and N,N-dimethylaminoethyl methacrylate (DMAEMA), was firstly carried out via reversible addition-fragmentation chain transfer (RAFT) polymerization successfully. The copolymerization kinetics was investigated under the molar ratio of n[GMA+DMAEMA]o/n[AIBN]o/n[CPDN]o=300/1/3 at 60℃. The copolymerization showed typical "living" features such as first-order polymerization kinetics, linear increase of molecular weight with monomer conversion and narrow molecular weight distribution. The reactivity ratios of GMA and DMAEMA were calculated by the extended Kelen-Tudos linearization methods. The epoxy group of the copolymer PGMA-co-PDMAEMA remained intact under the conditions of RAFT copolymerization and could easily be post-modified by ethylenedia- mine. Moreover, the modified copolymer could be used as a gene carrier.

  18. Electron degradation of poly(methyl methacrylate)

    International Nuclear Information System (INIS)

    Poly(methyl methacrylate) sheet exposed to electron radiation at a very high dose rate (109 rad/sec) under atmospheric pressure using a 300 KV electron accelerator resulted in main chain scission, side chain cleavage, reduction in material strength, yellow color formation, micro fracturing, production of white bubbles upon heating, and increased solubility in special solvent developers. In general the decrease in number average and weight average molecular weight of PMMA is linear with the logarithm of electron radiation dose. A significant increase in heterogeneity and a bimodal distribution of molecular weight where detected when PMMA was electron irradiated above 40 Mrads. The chain scission efficiency (G-value) of PMMA was determined to be 0.46 breaks/100 eV

  19. Azo···phenyl stacking: a persistent self-assembly motif guides the assembly of fluorinated cis-azobenzenes into photo-mechanical needle crystals.

    Science.gov (United States)

    Bushuyev, Oleksandr S; Tomberg, Anna; Vinden, Joanna R; Moitessier, Nicolas; Barrett, Christopher J; Friščić, Tomislav

    2016-02-01

    We describe a novel, persistent motif of molecular assembly in photo-mechanical crystals and cocrystals of fluorinated cis-azobenzenes. The azo···phenyl stacking, preserved upon either chemical substitution or halogen-bonded cocrystallization, guides the assembly of fluorinated cis-azobenzenes into columnar stacks and drives the formation of crystals with needle-like morphologies optimal for photo-mechanical motion. PMID:26691226

  20. Star-shaped poly(L-lactide)-b-poly(lactobionamidoethyl methacrylate) with porphyrin core: synthesis, self-assembly, singlet oxygen research and recognition properties.

    Science.gov (United States)

    Dai, Xiao-Hui; Wang, Zhi-Ming; Pan, Jian-Ming; Yuan, Si-Song; Yan, Yong-sheng; Liu, Dong-Ming; Sun, Lin

    2014-01-01

    Star-shaped porphyrin-cored poly(L-lactide)-b-poly(lactobionamidoethyl methacrylate) block copolymers (SPPLA-b-PLAMA) were synthesized via RAFT of unprotected Lactobionamidoethyl methacrylate (LAMA) in 1-methyl-2-pyrrolidinone (NMP) solution at 70 °C. The structure of this as-synthesized SPPLA-b-PLAMA block copolymer was thoroughly studied by nuclear magnetic resonance spectroscopy, gel permeation chromatography (GPC), and Fourier transforms infrared. Moreover, under the irradiation, such SPPLA-b-PGAMA copolymer exhibits efficient singlet oxygen generation (0.17) and indicates high fluorescence quantum yields (0.20). Notably, with UV-vis investigation, SPPLA-b-PLAMA showed a very specific recognition with RCA120 lectin. This will not only provide potentially prophyrin-cored star-shaped SPPLA-b-PLAMA block copolymers for targeted photodynamic therapy, but also improve the physical, biodegradation, biocompatibility properties of PLA-based biomaterials. PMID:25138060

  1. Synthesis of densely grafted copolymers with tert-butyl methacrylate/2-(dimethylamino ethyl) methacrylate side chains as precursors for brush polyelectrolytes and polyampholytes

    Energy Technology Data Exchange (ETDEWEB)

    Gromadzki, Daniel, E-mail: d_grom@interia.pl [Department of Polymer Chemistry, Vilnius University, Naugarduko 24, LT-03225 Vilnius (Lithuania); Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovsky Sq. 2, 162 06 Prague (Czech Republic); Stepanek, Petr [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovsky Sq. 2, 162 06 Prague (Czech Republic); Makuska, Ricardas [Department of Polymer Chemistry, Vilnius University, Naugarduko 24, LT-03225 Vilnius (Lithuania)

    2013-01-15

    Methacrylate-based densely grafted copolymers were synthesized by atom transfer radical polymerization (ATRP) and activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP) techniques. The linear poly(2-(2-bromoisobutyryloxy)ethyl methacrylate) PBIEM prepared by ATRP served as a macroinitiator backbone. The 'grafting from' strategy was used to initiate polymerization of tert-butyl methacrylate (tBuMA) from PBIEM under ATRP and/or AGET ATRP conditions yielding densely grafted copolymers PBIEM-graft-P(tBuMA). The low polydispersity indices (PDI) of the synthesized brushes evidenced by SEC analysis were consistent with a controlled/living radical polymerization (CLRP) mechanism. The chlorine-terminated PBIEM-graft-P(tBuMA)-Cl macroinitiators were subsequently employed for chain extension with 2-(dimethylamino ethyl) methacrylate (DMAEMA) yielding densely grafted copolymers with diblock copolymer side chains PBIEM-graft-P(tBuMA)-block-PDMAEMA. Further, PBIEM macroinitiator was used to initiate the copolymerization of a binary mixture of tBuMA and DMAEMA through both ATRP and AGET ATRP initiating systems, yielding densely grafted copolymers with statistical distribution of the side chains. The reactivity ratios for random graft copolymerization of tBuMA and DMAEMA from PBIEM backbone established by three different methods (Finemann-Ross, Kelen-Tuedoes and Error-in-Variable) did not substantially differ from literature values for conventional free-radical copolymerization of the same monomers. Polyampholyte brushes with PMAA-stat-PDMAEMA side chains were eventually synthesized by hydrolysis of the shielding tert-butyl groups. -- Graphical abstract: Synthesis of dense polyampholyte brushes by ATRP. A: synthesis of macroinitiator PBIEM; B: graft copolymerization of tBuMA and DMAEMA from PBIEM and hydrolysis of tBuMA units. Highlights: Black-Right-Pointing-Pointer tBuMA/DMAEMA based densely grafted brushes were prepared by ATRP

  2. Poly(esterimide) bearing azobenzene units as photoaligning layer for liquid crystals

    Science.gov (United States)

    Węgłowski, Rafał; Piecek, Wiktor; Kozanecka-Szmigiel, Anna; Konieczkowska, Jolanta; Schab-Balcerzak, Ewa

    2015-11-01

    The custom synthesized azobenzene side-chain poly(esterimide) was used as an aligning material for nematic liquid crystal molecules. The anisotropy of the poly(esterimide) layer was generated by a linearly polarized UV light, as a consequence of multiple trans-cis-trans isomerization cycles. The photoalignment effect was studied by assembling a twisted nematic cell with a proper liquid crystal mixture and geometry to fulfill Mauguin's limit. The polarizing microscope pictures of the fabricated cells confirmed the twisted arrangement of liquid crystal molecules. The results of electro-optic measurements indicated a stronger anchoring of the liquid crystal molecules by photoaligned poly(esterimide) than that obtained in the case of a rubbed polyimide.

  3. Near-field lithography on the azobenzene polymer liquid crystal films

    Institute of Scientific and Technical Information of China (English)

    Douguo Zhang; Jian Liu; Zebo Zhang; Li Cao; Anlian Pan; Pei Wang; Yonghua Lu; Ming Bai; Jun Yang; Lin Tang; Jiangying Zhang; Hai Ming; Qijin Zhang

    2005-01-01

    @@ In this article, we reported near-field research on azobenzene polymer liquid crystal films using scanning near-field optical microscopy (SNOM). Optical writing and subsequently topographic reading of the patterns with subwavelength resolution were carried out in our experiments. Nanometer scale dots and lines were successfully fabricated on the films and the smallest dot diameter is about 120 nm. The width of the line fabricated is about 250 nm. This method is also a choice for nanolithography. The mechanism of the surface deformation on the polymer films was briefly analyzed from the viewpoint of gradient force in the optical near field. The intensity distribution of the electric field near the tip aperture was numerically simulated using finite-difference time-domain (FDTD) method and the numerical simulation results were consistent with the experimental results.

  4. Synthesis of photoresponsive cholesterol-based azobenzene organogels: dependence on different spacer lengths.

    Science.gov (United States)

    Ren, Yuchun; Wang, Bin; Zhang, Xiuqing

    2015-01-01

    A series of azobenzene-cholesterol organogel compounds (M 0 -M 12 ) with different spacers were designed and synthesized. The molecular structures were confirmed by (1)H NMR and (13)C NMR spectroscopy. The rapid and reversible photoresponsive properties of the compounds were investigated by UV-vis spectroscopy. Their thermal phase behaviors were studied by DSC. The length of the spacer plays a crucial role in the gelation. Compound M 6 is the only one that can gelate in ethanol, isopropanol and 1-butanol and the reversible gel-sol transitions are also investigated. To obtain visual insight into the microstructure of the gels, the typical structures of the xerogels were studied by SEM. Morphologies of the aggregates change from flower-like, network and rod with different sizes. By using IR and XRD characterization, it is found that intermolecular H-bonding, the solvents and van der Waals interaction are the main contributions to the specific superstructure. PMID:26199664

  5. High diffraction efficiency polarization gratings recorded by biphotonic holography in an azobenzene liquid crystalline polyester

    International Nuclear Information System (INIS)

    High diffraction efficiencies have been achieved with polarization gratings recorded in thin films of an azobenzene side-chain liquid crystalline polyester by means of biphotonic processes. Efficiency values up to 30% have been reached after an induction period of 300 s and subsequent evolution with the sample in darkness. These values are at least two orders of magnitude higher than those previously reported for biphotonic recording. The gratings can be erased with unpolarized blue light and partial recovery of the diffraction efficiency has been observed after the erasure process when the sample is kept in darkness. Red light illumination of the erased film increases the recovered efficiency value and the recovery rate. [copyright] 2001 American Institute of Physics

  6. Synthesis of Carboxylic Block Copolymers via Reversible Addition Fragmentation Transfer Polymerization for Tooth Erosion Prevention

    OpenAIRE

    Lei, Y.; Wang, T.; Mitchell, J. W.; Qiu, J.; Kilpatrick-Liverman, L.

    2014-01-01

    Dental professionals are seeing a growing population of patients with visible signs of dental erosion. The approach currently being used to address the problem typically leverages the enamel protection benefits of fluoride. In this report, an alternative new block copolymer with a hydrophilic polyacrylic acid (PAA) block and a hydrophobic poly(methyl methacrylate) (PMMA) block was developed to similarly reduce the mineral loss from enamel under acidic conditions. This series of PMMA-b-PAA blo...

  7. Anionic polymerisation of methyl methacrylate with complex initiator system

    OpenAIRE

    Nugay, Turgut; Nugay, Nihan; Jérôme, Robert

    2002-01-01

    Polymerisation of methyl methacrylate was conducted by using alkyl lithium/dimethylsulfoxide (DMSO) system as initiator in toluene. A special attention was focused on using some lithium polyetheralkoxides as polymerisation promoters at ambient temperatures. Poly(methyl methacrylate) samples were characterized with Gel Permeation Chromatography (GPC), Nuclear Magnetic Resonance Spectroscopy (H-1 NMR) and Differential Scanning Calorimetry (DSC). The positive effect of the mu/sigma type ligands ...

  8. Biocompatible Bacterial Cellulose-Poly(2-hydroxyethyl methacrylate) Nanocomposite Films

    OpenAIRE

    Figueiredo, Andrea G. P. R.; Ana R. P. Figueiredo; Ana Alonso-Varona; Fernandes, Susana C. M.; Teodoro Palomares; Eva Rubio-Azpeitia; Ana Barros-Timmons; Silvestre, Armando J. D.; Carlos Pascoal Neto,; Freire, Carmen S. R.

    2013-01-01

    A series of bacterial cellulose-poly(2-hydroxyethyl methacrylate) nanocomposite films was prepared by in situ radical polymerization of 2-hydroxyethyl methacrylate (HEMA), using variable amounts of poly(ethylene glycol) diacrylate (PEGDA) as cross-linker. Thin films were obtained, and their physical, chemical, thermal, and mechanical properties were evaluated. The films showed improved translucency compared to BC and enhanced thermal stability and mechanical performance when compared to poly(...

  9. Synthetic gene involving azobenzene-tethered T7 promoter for the photocontrol of gene expression by visible light.

    Science.gov (United States)

    Kamiya, Yukiko; Takagi, Toshiki; Ooi, Hideaki; Ito, Hiroshi; Liang, Xingguo; Asanuma, Hiroyuki

    2015-04-17

    In the present study, we demonstrate photoregulation of gene expression in a cell-free translation system from a T7 promoter containing two azobenzene derivatives at specific positions. As photoswitches, we prepared azobenzene-4'-carboxlyic acid (Azo) and 2,6-dimethylazobenzene-4'-carboxylic acid (DM-Azo), which were isomerized from trans to cis upon irradiation with UV light (λ protein from a promoter modified with S-Azo or S-DM-Azo could be induced by harmless visible light whereas that from a promoter modified with Azo or DM-Azo was induced only by UV light (340-360 nm). Thus, efficient photoregulation of green fluorescent protein production was achieved in a cell-free translation system with visible light without photodamage. PMID:25144622

  10. Ghost Block

    OpenAIRE

    Webb, Neil

    2011-01-01

    Filmed on the English south coast 'Ghost Block' depicts the uncanny and eerie atmosphere at the site of a WW2 coastal defence line. The concrete cubes were used as an anti-invasion blockade against potential landing forces. This protection line now slowly decaying and becoming enmeshed into the environment still acts as a defence to repel unwanted visitors. The area is a natural reserve to nesting birds that often lay eggs directly onto the beach surface. The blocks act as a final barrier ...

  11. The effect of photoisomerization on the enzymatic hydrolysis of polymeric micelles bearing photo-responsive azobenzene groups at their cores.

    Science.gov (United States)

    Harnoy, Assaf J; Slor, Gadi; Tirosh, Einat; Amir, Roey J

    2016-06-28

    The design of stable polymeric micelles that can respond to specific stimuli is crucial for the development of smart micellar nanocarriers that can release their active cargo selectively at the target site, thus diminishing the therapeutic limitations due to non-selective damage to healthy tissues. Here we report the design and synthesis of photo- and enzyme-responsive amphiphilic PEG-dendron hybrids bearing one, two or four enzymatically cleavable azobenzene end-groups. These dual-responsive hybrids can respond to light through the reversible isomerization of the azobenzene end-groups from the non-polar trans isomer to the highly polar cis isomer and vice versa, upon UV and visible irradiation, respectively. The high structural precision of these hybrids, which emerges from the dendritic architecture, enabled a detailed study of the photoisomerization of the azobenzene end-groups with high molecular resolution. Remarkably, although the transition from trans-to-cis led to a significant increase in the polarity of the micellar cores, the micelles remained stable. Our kinetic studies show that although the trans isomer is a better substrate for the activating enzyme, the UV induced formation of the cis azobenzene end-groups led to significant acceleration of the enzymatic hydrolysis of the end-groups. These results provide strong indication that the enzyme cannot reach the core of the micelles and instead the end-groups have to leave the hydrophobic core in order to be exposed on the micelle's surface or even leave the micelle in order to allow their cleavage by the activating enzymes. PMID:27093537

  12. Luminescence and Magnetic Properties of Two Three -Dimensional Terbium and Dysprosium MOFs Based on Azobenzene-4,4 '-Dicarboxylic Linker

    OpenAIRE

    Fernández, Belén; Oyarzabal Epelde, Itziar; Seco Botana, José Manuel; San Sebastián Larzabal, Eider; Fairen-Jiménez, David; Gómez-Ruiz, Santiago; Salinas-Castillo, Alfonso; Calahorro, Antonio J.; Rodríguez-Diéguez, Antonio

    2016-01-01

    We report the in situ formation of two novel metal-organic frameworks based on terbium and dysprosium ions using azobenzene-4,4-dicarboxylic acid (H(2)abd) as ligand, synthesized by soft hydrothermal routes. Both materials show isostructural three-dimensional networks with channels along a axis and display intense photoluminescence properties in the solid state at room temperature. Textural properties of the metal-organic frameworks (MOFs) have been fully characterized although no appreciable...

  13. Luminescent polymethyl methacrylate modified by gamma radiation

    Energy Technology Data Exchange (ETDEWEB)

    Morais, Guilherme F. [Faculdade de Tecnologia de Sao Paulo (FATEC-ZL), Sao Paulo, SP (Brazil); Forster, Pedro L.; Marchini, Leonardo G.; Lugao, Ademar B.; Parra, Duclerc F., E-mail: dfparra@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2011-07-01

    Thin films of PMMA (polymethyl methacrylate) doped with luminescent complexes have been studied and developed for applications in advanced technologies. The problem of stability of these films is focused in this study. Films stabilization by reaction with fluorinated monomers is a recent study that aims to increase its luminescence properties for long time. The films were prepared by dilution of PMMA in chloroform with addition of europium complex, at proportion of 5% by weight of polymer. The luminescent polymer films were obtained by casting. Thin layer slides of the film were separated in three parts. One was reacted with fluorinated monomers (C{sub 2}F{sub 4}) in closed reactor for 48 hours. A second part was reacted with C{sub 2}F{sub 4} after irradiation in gamma source at 5 kGy in simultaneous process. The last part was used as obtained. The luminescent polymer matrices were characterized using the techniques of infrared (FTIR) and thermogravimetry (TGA/DTG). Samples of the films were, in presence of fluorine monomers, exposed to ionizing radiation in dose of 5 kGy, for react with monomers in the doped polymer surface. In this case the effects of radiation were evaluated on the luminescent films. (author)

  14. MOLECULAR MUTAGENESIS INDUCED BY GLYCIDYL METHACRYLATE

    Institute of Scientific and Technical Information of China (English)

    高惠兰; 左谨; 谢大英; 方福德

    1994-01-01

    Glycidyl methacrylate(GMA)is a recently recognized mutagen.In order to explore the mutagenicity and mechanism of GMA,plasmid pBR322 was used for in vitro binding,mutant screening,restriction enzyme map-ping,and DNA sequencing.To explore the mechanism by which an initial premutational event is converted into a stable heritable mutation,pBR322 and GMA-bound pBR322 were transformed into E.coli HB101,and the follow-ing results were obtainge:1)GMA-bound pBR322 induced phenotype changes in competent cells.Two stable and heritable mutants were isolated (ApRTcS and ApSTcR).2)When restriction enzyme mapping was used to analyze the mutant ApRTcS,four of seven maps showed changes,but no large DNA insertion or deletion were observed.3)The frequency of deletion and insertion forms counted about 10%.Sequence specificity and hot spot regions were evident in the sequence analysis of mutated plasmid.The above results indicate that the premutagenic lesions of plasmid induced by GMA can be converted into point mutatons in vivo.

  15. Luminescent polymethyl methacrylate modified by gamma radiation

    International Nuclear Information System (INIS)

    Thin films of PMMA (polymethyl methacrylate) doped with luminescent complexes have been studied and developed for applications in advanced technologies. The problem of stability of these films is focused in this study. Films stabilization by reaction with fluorinated monomers is a recent study that aims to increase its luminescence properties for long time. The films were prepared by dilution of PMMA in chloroform with addition of europium complex, at proportion of 5% by weight of polymer. The luminescent polymer films were obtained by casting. Thin layer slides of the film were separated in three parts. One was reacted with fluorinated monomers (C2F4) in closed reactor for 48 hours. A second part was reacted with C2F4 after irradiation in gamma source at 5 kGy in simultaneous process. The last part was used as obtained. The luminescent polymer matrices were characterized using the techniques of infrared (FTIR) and thermogravimetry (TGA/DTG). Samples of the films were, in presence of fluorine monomers, exposed to ionizing radiation in dose of 5 kGy, for react with monomers in the doped polymer surface. In this case the effects of radiation were evaluated on the luminescent films. (author)

  16. Furfuryl methacrylate plasma polymers for biomedical applications.

    Science.gov (United States)

    Shirazi, Hanieh Safizadeh; Rogers, Nicholas; Michelmore, Andrew; Whittle, Jason D

    2016-01-01

    Furfuryl methacrylate (FMA) is a promising precursor for producing polymers for biomedical and cell therapy applications. Herein, FMA plasma polymer coatings were prepared with different powers, deposition times, and flow rates. The plasma polymer coatings were characterized using atomic force microscopy (AFM), scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The results from AFM and SEM show the early growth of the coatings and the existence of particle aggregates on the surfaces. XPS results indicated no measureable chemical differences between the deposited films produced under different power and flow rate conditions. ToF-SIMS analysis demonstrated differing amounts of C5H5O (81 m/z) and C10H9O2 (161 m/z) species in the coatings which are related to the furan ring structure. Through judicious choice of plasma polymerization parameters, the quantity of the particle aggregates was reduced, and the fabricated plasma polymer coatings were chemically uniform and smooth. Primary human fibroblasts were cultured on FMA plasma polymer surfaces to determine the effect of surface chemical composition and the presence of particle aggregates on cell culture. Particle aggregates were shown to inhibit fibroblast attachment and proliferation. PMID:27609095

  17. Asymmetric Dimers of Chiral Azobenzene Dopants Exhibiting Unusual Helical Twisting Power upon Photoswitching in Cholesteric Liquid Crystals.

    Science.gov (United States)

    Kim, Yuna; Tamaoki, Nobuyuki

    2016-02-01

    In this study, we synthesized asymmetric dimeric chiral molecules as photon-mode chiral switches for reversible tuning of self-assembled helical superstructures. The chiral switches bearing two mesogen units-cholesterol and azobenzene moieties connected through flexible alkylenedioxy bridges-were doped into nematic liquid crystals, resulting in a chiral nematic (cholesteric) phase. Under irradiation with UV light, photoisomerization of the azobenzene units led to unprecedented switching of the cholesteric pitch and helical twisting power (HTP, β), with a higher HTP found in the cis-rich state (bent-form) than in the trans-state (rod-form). We attribute this behavior to the elongated cybotactic smectic clusters disrupting the helical orientation of the molecules in the cholesteric liquid crystals; their reversible decay and reassembly was evidenced upon sequential irradiation with UV and visible light, respectively. In addition to the photoisomerization of the azobenzene units, the odd/even parity of the alkylenedioxy linkers of the dimeric dopants also had a dramatic effect on the transitions of the cybotactic smectic domains. On the basis of the large rotational reorganization of the cholesteric helix and HTP switching (Δβ/βini of up to 50%), we could control the macroscopic rotational motion of microsized glass rods upon irradiating the surface of a cholesteric liquid crystal film featuring a polygonal fingerprint texture using UV and visible light. PMID:26815738

  18. Surface hopping dynamics of direct trans → cis photoswitching of an azobenzene derivative in constrained adsorbate geometries.

    Science.gov (United States)

    Floß, Gereon; Granucci, Giovanni; Saalfrank, Peter

    2012-12-21

    With ongoing miniaturization of electronic devices, the need for individually addressable, switchable molecules arises. An example are azobenzenes on surfaces which have been shown to be switchable between trans and cis forms. Here, we examine the "direct" (rather than substrate-mediated) channel of the trans → cis photoisomerization after ππ∗ excitation of tetra-tert-butyl-azobenzene physisorbed on surfaces mimicking Au(111) and Bi(111), respectively. In spirit of the direct channel, the electronic structure of the surface is neglected, the latter merely acting as a rigid platform which weakly interacts with the molecule via Van-der-Waals forces. Starting from thermal ensembles which represent the trans-form, sudden excitations promote the molecules to ππ∗-excited states which are non-adiabatically coupled among themselves and to a nπ∗-excited and the ground state, respectively. After excitation, relaxation to the ground state by internal conversion takes place, possibly accompanied by isomerization. The process is described here by "on the fly" semiclassical surface hopping dynamics in conjunction with a semiempirical Hamiltonian (AM1) and configuration-interaction type methods. It is found that steric constraints imposed by the substrate lead to reduced but non-vanishing, trans → cis reaction yields and longer internal conversion times than for the isolated molecule. Implications for recent experiments for azobenzenes on surfaces are discussed. PMID:23267492

  19. Epidural block

    Science.gov (United States)

    ... Drugs & Supplements Videos & Tools Español You Are Here: Home ... It numbs or causes a loss of feeling in the lower half your body. This lessens the pain of contractions during childbirth. An epidural block may also be used to ...

  20. Novel Polymer Architectures for Optical Storage

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Forcén, Patrica; Oriol, Luis; Sánchez, Carlos; Alcalá, Rafael; Ramanujam, P.S.

    Azobenzene containing polymers have been shown to have a large potential for high capacity olographic information storage. However, it has been difficult to fabricate thick films of the polymers with good op~ical quality so far. Liquid crystalline block copolymers prepared by Atom Transfer Radical...... Polymerization and based on azobenzene methacrylate and methyl methacrylate show some promise due to the observed block segregation. Thus, lamellar nanostructure was observed'when the azobenzene content was > 20% by weight, and both birefringence and dichroism can be induced by linearly polarized 488 nm light....... The formation of azo-aggregation inside the azo blocks is strongly,reduced when going from the homopolymer to the copolymers....

  1. Block and Graft Copolymers Containing Carboxylate or Phosphonate Anions

    OpenAIRE

    Hu, Nan

    2014-01-01

    This dissertation focuses on synthesis and characterization of graft and block copolymers containing carboxylate or phosphonate anions that are potential candidates for biomedical applications such as drug delivery and dental adhesives. Ammonium bisdiethylphosphonate (meth)acrylate and acrylamide phosphonate monomers were synthesized based on aza-Michael addition reactions. Free radical copolymerizations of these monomers with an acrylate-functional poly(ethylene oxide) (PEO) macromonomer...

  2. Study of copolymers of methyl methacrylate, divinylbenzene and a nonionic surfactant by solid state nuclear magnetic resonance

    International Nuclear Information System (INIS)

    In our research, we have studied the synthesis of compounds containing a nonionic surfactant composed by block copolymers of poly(propylene oxide-ethylene oxide) (Ppo-Peo) chemically attached on copolymers of methyl methacrylate (MMA) and divinylbenzene (DVB), in order to obtain the surfactant in the solid state. Since these copolymers are used in the spherical form, we have chosen polymerization in suspension as the synthetic route to obtain the samples. This work presents the NMR experiments used to characterize the MMA-DVB and MMA-DVB-PPO-PEO copolymers

  3. Poly(methacrylic acid)-mediated morphosynthesis of PbWO4 micro-crystals

    International Nuclear Information System (INIS)

    PbWO4 crystals with various morphologies were fabricated via a facile poly(methacrylic acid)-mediated hydrothermal route. Novel microsized PbWO4 single crystals with a needle-like shape as well as other morphologies, such as a fishbone, dendrite, sphere, spindle, ellipsoid, rod, and dumbbell with two dandelion-like heads, could be produced. The presence of PMAA, [Pb2+]/[WO42-] molar ratio (R), and aging temperature played key roles in the formation of the PbWO4 needle-like structures. Between temperatures of 60 to 150 C, the length and photoluminescence intensities of the PbWO4 micro needles significantly increased with aging temperature, while the diameter did not change remarkably. Time-dependent experiments revealed that the formation of PbWO4 microneedles involved an unusual growth process, involving nucleation, oriented assembly and controlled mesoscale restructuring of nanoparticle building blocks. (orig.)

  4. Optical storage in azobenzene-containing epoxy polymers processed as Langmuir Blodgett films

    Energy Technology Data Exchange (ETDEWEB)

    Fernández, Raquel; Mondragon, Iñaki [‘Materials - Technologies’ Group, Department of Chemical and Environmental Engineering, Polytechnic School, Universidad País Vasco/Euskal Herriko Unibertsitatea, Pza Europa 1, 20018 Donostia-San Sebastián (Spain); Sanfelice, Rafaela C.; Pavinatto, Felippe J.; Oliveira, Osvaldo N. [Instituto de Física de São Carlos, Universidade de São Paulo, Av. Trabalhador São Carlense, 400, Centro, CEP 13560-970, São Carlos (Brazil); Oyanguren, Patricia [Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and National Research Council (CONICET), J. B. Justo 4302, 7600 Mar del Plata (Argentina); Galante, María J., E-mail: galant@fi.mdp.edu.ar [Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and National Research Council (CONICET), J. B. Justo 4302, 7600 Mar del Plata (Argentina)

    2013-04-01

    In this study, azocopolymers containing different main-chain segments have been synthesized with diglycidyl ether of bisphenol A (DGEBA, DER 332, n = 0.03) and the azochromophore Disperse Orange 3 (DO3) cured with two monoamines, viz. benzylamine (BA) and m-toluidine (MT). The photoinduced birefringence was investigated in films produced with these azopolymers using the spin coating (SC) and Langmuir Blodgett (LB) techniques. In the LB films, birefringence increased with the content of azochromophore and the film thickness, as expected. The nanostructured nature of the LB films led to an enhanced birefringence and faster dynamics in the writing process, compared to the SC films. In summary, the combination of azocopolymers and the LB method may allow materials with tuned properties for various optical applications, including in biological systems were photoisomerization may be used to trigger actions such as drug delivery. Highlights: ► Langmuir Blodgett (LB) films of epoxy-based azopolymers were obtained and analyzed. ► Optical properties of LB and spin coated (SC) films were compared. ► Azo content, structure, laser power and number of layers were main factors studied. ► LB films had larger free volume for the azobenzenes isomerization than SC. ► LB films led to higher birefringence and faster dynamics compared to SC.

  5. Quantitative Structure-activity Relationships for Anaerobic Biodegradation of Substituted Azobenzenes

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xiao-yi; ZHU Huai-wu; LUO Shi-xia; WANG Zheng-wu; XIAO Han

    2004-01-01

    The degradation rates of the azo-bonds of a series of substituted azobenzenes caused by anaerobic sludge digestion were determined by measuring the biggest change of the absorption peak area of the UV-Vis spectra of the anaerobic sludge system before and after degradation. The electronic structure of the molecules was calculated by using the quantum chemistry semiempirical method AM1. The research on the correlation between the biodegradability of the azo-bond and the molecular structure descriptors has led to the following results. (1) There is an obvious relationship between the degradation rate D and the difference Δqπ in π-charge density of the azo-bond. (2) The different substituents in the molecules result in a wave pattern of π-charge distribution and the increasing of the flowability of π-electron. A good flowability of the π-charge favors the reduction between electron contributing azo groups. (3) The effect of the substituents on the π-electron system depends on the electromerization of the substituents in combination with the conjugated systems.

  6. Study on the prediction of visible absorption maxima of azobenzene compounds

    Institute of Scientific and Technical Information of China (English)

    LIU Jun-na; CHEN Zhi-rong; YUAN Shen-feng

    2005-01-01

    The geometries of azobenzene compounds are optimized with B3LYP/6-311 G* method, and analyzed with nature bond orbital, then their visible absorption maxima are calculated with TD-DFT method and ZINDO/S method respectively. The results agree well with the observed values. It was found that for the calculation of visible absorption using ZINDO/S method could rapidly yield better results by adjusting OWFπ-π (the relationship between π-π overlap weighting factor) value than by the TD-DFT method. The method of regression showing the linear relationship between OWFπ-π and BLN-N (nitrogen-nitrogen bond lengths) as OWFπ-π=-8.1537+6.5638BLN-N, can be explained in terms of quantum theory, and also be used for prediction of visible absorption maxima of other azobenzne dyes in the same series. This study on molecules' orbital geometry indicates that their visible absorption maxima correspond to the electron transition from HOMO (the highest occupied molecular orbital) to LUMO (the lowest unoccupied molecular orbital).

  7. Photopatterned surface relief gratings in azobenzene-amorphous polycarbonate thin films

    Science.gov (United States)

    Vollmann, Morten; Getek, Peter; Olear, Kellie; Combs, Cody; Campos, Benjamin; Witkowski, Edmund; Cain, Erin; McGee, David

    Photoinduced orientation of azobenzene chromophores in polymeric host materials has been broadly explored for optical processing applications. Illumination of the chromophore with polarized light rotates the trans isomer perpendicular to the polarization, resulting in spatially modulated birefringence. The photoinduced anisotropy may also drive mass transport, with surface relief patterns being observed in a wide variety of systems. Here we report photoinduced birefringence in a guest-host system of Disperse Red 1- amorphous polycarbonate (DR1-APC). Birefringence was induced with a 490 nm laser and probed at 633 nm, with typical values of Δn = 0.01 in 2 micron thick films. Illumination of DR1-APC with intensity and/or polarization gratings also resulted in sinusoidal surface relief patterns with periodicity 1- 3 micron as controlled by the interbeam crossing angle of the 490 nm writing beams; the surface modulation was +/- 20 nm as measured by atomic force microscopy. Photopatterned DR1-APC is advantageous for applications given the ease of thin-film fabrication and the high glass transition temperature of APC, resulting in robust optically-induced surface gratings. We acknowledge support from NSF-DMR Award No. 1138416.

  8. Photocontrol of Voltage-Gated Ion Channel Activity by Azobenzene Trimethylammonium Bromide in Neonatal Rat Cardiomyocytes.

    Directory of Open Access Journals (Sweden)

    Sheyda R Frolova

    Full Text Available The ability of azobenzene trimethylammonium bromide (azoTAB to sensitize cardiac tissue excitability to light was recently reported. The dark, thermally relaxed trans- isomer of azoTAB suppressed spontaneous activity and excitation propagation speed, whereas the cis- isomer had no detectable effect on the electrical properties of cardiomyocyte monolayers. As the membrane potential of cardiac cells is mainly controlled by activity of voltage-gated ion channels, this study examined whether the sensitization effect of azoTAB was exerted primarily via the modulation of voltage-gated ion channel activity. The effects of trans- and cis- isomers of azoTAB on voltage-dependent sodium (INav, calcium (ICav, and potassium (IKv currents in isolated neonatal rat cardiomyocytes were investigated using the whole-cell patch-clamp technique. The experiments showed that azoTAB modulated ion currents, causing suppression of sodium (Na+ and calcium (Ca2+ currents and potentiation of net potassium (K+ currents. This finding confirms that azoTAB-effect on cardiac tissue excitability do indeed result from modulation of voltage-gated ion channels responsible for action potential.

  9. Fast photodynamics of azobenzene probed by scanning excited-state potential energy surfaces using slow spectroscopy.

    Science.gov (United States)

    Tan, Eric M M; Amirjalayer, Saeed; Smolarek, Szymon; Vdovin, Alexander; Zerbetto, Francesco; Buma, Wybren Jan

    2015-01-01

    Azobenzene, a versatile and polymorphic molecule, has been extensively and successfully used for photoswitching applications. The debate over its photoisomerization mechanism leveraged on the computational scrutiny with ever-increasing levels of theory. However, the most resolved absorption spectrum for the transition to S1(nπ*) has not followed the computational advances and is more than half a century old. Here, using jet-cooled molecular beam and multiphoton ionization techniques we report the first high-resolution spectra of S1(nπ*) and S2(ππ*). The photophysical characterization reveals directly the structural changes upon excitation and the timescales of dynamical processes. For S1(nπ*), we find that changes in the hybridization of the nitrogen atoms are the driving force that triggers isomerization. In combination with quantum chemical calculations we conclude that photoisomerization occurs along an inversion-assisted torsional pathway with a barrier of ~2 kcal mol(-1). This methodology can be extended to photoresponsive molecular systems so far deemed non-accessible to high-resolution spectroscopy. PMID:25562840

  10. Ultrafast vectorial and scalar dynamics of ionic clusters: Azobenzene solvated by oxygen

    Science.gov (United States)

    Paik, D. Hern; Baskin, J. Spencer; Kim, Nam Joon; Zewail, Ahmed H.

    2006-10-01

    The ultrafast dynamics of clusters of trans-azobenzene anion (A-) solvated by oxygen molecules was investigated using femtosecond time-resolved photoelectron spectroscopy. The time scale for stripping off all oxygen molecules from A- was determined by monitoring in real time the transient of the A- rise, following an 800nm excitation of A- (O2)n, where n =1-4. A careful analysis of the time-dependent photoelectron spectra strongly suggests that for n >1 a quasi-O4 core is formed and that the dissociation occurs by a bond cleavage between A- and conglomerated (O2)n rather than a stepwise evaporation of O2. With time and energy resolutions, we were able to capture the photoelectron signatures of transient species which instantaneously rise (rupture of the A--(O2)n nuclear coordinate and a slower component (1.6-36ps, increasing with n) attributed to an indirect channel exhibiting a quasistatistical behavior. The photodetachment transients exhibit a change in the transition dipole direction as a function of time delay. Rotational dephasing occurs on a time scale of 2-3ps, with a change in the sign of the transient anisotropy between A-O2 and the larger clusters. This behavior is a key indicator of an evolving cluster structure and is successfully modeled by calculations based on the structures and inertial motion of the parent clusters.

  11. POLYMER SCAFFOLDS BEARING AZOBENZENE —— POTENTIAL FOR OPTICAL INFORMATION STORAGE

    Institute of Scientific and Technical Information of China (English)

    Sφren Hvilsted; P.S. Ramanujam

    2001-01-01

    The fundamental optical storage mechanism of the laser light addressable azobenzene moiety is briefly introduced.A modular and flexible synthesis design furnishes polyester matrices covalently integrating cyanoazobenzene in regularly spaced side chains. Thin films of these materials are particularly well suited for holographic storage. Notable figures of merits of liquid crystalline polyesters are response time to blue-green laser light of the order of nanoseconds, storage capacity expressed as 5000 lines/mm, and high, permanent (almost nine years) diffraction efficiency of the order of 50% or greater,and erasability. The implications of the main chain nature for polyester morphology and for the permanency of the induced anisotropy are discussed. The design and methods of preparation of other significantly different polymer scaffolds supporting cyanoazobenzene are elaborated. Oligopeptides always result in amorphous materials, whereas copolymethacrylates and dendritic or hyperbranched polyesters provide some materials that exhibit liquid crystallinity. However, none of these scaffolds affords materials that result in permanent anisotropy when exposed to interfering laser light.

  12. Thermal and Electronic Fluctuations of Flexible Adsorbed Molecules: Azobenzene on Ag(111)

    Science.gov (United States)

    Maurer, Reinhard J.; Liu, Wei; Poltavsky, Igor; Stecher, Thomas; Oberhofer, Harald; Reuter, Karsten; Tkatchenko, Alexandre

    2016-04-01

    We investigate the thermal and electronic collective fluctuations that contribute to the finite-temperature adsorption properties of flexible adsorbates on surfaces on the example of the molecular switch azobenzene C12 H10 N2 on the Ag(111) surface. Using first-principles molecular dynamics simulations, we obtain the free energy of adsorption that accurately accounts for entropic contributions, whereas the inclusion of many-body dispersion interactions accounts for the electronic correlations that govern the adsorbate binding. We find the adsorbate properties to be strongly entropy driven, as can be judged by a kinetic molecular desorption prefactor of 1024 s-1 that largely exceeds previously reported estimates. We relate this effect to sizable fluctuations across structural and electronic observables. A comparison of our calculations to temperature-programed desorption measurements demonstrates that finite-temperature effects play a dominant role for flexible molecules in contact with polarizable surfaces, and that recently developed first-principles methods offer an optimal tool to reveal novel collective behavior in such complex systems.

  13. Calculated photo-isomerization efficiencies of functionalized azobenzene derivatives in solar energy materials: azo-functional organic linkers for porous coordinated polymers

    International Nuclear Information System (INIS)

    Recently, we used a local orbital density functional theory code called FIREBALL, to study the photoisomerization process in azobenzene derivatives for solar energy materials. Azobenzene functional groups undergo photoisomerization upon light irradiation or application of heat. Zhou et al (2012 J. Am. Chem. Soc. 134 99–102) showed that these azobenzenes can then be introduced into metal–organic frameworks via an organic linker in order to create a reversible switch for CO2 adsorption. In this manuscript, we examined how the addition of organic linkers (isophthalic acid) changes the relaxation times, isomerization mechanism, and quantum yield for both the cis↔trans pathways. We then tuned these properties by substituting functional groups, finding an increase in quantum yield as well as improved optical properties. (paper)

  14. Blocked strainers

    International Nuclear Information System (INIS)

    Thermal insulation was the cause of the blockages that shut down five BWRs in Sweden. The main culprit was mineral wool installed when the plants started up. Physical degradation of the wool over the lifetime of the plant meant it could easily be washed out of place during a loss of coolant accident and could quickly block strainers in the emergency core cooling systems. The five BWRs are almost all back on line, equipped with larger strainers and faster backwashing capability. But the incident prompted more detailed investigation into how materials in the containment would behave during an accident. One material that caused particular concern is Caposil, a material often used to insulate the reactor vessel. Composed of natural calcium, aluminium silicates and cellulose fibres, in the event of a LOCA Caposil becomes particularly hazardous. Under high pressure, or when brought into contact with high pressure water and steam, Caposil fragments into 1 cm clumps, free fibres, and ''fines''. It is these fines which cause major problems and can block a strainer extremely quickly. The successful testing of a high performance water filter which can handle Caposil is described. (4 figures) (Author)

  15. Metal Nanoparticle/Block Copolymer Composite Assembly and Disassembly

    OpenAIRE

    Li, Zihui; Sai, Hiroaki; Warren, Scott C.; Kamperman, Marleen; Arora, Hitesh; Gruner, Sol M.; Wiesner, Ulrich

    2009-01-01

    Ligand-stabilized platinum nanoparticles (Pt NPs) were self-assembled with poly(isoprene-block-dimethylaminoethyl methacrylate) (PI-b-PDMAEMA) block copolymers to generate organic-inorganic hybrid materials. High loadings of NPs in hybrids were achieved through usage of N,N-di-(2-(allyloxy)ethyl)-N-3-mercaptopropyl-N-3-methylammonium chloride as the ligand, which provided high solubility of NPs in various solvents as well as high affinity to PDMAEMA. From NP synthesis, existence of sub-1 nm P...

  16. Acrylic resins. Part II. Methacrylate polymers (citations from NTIS data base). Report for 1964--Mar 1976

    International Nuclear Information System (INIS)

    Polymethyl methacrylate, polymethacrylic acid, and all other methacrylate and methacrylic polymers, copolymers, and resins are covered in Part 2 of this bibliography. The citations include references concerning physical, chemical, and mechanical properties, synthesis, polymerization and processing. (This updated bibliography contains 172 abstracts, 25 of which are new entries to the previous edition.)

  17. Chemoenzymatic Synthesis of Amphiphilic Core-Shell TMP-(PCL-b-PGMA2)3 Star-Block Copolymer.

    Science.gov (United States)

    Wang, Shuwei; Li, Yapeng; Zhang, Xiaonan; Chen, Xuesi; Wang, Jingyuan; Zhang, He-Xin; Yoon, Keun-Byoung

    2015-06-01

    A novel well-defined amphiphilic Core-Shell star-block copolymer was synthesized from trimethylolpropane, ε-caprolactone, and glycidyl methacrylate by a combination of enzymatic ring-opening polymerization and atom transfer radical polymerization. The structure and molecular weight of the macroinitiator and the star-block copolymer were confirmed by means of nuclear magnetic resonance and gel permeation chromatography. The effects of the glycidyl methacrylate sequence length on the hydrodynamic diameter and morphology of the polymer micelles were investigated by dynamic light scattering and transmission electron microscopy, respectively. PMID:26369103

  18. Photo-orientation of azobenzene side chain polymers parallel or perpendicular to the polarization of red HeNe light

    International Nuclear Information System (INIS)

    The mechanism of the light-induced orientation process of azobenzene-containing polymers caused by irradiation with linearly polarized red light is investigated. This process is surprising because there is almost no absorption at 633 nm. Depending on the photochemical pre-treatment and the exposure time, the azobenzene moieties can undergo two different orientation processes resulting in either a parallel or a perpendicular orientation with respect to the electric field vector of the incident light. The fast orientation of the photochromic groups with their long axis in the direction of the light polarization requires a photochemical pre-treatment in which non-polarized UV light generates Z-isomers. Due to this procedure the film becomes 'photochemically activated' for the subsequent polarized irradiation with red light. But on continued exposure a second, much slower reorientation process occurs which establishes an orientation of the azobenzene groups perpendicular to the electric field vector. The fast mechanism is probably caused by an angle-selective photo-isomerization of the Z-isomers to the E-isomers, while the subsequent slow reorientation process is caused by the well-known conventional photo-orientation taking place via the accumulation of a number of photoselection steps and the rotational diffusion minimizing the absorbance of the E-isomer. This process occurs in the steady state but at this wavelength with a very small concentration of Z-isomers. The competing mechanisms take place in the same polymer film under almost identical irradiation conditions, differing only in the actual concentration of the Z-isomers

  19. Bioinspired amphiphilic phosphate block copolymers as non-fluoride materials to prevent dental erosion

    OpenAIRE

    Lei, Yanda; Wang, Tongxin; Mitchell, James W; Zaidel, Lynette; Qiu, Jianhong; Kilpatrick-Liverman, LaTonya

    2014-01-01

    Inspired by the fact that certain natural proteins, e.g. casein phosphopeptide or amelogenin, are able to prevent tooth erosion (mineral loss) and to enhance tooth remineralization, a synthetic amphiphilic diblock copolymer, containing a hydrophilic methacryloyloxyethyl phosphate block (MOEP) and a hydrophobic methyl methacrylate block (MMA), was designed as a novel non-fluoride agent to prevent tooth erosion under acidic conditions. The structure of the polymer, synthesized by reversible add...

  20. Amphiphilic Fluorinated Block Copolymer Synthesized by RAFT Polymerization for Graphene Dispersions

    OpenAIRE

    Hyang Moo Lee; Suguna Perumal; In Woo Cheong

    2016-01-01

    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 assiste...

  1. Base-Catalyzed Hydrophosphination of Azobenzenes with Diarylphosphine Oxides: A Precise Construction of N-N-P Unit.

    Science.gov (United States)

    Hong, Gang; Zhu, Xiaoyan; Hu, Chen; Aruma, Alfred Njasotapher; Wu, Shengying; Wang, Limin

    2016-08-01

    Addition of diarylphosphine oxides to the N═N double bond of azobenzenes leads to the formation of the P-substituted hydrazines in up to 98% yield for 24 examples, and the formation of diphenylphosphinic amides was observed in three substrates. This strategy features tolerance of a wide range of functional groups, simple operation, and mild reaction conditions. Specially, this method can be also applied to the gram-scale synthesis of the product. A polar reaction mechanism is also proposed based on control experiments. PMID:27387595

  2. Covalent functionalization of graphene by azobenzene with molecular hydrogen bonds for long-term solar thermal storage

    OpenAIRE

    Feng, Yiyu; Liu, Hongpo; Luo, Wen; Liu, Enzuo; Zhao, Naiqin; Yoshino, Katsumi; Feng, Wei

    2013-01-01

    Reduced graphene oxide-azobenzene (RGO-AZO) hybrids were prepared via covalent functionalization for long-term solar thermal storage. Thermal barrier (ΔEa ) of cis to tran reversion and thermal storage (ΔH) were improved by molecular hydrogen bonds (H-bonds) through ortho- or para-substitution of AZO. Intramolecular H-bonds thermally stabilized cis-ortho-AZO on RGO with a long-term half-life of 5400 h (ΔEa = 1.2 eV), which was much longer than that of RGO-para-AZO (116 h). RGO-para-AZO with o...

  3. Formation and Characterization of Anisotropic Block Copolymer Gels

    Science.gov (United States)

    Liaw, Chya Yan; Joester, Derk; Burghardt, Wesley; Shull, Kenneth

    2012-02-01

    Cylindrical micelles formed from block copolymer solutions closely mimic biological fibers that are presumed to guide mineral formation during biosynthesis of hard tissues like bone. The goal of our work is to use acrylic block copolymers as oriented templates for studying mineral formation reactions in model systems where the structure of the underlying template is well characterized and reproducible. Self-consistent mean field theory is first applied to investigate the thermodynamically stable micellar morphologies as a function of temperature and block copolymer composition. Small-angle x-ray scattering, optical birefringence and shear rheometry are used to study the morphology development during thermal processing. Initial experiments are based on a thermally-reversible alcohol-soluble system that can be converted to an aqueous gel by hydrolysis of a poly(t-butyl methacrylate) block to a poly(methacrylic acid) block. Aligned cylindrical domains are formed in the alcohol-based system when shear is applied in an appropriate temperature regime, which is below the critical micelle temperature but above the temperature at which the relaxation time of the gels becomes too large. Processing strategies for producing the desired cylindrical morphologies are being developed that account for both thermodynamic and kinetic effects.

  4. Redox Polymerization of Methyl Methacrylate in the Fluorous Triphasic System

    Institute of Scientific and Technical Information of China (English)

    Shi Zhen CHEN; Yun Peng BAI; Zhao Long LI

    2006-01-01

    Methyl methacrylate (MMA) was polymerized by using of benzoyl peroxide (BPO) and N, N-dimethylaniline (DMA) as an redox initiator in fluorous triphasic system at room temperature.The polymerization was occurred in both initiator layer and monomer layer in a U-tube. It was found that PMMA obtained from the initiator layer with relatively narrow polydispersity.(PDI =1.38)

  5. Synthesis of acrylates and methacrylates from coal-derived syngas

    Energy Technology Data Exchange (ETDEWEB)

    Spivey, J.J.; Gogate, M.R.; Jang, B.W.L. [Bechtel, San Francisco, CA (United States)] [and others

    1995-12-31

    Acrylates and methacrylates are among the most widely used chemical intermediates in the world. One of the key chemicals of this type is methyl methacrylate. Of the 4 billion pounds produced each year, roughly 85% is made using the acetone-cyanohydrin process, which requires handling of large quantities of hydrogen cyanide and produces ammonium sulfate wastes that pose an environmental disposal challenge. The U.S. Department of Energy and Eastman Chemical Company are sharing the cost of research to develop an alternative process for the synthesis of methyl methacrylate from syngas. Research Triangle Institute is focusing on the synthesis and testing of active catalysts for the condensation reactions, and Bechtel is analyzing the costs to determine the competitiveness of several process alternatives. Results thus far show that the catalysts for the condensation of formaldehyde and the propionate are key to selectively producing the desired product, methacrylic acid, with a high yield. These condensation catalysts have both acid and base functions and the strength and distribution of these acid-base sites controls the product selectivity and yield.

  6. Polymethyl Methacrylate as a Binder for Pyrotechnic Compositions

    OpenAIRE

    S. P. Sontakke; S. D. Kakade; R. M. Wagh; A. G. Dugam; P. P. Sane

    1995-01-01

    Studies on polymethyl methacrylate (PMMA) as a binder for igniter and delay compositions are reported. Igniter compositions based on magnesium and boron as fuels and potassium nitrate as oxidiser, delay compositions comprising ferrosilicon and red lead, have been investigated. These compositions were subjected to various tests, such as linear burning rate, sensitivity, calorimetric value, compatibility, pelleting properties, spark sensitivity, ignition temperatures and performance char...

  7. A study of the system of polymethyl methacrylate: Pt.4

    International Nuclear Information System (INIS)

    The effect of radiation on the temperature-deformation properties of linear and cross-linked polymethyl methacrylate was studied. The glass transition temperature (Tg) of linear polymethyl methacrylate with high molecular weight was found to be almost independant of molecular weight. It's Tg ualue decreases slightly with increasing radiation dose. On the other hand, its flow temperature (Tf) is dependent on molecular weight and reduced markedly with increasing radiation dose. A relationship between molecular weight and Tf was proposed. It was also observed that there are no obvious flow temperature and viscous liquid state for high cross-linked polymethyl methacrylate with Me (average molecular weight between cross-links) 4. An additional cross-link will cause an additional restriction to the flexibility of the molecules. Because Tg deterimnes the upper limit of temperature of glass-like thermoplastic and its value raise 20-30 deg C, as compared with the linear polymer, the heat resistance of cross-linked polymethyl methacrylate improves considerably. Morever this polymer exhibits a considerable possibility for heat processing because its Tf value is only 3-10 deg C higher than that of commerical linear polymer

  8. Novel fluorescent poly(glycidyl methacrylate) - silica microspheres

    Czech Academy of Sciences Publication Activity Database

    Grama, Silvia; Boiko, N.; Bilyy, R.; Klyuchivska, O.; Antonyuk, V.; Stoika, R.; Horák, Daniel

    2014-01-01

    Roč. 56, July (2014), s. 92-104. ISSN 0014-3057 R&D Projects: GA MŠk EE2.3.30.0029; GA MŠk(CZ) ED1.1.00/02.0109 Institutional support: RVO:61389013 Keywords : microspheres * silica * poly(glycidyl methacrylate) Subject RIV: CE - Biochemistry Impact factor: 3.005, year: 2014

  9. MONOLAYER BEHAVIOR OF SOME STEREOREGULAR POLY(METHACRYLATES)

    NARCIS (Netherlands)

    BRINKHUIS, RHG; SCHOUTEN, AJ

    1992-01-01

    The monolayer behavior of some poly(methacrylates) with short ester side chains (methyl, ethyl, and isobutyl) is studied as a function of the tacticity. In all cases, the isotactic polymers are observed to form expanded monolayers, whereas the syndiotactic materials yield more condensed monolayers.

  10. Pore structure of poly(2-hydroxyethyl methacrylate) scaffolds

    Czech Academy of Sciences Publication Activity Database

    Horák, Daniel; Hlídková, Helena

    Oakville: Apple Academic Press, 2014 - (Guarrotxena, N.), s. 79-99 ISBN 978-1-77188-011-4 R&D Projects: GA ČR GAP304/11/0731 Institutional support: RVO:61389013 Keywords : hydrogels * low-vacuum scanning electron mMicroscopy * poly(2-hydroxyethyl methacrylate) Subject RIV: FH - Neurology http://www.appleacademicpress.com/title.php?id=9781771880114

  11. Azobenzene-aminoglycoside: Self-assembled smart amphiphilic nanostructures for drug delivery.

    Science.gov (United States)

    Deka, Smriti Rekha; Yadav, Santosh; Mahato, Manohar; Sharma, Ashwani Kumar

    2015-11-01

    Here, we have designed and synthesized a novel cationic amphiphilic stimuli-responsive azobenzene-aminoglycoside (a small molecule) conjugate, Azo-AG 5, and characterized it by UV and FTIR. Light responsive nature of Azo-AG 5 was assessed under UV-vis light. Self- assembly of Azo-AG 5 in aqueous solutions into nanostructures and their ability to act as drug carrier were also investigated. The nanostructures of Azo-AG 5 showed average hydrodynamic diameter of ∼ 255 nm with aminoglycoside moiety (neomycin) and 4-dimethylaminoazobenzene forming hydrophilic shell and hydrophobic core, respectively. In the hydrophobic core, eosin and aspirin were successfully encapsulated. Dynamic light scattering (DLS) measurements demonstrated that the nanoassemblies showed expansion and contraction on successive UV and visible light irradiations exhibiting reversible on-off switch for controlling the drug release behavior. Similar behavior was observed when these nanostructures were subjected to pH-change. In vitro drug release studies showed a difference in UV and visible light-mediated release pattern. It was observed that the release rate under UV irradiation was comparatively higher than that observed under visible light. Further, azoreductase-mediated cleavage of the azo moiety in Azo-AG 5 nanoassemblies resulted in the dismantling of the structures into aggregated microstructures. Azo-AG 5 nanostructures having positive surface charge (+9.74 mV) successfully interacted with pDNA and retarded its mobility on agarose gel. Stimuli responsiveness of nanostructures and their on-off switch like behavior ensure the great potential as controlled drug delivery systems and in other biomedical applications such as colon-specific delivery and gene delivery. PMID:26255160

  12. The influence of monomer molar ratio on the properties of copolymers based on methyl methacrylate and methacrylic acid

    Directory of Open Access Journals (Sweden)

    Ristić Ivan S.

    2009-01-01

    Full Text Available The application of polymers for controlled drug delivery is influenced by no toxicity and solubility in different pH mediums. There already are existing pharmaceutical medicaments based on aqueous dispersion of an anionic copolymer methyl acrylate, methyl methacrylate and methacrylic acid. The aim of this work was to synthesise copolymers of methyl methacrylate and methacrylic acid and to estimate the effects of monomers ratio (1:1 and 1:2 on the molecular mass, polydispersity index, and solubility of obtained polymers. Acetone was used as a solvent because both monomers and the initiator azobisisobutyronitrile are soluble in it. FTIR method was used for functional group characterization, the gel permeation chromatography method for average molecular weights and the distribution of molecular weights determinations. High pressure liquid chromatography (HPLC was applied for the estimation of residual monomers in obtained copolymers. The titration with ethanol solution of NaOH was used for assessing of monomer units in copolymers. The copolymer with the molar ratio of monomers 1:1 was soluble in water bufer with pH values higher then 6, while the copolymer with the molar ratio of monomers 1:2 was soluble in bufer with pH higher then 9.

  13. Triazene UV-triggered photogeneration of silver/gold nanoparticles in block copolymer templates

    Energy Technology Data Exchange (ETDEWEB)

    Melinte, Violeta; Chibac, Andreea; Buruiana, Tinca; Hitruc, Gabriela; Buruiana, Emil C., E-mail: emilbur@icmpp.ro [Petru Poni Institute of Macromolecular Chemistry, Polyaddition and Photochemistry Department (Romania)

    2015-10-15

    This article describes an attractive way to in situ create noble metal nanoparticles in block copolymer matrixes through the UV-triggered photodecomposition of the photolabile triazene units without the use of any conventional reducing agent. The poly(isodecyl methacrylate-co-triazene urethane methacrylate) random copolymer containing pendent photocleavable triazene junctions (COP-1) was synthesized under RAFT conditions and subsequently employed as macroinitiator to obtain a block copolymer, namely poly(isodecyl methacrylate-co-triazene urethane methacrylate)-block-poly(acrylic acid) (COP-2). The photogeneration of silver/gold metal nanoparticles (NPs) from noble metal precursors (1 wt% AgNO{sub 3} or AuBr{sub 3} metal salts) induced through the UV decomposition of triazene units with the formation of some radical active species was monitored in solution and thin films. The in situ growth of Ag/Au nanostructures into polymer matrixes for which the light is a key element has been confirmed by UV spectroscopy and TEM analysis. The TEM images allowed the visualization of the silver NPs (sizes of 4–16 nm in COP-1 and of 2–6 nm in COP-2) as well as of the gold NPs (sizes between 10 and 20 nm in COP-1 and from 15 to 25 nm in COP-2), which are mainly spherical in shape, even though there is some triangular or hexagonal gold nanoparticles.

  14. Triazene UV-triggered photogeneration of silver/gold nanoparticles in block copolymer templates

    International Nuclear Information System (INIS)

    This article describes an attractive way to in situ create noble metal nanoparticles in block copolymer matrixes through the UV-triggered photodecomposition of the photolabile triazene units without the use of any conventional reducing agent. The poly(isodecyl methacrylate-co-triazene urethane methacrylate) random copolymer containing pendent photocleavable triazene junctions (COP-1) was synthesized under RAFT conditions and subsequently employed as macroinitiator to obtain a block copolymer, namely poly(isodecyl methacrylate-co-triazene urethane methacrylate)-block-poly(acrylic acid) (COP-2). The photogeneration of silver/gold metal nanoparticles (NPs) from noble metal precursors (1 wt% AgNO3 or AuBr3 metal salts) induced through the UV decomposition of triazene units with the formation of some radical active species was monitored in solution and thin films. The in situ growth of Ag/Au nanostructures into polymer matrixes for which the light is a key element has been confirmed by UV spectroscopy and TEM analysis. The TEM images allowed the visualization of the silver NPs (sizes of 4–16 nm in COP-1 and of 2–6 nm in COP-2) as well as of the gold NPs (sizes between 10 and 20 nm in COP-1 and from 15 to 25 nm in COP-2), which are mainly spherical in shape, even though there is some triangular or hexagonal gold nanoparticles

  15. Calculated photo-isomerization efficiencies of functionalized azobenzene derivatives in solar energy materials: azo-functional organic linkers for porous coordinated polymers

    Czech Academy of Sciences Publication Activity Database

    Neukirch, A.J.; Park, J.; Zobač, Vladimír; Wang, H.; Jelínek, Pavel; Prezhdo, O.V.; Zhou, H.-C.; Lewis, J.P.

    2015-01-01

    Roč. 27, č. 13 (2015), s. 134208. ISSN 0953-8984 R&D Projects: GA ČR(CZ) GA14-02079S Institutional support: RVO:68378271 Keywords : photoisomerization * azobenzene * metal - organic frameworks * molecular switches Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.346, year: 2014

  16. Cis-trans photoisomerization of azobenzene upon excitation to the S-1 state: An ab initio molecular dynamics and QM/MM study

    Czech Academy of Sciences Publication Activity Database

    Pederzoli, Marek; Pittner, Jiří; Barbatti, M.; Lischka, H.

    Bellingham: SPIE-INT SOC OPTICAL ENGINEERING, 2012 - (Dobisz, E.; Eldada, L.), s. 846318 ISBN 978-0-8194-9180-0. [Conference on Nanoengineering - Fabrication, Properties, Optics, and Devices /9./. San Diego (US), 14.08.2012-16.08.2012] Institutional support: RVO:61388955 Keywords : azobenzene * ab initio molecular dynamics * excited states Subject RIV: CF - Physical ; Theoretical Chemistry

  17. Holographic investigations of azobenzene-containing low-molecular-weight compounds in pure materials and binary blends with polystyrene.

    Science.gov (United States)

    Audorff, Hubert; Walker, Roland; Kador, Lothar; Schmidt, Hans-Werner

    2011-11-01

    This paper reports on the synthesis and the thermal and optical properties of photochromic low-molecular-weight compounds, especially with respect to the formation of holographic volume gratings in the pure materials and in binary blends with polystyrene. Its aim is to provide a basic understanding of the holographic response with regard to the molecular structure, and thus to show a way to obtain suitable rewritable materials with high sensitivity for holographic data storage. The photoactive low-molecular-weight compounds consist of a central core with three or four azobenzene-based arms attached through esterification. Four different cores were investigated that influence the glass transition temperature and the glass-forming properties. Additional structural variations were introduced by the polar terminal substituent at the azobenzene chromophore to fine-tune the optical properties and the holographic response. Films of the neat compounds were investigated in holographic experiments, especially with regard to the material sensitivity. In binary blends of the low-molecular-weight compounds with polystyrene, the influence of a polymer matrix on the behavior in holographic experiments was studied. The most promising material combination was also investigated at elevated temperatures, at which the holographic recording sensitivity is even higher. PMID:21956207

  18. Preparation and characterization of organic-inorganic hybrid nanomaterials using polyurethane-b-poly[3-(trimethoxysilyl propyl methacrylate] via RAFT polymerization

    Directory of Open Access Journals (Sweden)

    2010-01-01

    Full Text Available A series of novel block-type amphiphilic copolymers have been prepared by copolymerizing methacrylate endcapped oligo-urethane and 3-(trimethoxysilyl propyl methacrylate (TPM via the sol-gel process. Copolymers with welldefined end groups and narrow polydispersity were prepared through Reversible Addition Fragmentation Chain Transfer (RAFT polymerization. As-synthesized copolymer was characterized 1H nuclear magnetic resonance (1H NMR, gel permeation chromatography (GPC, Fourier transform infrared (FTIR. The copolymer precursors self-assembled in form of spherical micelles (in selective solvents have been hydrolyzed and then condensed via sol-gel process in order to generate polyurethane-silica (PU-SiO2 hybrid materials. The hybrid copolymers thus prepared possess excellent thermal stability and mechanical property. The structures and properties of the copolymer precursors and their hybrid copolymers were characterized by thermogravimetric analysis (TGA, tensile test and atomic force microscopy (AFM.

  19. Positron annihilation investigations on poly(methyl methacrylate)

    International Nuclear Information System (INIS)

    Positron lifetime and Doppler broadened annihilation radiation were measured for seven different samples of poly(methyl methacrylate) at room temperature in vacuum. The polymerisation of methyl methacrylate was carried out as a bulk polymerisation in the presence of benzoyl peroxide as an initiator. The effect of the amount of the initiator on the viscosity-average molecular weight was studied. It was found that the viscosity-average molecular weight decreased with increasing amount of the initiator. The average lifetime and intensity of ortho-positronium (o-Ps) increased with increasing viscosity-average molecular weight up to 6.85x104 and remained constant after that. The S-parameter showed a similar behaviour as that of the o-Ps intensity.

  20. Preparation and characterization of methacrylate hydrogels for zeta potential control

    Science.gov (United States)

    Gregonis, D. E.; Ma, S. M.; Vanwagenen, R.; Andrade, J. D.

    1976-01-01

    A technique based on the measurement of streaming potentials has been developed to evaluate the effects of hydrophilic coatings on electroosmotic flow. The apparatus and procedure are described as well as some results concerning the electrokinetic potential of glass capillaries as a function of ionic strength, pH, and temperature. The effect that turbulence and entrance flow conditions have on accurate streaming potential measurements is discussed. Various silane adhesion promoters exhibited only a slight decrease in streaming potential. A coating utilizing a glycidoxy silane base upon which methylcellulose is applied affords a six-fold decrease over uncoated tubes. Hydrophilic methacrylate gels show similar streaming potential behavior, independent of the water content of the gel. By introduction of positive or negative groups into the hydrophilic methacrylate gels, a range of streaming potential values are obtained having absolute positive or negative signs.

  1. Physical properties of agave cellulose graft polymethyl methacrylate

    Science.gov (United States)

    Rosli, Noor Afizah; Ahmad, Ishak; Abdullah, Ibrahim; Anuar, Farah Hannan

    2013-11-01

    The grafting polymerization of methyl methacrylate and Agave cellulose was prepared and their structural analysis and morphology were investigated. The grafting reaction was carried out in an aqueous medium using ceric ammonium nitrate as an initiator. The structural analysis of the graft copolymers was carried out by Fourier transform infrared and X-ray diffraction. The graft copolymers were also characterized by field emission scanning electron microscopy (FESEM). An additional peak at 1732 cm-1 which was attributed to the C=O of ester stretching vibration of poly(methyl methacrylate), appeared in the spectrum of grafted Agave cellulose. A slight decrease of crystallinity index upon grafting was found from 0.74 to 0.68 for cellulose and grafted Agave cellulose, respectively. Another evidence of grafting showed in the FESEM observation, where the surface of the grafted cellulose was found to be roughed than the raw one.

  2. Physical properties of agave cellulose graft polymethyl methacrylate

    Energy Technology Data Exchange (ETDEWEB)

    Rosli, Noor Afizah; Ahmad, Ishak; Abdullah, Ibrahim; Anuar, Farah Hannan [Polymer Research Centre (PORCE), School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi Selangor (Malaysia)

    2013-11-27

    The grafting polymerization of methyl methacrylate and Agave cellulose was prepared and their structural analysis and morphology were investigated. The grafting reaction was carried out in an aqueous medium using ceric ammonium nitrate as an initiator. The structural analysis of the graft copolymers was carried out by Fourier transform infrared and X-ray diffraction. The graft copolymers were also characterized by field emission scanning electron microscopy (FESEM). An additional peak at 1732 cm{sup −1} which was attributed to the C=O of ester stretching vibration of poly(methyl methacrylate), appeared in the spectrum of grafted Agave cellulose. A slight decrease of crystallinity index upon grafting was found from 0.74 to 0.68 for cellulose and grafted Agave cellulose, respectively. Another evidence of grafting showed in the FESEM observation, where the surface of the grafted cellulose was found to be roughed than the raw one.

  3. SYNTHESIS OF METHACRYLATES FROM COAL-DERIVED SYNGAS

    Energy Technology Data Exchange (ETDEWEB)

    Jang, B.W.L.; Spivey, J.J.; Gogate, M.R.; Zoeller, J.R.; Colberg, R.D.; Choi, G.N.

    1999-12-01

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel have developed a novel process for synthesis of methyl methacrylate (MMA) from coal-derived syngas, under a contract from the US Department of Energy/Fossil Energy Technology Center (DOE/FETC). This project has resulted in five US patents (four already published and one pending publication). It has served as the basis for the technical and economic assessment of the production of this high-volume intermediate from coal-derived synthesis gas. The three-step process consists of the synthesis of a propionate from ethylene carbonylation using coal-derived CO, condensation of the propionate with formaldehyde to form methacrylic acid (MAA); and esterification of MAA with methanol to yield MMA. The first two steps, propionate synthesis and condensation catalysis, are the key technical challenges and the focus of the research presented here.

  4. Physical properties of agave cellulose graft polymethyl methacrylate

    International Nuclear Information System (INIS)

    The grafting polymerization of methyl methacrylate and Agave cellulose was prepared and their structural analysis and morphology were investigated. The grafting reaction was carried out in an aqueous medium using ceric ammonium nitrate as an initiator. The structural analysis of the graft copolymers was carried out by Fourier transform infrared and X-ray diffraction. The graft copolymers were also characterized by field emission scanning electron microscopy (FESEM). An additional peak at 1732 cm−1 which was attributed to the C=O of ester stretching vibration of poly(methyl methacrylate), appeared in the spectrum of grafted Agave cellulose. A slight decrease of crystallinity index upon grafting was found from 0.74 to 0.68 for cellulose and grafted Agave cellulose, respectively. Another evidence of grafting showed in the FESEM observation, where the surface of the grafted cellulose was found to be roughed than the raw one

  5. States of Water in Hydrogels Containing with Glyceryl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    LI Qin-hua; LIU Li; HUANG Zhi-rong; LIN Dong-qing

    2014-01-01

    Hydrogel materials were prepared by thermopolymerization with different content of glyceryl methacrylate and hydroxyethyl methacrylate. The different states of water in swelling hydrogels were described and studied by differential scanning calorimetry (DSC). It was found that the hydrophilicity of GMA was stronger than HEMA, the water content and bound water of GMA hydrogel are higher than HEMA hydrogel. With the increase of GMA content, the content of free water in hydrogel increased. When GMA content was lower than 50%, the increase of GMA content also increased the content of bound water; but when GMA content was higher than 50%, the increase of GMA content decreased the content of bound water, which was caused by the chain hydrogen bond formed on the GMA chain with hydroxyl group each other.

  6. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    Energy Technology Data Exchange (ETDEWEB)

    Makarand R. Gogate; James J. Spivey; Joseph R. Zoeller; Richard D. Colberg; Gerald N. Choi; Samuel S. Tam

    1999-04-21

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. The research team has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, we are currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last quarter (January-March/99), in-situ formaldehyde generation and condensation with methyl propionate were tested over various catalysts and reaction conditions. The patent application is in preparation and the results are retained for future reports.

  7. Penile enlargement with methacrylate injection: is it safe?

    Science.gov (United States)

    Torricelli, Fabio Cesar Miranda; Andrade, Enrico Martins de; Marchini, Giovanni Scala; Lopes, Roberto Iglesias; Claro, Joaquim Francisco Almeida; Cury, Jose; Srougi, Miguel

    2013-01-01

    CONTEXT Penis size is a great concern for men in many cultures. Despite the great variety of methods for penile augmentation, none has gained unanimous acceptance among experts in the field. However, in this era of minimally invasive procedure, injection therapy for penile augmentation has become more popular. Here we report a case of methacrylate injection in the penis that evolved with penile deformity and sexual dysfunction. This work also reviews the investigation and management of this pathological condition. CASE REPORT A 36-year-old male sought medical care with a complaint of penile deformity and sexual dysfunction after methacrylate injection. The treatment administered was surgical removal. Satisfactory cosmetic and functional results were reached after two months. CONCLUSIONS There is a need for better structured scientific research to evaluate the outcomes and complication rates from all penile augmentation procedures. PMID:23538596

  8. Biodegradation of polystyrene, poly(metnyl methacrylate), and phenol formaldehyde.

    Science.gov (United States)

    Kaplan, D L; Hartenstein, R; Sutter, J

    1979-01-01

    The biodegradation of three synthetic 14C-labeled polymers, poly(methyl methacrylate), phenol formaldehyde, and polystyrene, was studied with 17 species of fungi in axenic cultures, five groups of soil invertebrates, and a variety of mixed microbial communities including sludges, soils, manures, garbages, and decaying plastics. Extremely low decomposition rates were found. The addition of cellulose and mineral failed to increase decomposition rates significantly. PMID:533278

  9. Synthesis and Characterization of Responsive Poly(Alkyl Methacrylate) Topologies

    OpenAIRE

    Kilian, Lars

    2004-01-01

    Dimethacrylate monomers containing two cleavable tert-butyl ester groups were synthesized and utilized in the synthesis of star-shaped polymers. Star polymer coupling was achieved by reacting the living poly(alkyl methacrylate) using 2,5-dimethyl-2,5-hexanediol dimethacrylate (DHDMA) or dicumyl dimethacrylate (DCDMA). These starshaped polymers were cleaved under hydrolytic conditions, leading to significant reductions in molecular weights. The cleavable star-shaped polymers also underwent unc...

  10. Magnetic poly(glycidyl methacrylate) microspheres for protein capture

    Czech Academy of Sciences Publication Activity Database

    Koubková, Jana; Müller, P.; Hlídková, Helena; Plichta, Zdeněk; Proks, Vladimír; Vojtěšek, B.; Horák, Daniel

    2014-01-01

    Roč. 31, č. 5 (2014), s. 482-491. ISSN 1871-6784 R&D Projects: GA ČR GCP207/12/J013; GA MŠk 7E12053 EU Projects: European Commission(XE) 246513 - NADINE Institutional support: RVO:61389013 Keywords : glycidyl methacrylate * microspheres * protein p53 Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.898, year: 2014

  11. Physical Properties of Ethyl Methacrylate as a Bolus in Radiotherapy

    International Nuclear Information System (INIS)

    Bolus is a soft and resilient material which is used for increasing skin dose or to even out the irregular patient contour. The main property of various materials used presently as bolus is the water-equivalent electron density. Ethyl methacrylate is used as a soft-liner in dentistry and its physical and chemical properties are proved to be nontoxic for human body. The goal of this study was to assess the feasibility of using this material as bolus in radiotherapy and also evaluating some parameters such as mass, electron densities, and transmission factors. Computed tomography data from the sample material were acquired to assess mass and electron densities with various techniques (mA and kVp). Circular ROIs were delineated on CT DICOM images and densities were calculated using CT numbers. Transmission factors were calculated for 6 and 18 MV. Evaluation of our results are evident that showed that mass and electron densities of ethyl methacrylate are similar to those of water and soft tissue. Furthermore, transmission factors are close to those of water. According to the results of this study and other properties such as flexibility and harmlessness, it seems that ethyl methacrylate is a suitable material to be used as bolus in radiotherapy.

  12. PolyGuanine methacrylate cryogels for ribonucleic acid purification.

    Science.gov (United States)

    Köse, Kazım; Uzun, Lokman

    2016-05-01

    The isolation and purification of ribonucleic acid have attracted attention recently for the understanding of the functions in detail because of the necessity for the treatment of genetic diseases. In this study, guanine-incorporated polymeric cryogels were developed to obtain highly purified ribonucleic acid. The satisfactory purification performance was achieved with the guanine-incorporated poly (2-hydroxyethyl methacrylate-guanine methacrylate) cryogels. The most crucial advantages to use guanine as a functional monomer are to obtain a real natural interaction between guanine on the polymeric material and cytosine on the ribonucleic acid. Moreover, using cryogel with a highly porous structure and high swelling ratio provide advantages of getting more water within the structure to get more analyte to interact. The characterization of cryogels has proved the success of the synthesis and the perfect natural interaction to be taken place between the ligand (guanine methacrylate) and the cytosine in the ribonucleic acid molecules. Although the pores within the structure of cryogels are small, they provide efficient and fast adsorption. The chromatographic separation performance was investigated for different conditions (pH, temperature etc.). The desorption ratio and reusability were also analyzed at the end of the five adsorption-desorption cycles with no significant changes. PMID:27004613

  13. Performance Improvement of Organic Thin Film Transistors Based on Gate Insulator Polymethyl-Methacrylate-co-Glyciclyl-Methacrylate

    International Nuclear Information System (INIS)

    Organic thin transistors (OTFTs) on indium tin oxide glass substrates are prepared with polymethyl-methacrylate-co-glyciclyl-methacrylate (PMMA-GMA) as the gate insulator layer and copper phthalocyanine as the organic semiconductor layer. By controlling the thickness, the average roughness of surface is reduced and the OTFT performance is improved with leak current decreasing to 10−11 A and on/off ratio of 104. Under the condition of drain-source voltage −20 V, a threshold voltage of −3.5 V is obtained. The experimental results show that PMMA-GMA is a promising insulator material with a dielectric constant in a range of 3.9–5.0

  14. Ultrasound guided supraclavicular block.

    LENUS (Irish Health Repository)

    Hanumanthaiah, Deepak

    2013-09-01

    Ultrasound guided regional anaesthesia is becoming increasingly popular. The supraclavicular block has been transformed by ultrasound guidance into a potentially safe superficial block. We reviewed the techniques of performing supraclavicular block with special focus on ultrasound guidance.

  15. Evaluation of bond strength of silorane and methacrylate based restorative systems to dentin using different cavity models

    Directory of Open Access Journals (Sweden)

    Stephano Zerlottini Isaac

    2013-09-01

    Full Text Available OBJECTIVE: The aim of this in vitro study was to evaluate the microtensile bond strength (µTBS to dentin of two different restorative systems: silorane-based (P90, and methacrylate-based (P60, using two cavity models. MATERIAL AND METHODS: Occlusal enamel of 40 human third molars was removed to expose flat dentin surface. Class I cavities with 4 mm mesial-distal width, 3 mm buccal-lingual width and 3 mm depth (C-factor=4.5 were prepared in 20 teeth, which were divided into two groups (n=10 restored with P60 and P90, bulk-filled after dentin treatment according to manufacturer's instructions. Flat buccal dentin surfaces were prepared in the 20 remaining teeth (C-factor=0.2 and restored with resin blocks measuring 4x3x3 mm using the two restorative systems (n=10. The teeth were sectioned into samples with area between 0.85 and 1.25 mm2 that were submitted to µTBS testing, using a universal testing machine (EMIC at speed of 0.5 mm/min. Fractured specimens were analyzed under stereomicroscope and categorized according to fracture pattern. Data were analyzed using ANOVA and Tukey Kramer tests. RESULTS: For flat surfaces, P60 obtained higher bond strength values compared with P90. However, for Class I cavities, P60 showed significant reduction in bond strength (p0.05, or between Class I Cavity and Flat Surface group, considering P90 restorative system (p>0.05. Regarding fracture pattern, there was no statistical difference among groups (p=0.0713 and 56.3% of the fractures were adhesive. CONCLUSION: It was concluded that methacrylate-based composite µTBS was influenced by cavity models, and the use of silorane-based composite led to similar bond strength values compared to the methacrylate-based composite in cavities with high C-factor.

  16. SYNTHESIS OF POLY(METHYL METHACRYLATE)-graft-POLYSTYRENE BY ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Sheng-min Gong; Qun-sheng Li; Yan Shi; Zhi-feng Fu; Shu-ke Jiao; Wan-tai Yang

    2003-01-01

    The radical copolymerization of methyl methacrylate and 2-hydroxyethyl methacrylate was carried out via atom complex. This polymerization proceeds in a living fashion with controlled molecular weight and low polydispersity. The obtained copolymer was esterified with 2-bromoisobutylryl bromide yielding a macroinitiator, poly(methyl methacrylate-co-2-hydroxyethyl methacrylate-co-2-(2-bromoisobutyryloxy)ethyl methacrylate), and its structure was characterized by 1HNMR. This macroinitiator was used for ATRP of styrene to synthesize poly(methyl methacrylate)-grafi-polystyrene. The molecular weight of graft copolymer increased with the monomer conversion, and the polydispersity remained relatively low.The individual grafted polystyrene chains were cleaved from the macroinitiator backbone by hydrolysis and the hydrolyzed product was characterized by 1H-NMR and GPC.

  17. Self-assembling Behavior of Amphiphilic Copolymer Containing Cross-linked Hydrophilic Block in Ethanol

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The self-assembly behavior of the amphiphilic block copolymer poly( methyl methacrylate)-block-poly( lead dimethacrylate) (PMMA-b-PLDMA) with cross-linked hydrophilic block (PLDMA) in ethanol was investigated. The results show that the size and morphology of the resulting micelle or micellar aggregates are ascribed to the content of ethanol and the nature of the solvent mixture. PbS nanoparticles were formed in the micelle by in situ reaction with H2S gas. The morphology and size of the self-assembly objects were investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

  18. Effects of Surfactants on the Properties of Mortar Containing Styrene/Methacrylate Superplasticizer

    OpenAIRE

    El-Sayed Negim; Latipa Kozhamzharova; Jamal Khatib; Lyazzat Bekbayeva; Craig Williams

    2014-01-01

    The physical and mechanical properties of mortar containing synthetic cosurfactants as air entraining agent are investigated. The cosurfactants consist of a combination of 2% dodecyl benzene sodium sulfonate (DBSS) and either 1.5% polyvinyl alcohol (PVA) or 1.5% polyoxyethylene glycol monomethyl ether (POE). Also these cosurfactants were used to prepare copolymers latex: styrene/butyl methacrylate (St/BuMA), styrene/methyl methacrylate (St/MMA), and styrene/glycidyl methacrylate (St/GMA), in...

  19. Detection of NO2 Based on 4-Carboxyl-4'-hydroxy Azobenzene and Its Cu(Ⅱ) Complex

    Institute of Scientific and Technical Information of China (English)

    LI Jian; GONG Yun; QIN Jian-Bo; LIN Jian-Hua

    2013-01-01

    An organic ligand and its Cu(Ⅱ) complex formulated as (C13H10N2O3)·5H2O (H2L·5H2O,1) and Cu(HL)2(phen)·0.125H2O (2,H2L =4-carboxyl-4'-hydroxy azobenzene,phen =1,10-phenanthroline) have been synthesized and structurally characterized by single-crystal X-ray diffraction.In the two compounds,H2L and HL exhibit a trans-conformation.Complex 2 shows a mononuclear Cu(Ⅱ) structure with the hydroxyl group of HL uncoordinated.Complex 2 is assembled into a three-dimensional (3D) supramolecular architecture by hydrogen bonds and π-π stacking interactions,H2L and compound 2 can detect NO2 via reversible and irreversible color changes,respectively.The mechanism for the color changes is investigated.

  20. Engineering Light-Mediated Bistable Azobenzene Switches Bearing Urea d-Aminoglucose Units for Chiral Discrimination of Carboxylates.

    Science.gov (United States)

    Dąbrowa, Kajetan; Niedbała, Patryk; Jurczak, Janusz

    2016-05-01

    The symmetrical molecular receptors 1a and 1b consisting of a photochemically addressable azobenzene tether functionalized with urea hydrogen-bonding groups and d-carbohydrates as chiral selectors were developed to achieve control over the chiral recognition of α-amino acid-derived carboxylates. The photo- and thermally interconvertible planar E-1 and concaved Z-1 were found to exhibit different affinities, selectivities, and binding modes toward these biologically important anions in a highly polar medium (DMSO + 0.5% H2O). Binding affinity for the same enantiomerically pure guest was up to 3 times higher for E-1 than for Z-1 (cf. parameter β). In addition, the rate of thermal Z → E isomerization was found to depend on the chiral binding ability of Z-1, i.e., more strongly bound carboxylate enantiomer as well as higher enantiomer concentration caused faster relaxation to E-1. PMID:27057921

  1. PHOTOINDUCED BIREFRINGENCE AND NUMERICAL SOLUTION OF A NEW DYNAMIC MODEL IN AN AMORPHOUS COPOLYMER CONTAINING AZOBENZENE GROUPS

    Institute of Scientific and Technical Information of China (English)

    Ling-zhi Zhang; Zhi-gang Cai; Valerica Ninulescu; Ke Jin; Zhao-xi Liang

    2001-01-01

    Photoinduced birefringence is investigated in a new amorphous copolymer containing azobenzene groups. The levels of birefringence signal are found to depend on the polarization angle between the pump beam and the probe beam, and on the ellipticity of the pump beam. Both the growth and decay processes of the birefringence signal can be described by known biexponential equations. The rate constants and the amplitudes associated with the growth process of the photoinduced birefringence are observed to display a linear dependence with the pump beam intensity. A new dynamic model of the photoinduced birefringence is presented taking into account the contributions of both the trans and cis isomers ofazobenzene groups and the local polymer segments. The numerical treatment of this model shows good agreement with the experimental data in the whole writing-erasing processes of the photoinduced birefringence conducted in our polymer samples.

  2. Responsive behavior of 4-(N-maleimido)azobenzene in polymers with aromatic main chain and side chain linked units

    Energy Technology Data Exchange (ETDEWEB)

    Airinei, Anton; Rusu, Elena; Barboiu, Virgil, E-mail: airineia@icmpp.r [Romanian Academy, Iasi (Romania). Petru Poni Institute of Macromolecular Chemistry

    2010-07-01

    Polymer matrices with aromatic main chain and side chain linked units (polystyrene, polysulfone) were employed to construct thin films containing maleimidoazobenzene molecules in order to develop new materials with responsive properties. The photochromic behavior of the active compound was studied both in the solid and solution state for comparison. The thermal cis-trans isomerization of azobenzene chromophores in polymer films follows two different kinetic pathways. A double-exponential relaxation process (fast and slow) took place in polystyrene matrix under 70 deg C while the thermal isomerization at 70 deg C and higher follows a first-order kinetics. The cis isomer content corresponding to the photostationary state was found to be lower in polymer films than in solution. (author)

  3. Synthesis, micellar properties and application of amphiphilic linear block copolymers with different microstructure but same molecular weight

    OpenAIRE

    Schmitz, Christof Jan Wilhelm

    2009-01-01

    This dissertation is concerned with the synthesis and micellisation behaviour of linear block copolymers based on methacrylates by means of the modern controlled radical polymerisation technique, namely the atom transfer radical polymerisation (ATRP). The objective was the synthesis of linear block copolymers with different microstructure but same molecular weight. The chosen synthesis strategy should be applicable for various monomer pairs with different polarities and should include the use...

  4. STUDY ON FLUORESCENCE BEHAVIOUR OF EU3+ CONTAINING POLY(METHYL METHACRYLATE)

    Institute of Scientific and Technical Information of China (English)

    ZHANG Qijin; WANG Pin

    1997-01-01

    Fluorimetry has been used to characterize ionomers synthesized by copolymerization of methyl methacrylate, methacrylic acid and europium methacrylate (EMA). Under excitation of UV light at 375 nm no self-quenching was found in fluorescence of EMA containing ionomers at 615nm within the concentration range of 1.6 × 10-2 to 11.49 ×10-2 mol%. This means that the distance between two Eu3+ ions is larger than 5 nm. In the same concentration range self-quenching took place in europium octanoate (EOA) containing poly(methyl methacrylate) in which EOA was doped as an additive.

  5. Block clustering with collapsed latent block models

    OpenAIRE

    Wyse, Jason; Friel, Nial

    2010-01-01

    We introduce a Bayesian extension of the latent block model for model-based block clustering of data matrices. Our approach considers a block model where block parameters may be integrated out. The result is a posterior defined over the number of clusters in rows and columns and cluster memberships. The number of row and column clusters need not be known in advance as these are sampled along with cluster memberhips using Markov chain Monte Carlo. This differs from existing work on latent bloc...

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

    Science.gov (United States)

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

    2015-08-01

    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.

  7. Catalytic transfer hydrogenation of azobenzene by low-valent nickel complexes: a route to 1,2-disubstituted benzimidazoles and 2,4,5-trisubstituted imidazolines.

    Science.gov (United States)

    Zurita, Daniel A; Flores-Alamo, Marcos; García, Juventino J

    2016-06-21

    The one-pot synthesis of 1,2-disubstituted benzimidazoles by the transfer hydrogenation of azobenzene, using benzylamine as a hydrogen donor, sequential rearrangement of hydrazobenzene to semidine and further condensation with N-benzylideneamine is reported, catalyzed by 2 mol% of [Ni(COD)2] : dippe. The N2 substitution on benzimidazole can be controlled by the selection of different azobenzenes and C2 substitution will only depend on the chosen benzylamine. The current methodology avoids the addition of external oxidants, which are needed in the classical benzimidazole synthesis. In addition, the byproduct, N-benzylideneamine, obtained from dehydrogenation of benzylamine produced 2,4,5-trisubstituted imidazolines by cyclization and C-H functionalization, and this route was optimized with the use of 2 mol% of [Ni(COD)2] : 2PPh3. PMID:27254530

  8. The Radiation Induced Graft Copolymerization of Methacrylic Acid to Nylon

    International Nuclear Information System (INIS)

    The grafting of methacrylic acid to nylon by the preirradiation technique has been studied. The rate of grafting is appreciably larger than that of homopolymerization. No simple relation exists between reaction rate and total dose. The temperature dependence of the rate of grafting to the fibre, preirradiated in air, indicates that initiation of grafting is likely to take place by decomposition of peroxide groups formed on irradiation. Electrical resistance measurements on the irradiated fibre indicate that this has been reduced by a factor of 10. (author)

  9. Density of radiolytic gas bubbles in polymethyl methacrylate

    Science.gov (United States)

    Makkonen, T.; Tiainen, O. J. A.; Valkiainen, M.; Winberg, M.

    The density of the radiolytic gas bubbles in irradiated polymethyl methacrylate was measured during subsequent heat treatment as a function of radiation dose. The samples were irradiated in the core of the Triga Mark II reactor in Otaniemi. After the irradiation periods the samples were heat treated at 393 K. The number of the bubbles could be explained by a thermal activation model. The bubbles are born in material inhomogeneities and the threshold dose for the bubble initiation was about 25 Mrad for the heat treatment at 393 K under the atmospheric pressure.

  10. Computational studies of ultraviolet ablation of poly(methyl methacrylate)

    International Nuclear Information System (INIS)

    The results from our recent molecular dynamics and electronic calculations studies of the interaction of ultraviolet light with poly(methyl methacrylate) are discussed. Molecular dynamics simulations in the photochemical and photothermal regimes demonstrate the delayed onset of ablation due to the slow pressure relaxation in the polymeric material. Electronic structure calculations show the possible wavelength-dependent pathways of exothermic and endothermic release of gaseous and small molecules which could induce the ablation pocess. The results from our studies are the centerpiece for the current development of the mesoscale model of the light irradiation of polymeric material

  11. Preparation of Pickering double emulsions using block copolymer worms.

    Science.gov (United States)

    Thompson, Kate L; Mable, Charlotte J; Lane, Jacob A; Derry, Mathew J; Fielding, Lee A; Armes, Steven P

    2015-04-14

    The rational formulation of Pickering double emulsions is described using a judicious combination of hydrophilic and hydrophobic block copolymer worms as highly anisotropic emulsifiers. More specifically, RAFT dispersion polymerization was utilized to prepare poly(lauryl methacrylate)-poly(benzyl methacrylate) worms at 20% w/w solids in n-dodecane and poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate)-poly(benzyl methacrylate) worms at 13% w/w solids in water by polymerization-induced self-assembly (PISA). Water-in-oil-in-water (w/o/w) double emulsions can be readily prepared with mean droplet diameters ranging from 30 to 80 μm using a two-stage approach. First, a w/o precursor emulsion comprising 25 μm aqueous droplets is prepared using the hydrophobic worms, followed by encapsulation within oil droplets stabilized by the hydrophilic worms. The double emulsion droplet diameter and number of encapsulated water droplets can be readily varied by adjusting the stirring rate employed during the second stage. For each stage, the droplet volume fraction is relatively high at 0.50. The double emulsion nature of the final formulation was confirmed by optical and fluorescence microscopy studies. Such double emulsions are highly stable to coalescence, with little or no change in droplet diameter being detected over storage at 20 °C for 10 weeks as judged by laser diffraction. Preliminary experiments indicate that the complementary o/w/o emulsions can also be prepared using the same pair of worms by changing the order of homogenization, although somewhat lower droplet volume fractions were required in this case. Finally, we demonstrate that triple and even quadruple emulsions can be formulated using these new highly anisotropic Pickering emulsifiers. PMID:25834923

  12. The immobilization of enzymes onto poly(ethylene)-g. co-methacrylic acid, (poly(ethylene)-g. co-hydroxyethyl methacrylate)-g. co-methacrylic acid and (poly(ethylene)-g. co-methacrylic acid)-g. co-hydroxyethyl methacrylate

    Energy Technology Data Exchange (ETDEWEB)

    Da Silva, M.A.; Gil, M.H.; Guiomar, J.; Lapa, E.; Machado, E.; Moreira, M. (Coimbra Univ. (Portugal). Dept. of Chemistry); Guthrie, J.T. (Leeds Univ. (UK). Dept. of Colour Chemistry); Kotov, S. (Higher Inst. of Chemical Technology, Burgas (Bulgaria))

    1990-01-01

    A series of graft copolymers has been prepared on the poly(ethylene) backbone. These carry functional groups which are effective in coupling and provide a level of hydrophilicity which is thought to be consistent with generating a suitable micro-environment for enzyme immobilization and subsequent enhanced biocatalyst stability. Four enzymes have been immobilized. These are papain, trypsin, glucose oxidase and {alpha}-chymotrypsin. The parent copolymers were assembled via radiation-induced grafting. Secondary grafting was achieved in two ways. The first involved grafting methacrylic acid onto poly(ethylene)-g.co-hydroxyethyl methacrylate, while the second involved grafting hydroxyethyl methacrylate onto poly(ethylene)-g.co-methacrylic acid. The results suggest that a high degree of specificity arises in the systems examined with regard to the enzymes, the type of copolymers and the coupling procedures. Generally, relatively large amounts of enzyme become covalently attached to the copolymers, though the overall level of activity is low. In this work it has been observed that the most satisfactory results were obtained when the partly hydrolyzed poly(ethylene)-g.co-hydroxyethyl methacrylate was used in the immobilization of the biocatalysts. (author).

  13. The immobilization of enzymes onto poly(ethylene)—g.co—methacrylic acid, [poly(ethylene)—g.co—hydroxyethyl methacrylate]—g.co—methacrylic acid and [poly(ethylene)—g.co—methacrylic acid]—g.co—hydroxyethyl methacrylate

    Science.gov (United States)

    Da Silva, M. Alves; Gil, M. H.; Guiomar, J.; Lapa, E.; Machado, E.; Moreira, M.; Guthrie, J. T.; Kotov, S.

    A series of graft copolymers has been prepared based on the poly(ethylene) backbone. These carry functional groups which are effective in coupling and provide a level of hydrophilicity which is thought to be consistent with generating a suitable micro-environment for enzyme immobilization and subsequent enhanced biocatalyst stability. Four enzymes have been immobilized. These are papain, trypsin, glucose oxidase and α-chymotrypsin. The parent copolymers were assembled via radiation-induced grafting. Secondary grafting was achieved in two ways. The first involved grafting methacrylic acid onto poly(ethylene)—g.co—hydroxyethyl methacrylate, while the second involved grafting hydroxyethyl methacrylate onto poly(ethylene)—g.co—methacrylic acid. The results suggest that a high degree of specificity arises in the systems examined with regard to the enzymes, the type of copolymers and the coupling procedures. Generally, relatively large amounts of enzyme become covalently attached to the copolymers, though the overall level of activity is low. In this work it has been observed that the most satisfactory results were obtained when the partly hydrolyzed poly(ethylene)—g.co—hydroxyethyl methacrylate was used in the immobilization of the biocatalysts.

  14. Supramolecular Phase-Selective Gelation by Peptides Bearing Side-Chain Azobenzenes: Effect of Ultrasound and Potential for Dye Removal and Oil Spill Remediation

    OpenAIRE

    Jürgen Bachl; Stefan Oehm; Judith Mayr; Carlos Cativiela; José Juan Marrero-Tellado; David Díaz Díaz

    2015-01-01

    Phase selective gelation (PSG) of organic phases from their non-miscible mixtures with water was achieved using tetrapeptides bearing a side-chain azobenzene moiety. The presence of the chromophore allowed PSG at the same concentration as the minimum gelation concentration (MGC) necessary to obtain the gels in pure organic phases. Remarkably, the presence of the water phase during PSG did not impact the thermal, mechanical, and morphological properties of the corresponding organogels. In the ...

  15. 石墨烯/偶氮杂化材料研究进展%Progress on graphene/azobenzene hybrid materials

    Institute of Scientific and Technical Information of China (English)

    王东瑞; 王晓工

    2012-01-01

    Graphene, a true two dimensional nanomaterial with the layer thickness of one atom, has showed many outstanding properties and aroused tremendous research enthusiasm. Azobenzene-containing polymers and other materials have also attracted considerable attention because of the unique photoresponsive properties. Graphene/ azobenzene hybrids materials can combine interesting properties of graphere and azobenzene-containing materials and have been studied in authors and other laboratories in recent years. This review highlighted some recent research progresses in this area. The content of this article included the preparations of graphene/azobenzene hybrids materials through surface-grafting of azo polymers, covalent-bonding modification with low-molecular-weight azo compounds and electrostatic layer-by-layer deposition. The photoresponsive properties and application in the electronchemical energy storage device of the materials were also reviewed in some detail.%石墨烯作为一种新型二维平面纳米材料,表现出许多优异的物理性质.含偶氮苯的化合物和聚合物作为功能材料具有独特的光响应性质.将石墨烯的特性与偶氮材料的光响应性相结合,有望发展一类具有卓越性能的新型光电功能材料.本文总结了石墨烯/偶氮杂化材料这一研究方向的最新进展,重点介绍了杂化材料的制备、表征和光电功能性质等,并简要展望了这类材料的发展前景.

  16. Surface Roughening of Polystyrene and Poly(methyl methacrylate in Ar/O2 Plasma Etching

    Directory of Open Access Journals (Sweden)

    Amy E. Wendt

    2010-12-01

    Full Text Available Selectively plasma-etched polystyrene-block-poly(methyl methacrylate (PS-b-PMMA diblock copolymer masks present a promising alternative for subsequent nanoscale patterning of underlying films. Because mask roughness can be detrimental to pattern transfer, this study examines roughness formation, with a focus on the role of cross-linking, during plasma etching of PS and PMMA. Variables include ion bombardment energy, polymer molecular weight and etch gas mixture. Roughness data support a proposed model in which surface roughness is attributed to polymer aggregation associated with cross-linking induced by energetic ion bombardment. In this model, RMS roughness peaks when cross-linking rates are comparable to chain scissioning rates, and drop to negligible levels for either very low or very high rates of cross-linking. Aggregation is minimal for very low rates of cross-linking, while very high rates produce a continuous cross-linked surface layer with low roughness. Molecular weight shows a negligible effect on roughness, while the introduction of H and F atoms suppresses roughness, apparently by terminating dangling bonds. For PS etched in Ar/O2 plasmas, roughness decreases with increasing ion energy are tentatively attributed to the formation of a continuous cross-linked layer, while roughness increases with ion energy for PMMA are attributed to increases in cross-linking from negligible to moderate levels.

  17. Poly(methacrylic acid)-mediated morphosynthesis of PbWO{sub 4} micro-crystals

    Energy Technology Data Exchange (ETDEWEB)

    Yu, J.G.; Zhao, X.F.; Liu, S.W. [Wuhan University of Technology, State Key Lab of Advanced Technology for Materials Synthesis and Processing, Wuhan (China); Li, M.; Mann, S. [University of Bristol, School of Chemistry, Bristol (United Kingdom); Ng, D.H.L. [The Chinese University of Hong Kong, Department of Physics, Hong Kong (China)

    2007-04-15

    PbWO{sub 4} crystals with various morphologies were fabricated via a facile poly(methacrylic acid)-mediated hydrothermal route. Novel microsized PbWO{sub 4} single crystals with a needle-like shape as well as other morphologies, such as a fishbone, dendrite, sphere, spindle, ellipsoid, rod, and dumbbell with two dandelion-like heads, could be produced. The presence of PMAA, [Pb{sup 2+}]/[WO{sub 4} {sup 2-}] molar ratio (R), and aging temperature played key roles in the formation of the PbWO{sub 4} needle-like structures. Between temperatures of 60 to 150 C, the length and photoluminescence intensities of the PbWO{sub 4} micro needles significantly increased with aging temperature, while the diameter did not change remarkably. Time-dependent experiments revealed that the formation of PbWO{sub 4} microneedles involved an unusual growth process, involving nucleation, oriented assembly and controlled mesoscale restructuring of nanoparticle building blocks. (orig.)

  18. Symmetrical trimeric star-shaped mesogens based on 1,3,5-trisubstituted benzene incorporating Schiff base and azobenzene fragments as the peripheral units: Synthesis and mesomorphic properties

    Indian Academy of Sciences (India)

    Guan-Yeow Yeap; Yew-Hong Ooi; Nozomi Uchida; Masato M Ito

    2014-05-01

    Two series of symmetrical three-armed star-shaped mesogens based on 1,3,5-trihydroxybenzene as a core unit, interconnecting three Schiff base or azobenzene moieties via oxymethylene spacers have been synthesized and characterized by spectroscopic techniques. Every member in these series possesses either chlorine (Cl) or bromine (Br) terminal atom, with different alkyl spacer length (CH2 whereby ranging from 3 to 6). Their thermal stability and mesomorphic properties are investigated by employing DSC and POM. The dependence of phase transition in relation to the alkyl spacer length is shown by both series. These star-shaped mesogens exhibit only nematic and smectic phases. The difference between the two series lies on the structure of linking group in the peripheral units (-CH=N- for series PSB-X- and -N=N- for series PAZ-X-). Therefore, a comparison study of the mesomorphic properties between these two series of star-shaped mesogens is discussed whereby the azobenzene-basedmesogens are thermally more stable than the Schiff base counterpart. In addition, soft crystalline phase is observed for the azobenzene-based star-shaped mesogens possessing hexyl alkyl spacer.

  19. Backfilling-Free Strategy for Biopatterning on Intrinsically Dual-Functionalized Poly[2-Aminoethyl Methacrylate-co-Oligo(Ethylene Glycol) Methacrylate] Films.

    Science.gov (United States)

    Lee, Bong Soo; Lee, Juno; Han, Gyeongyeop; Ha, EunRae; Choi, Insung S; Lee, Jungkyu K

    2016-07-20

    We demonstrated protein and cellular patterning with a soft lithography technique using poly[2-aminoethyl methacrylate-co-oligo(ethylene glycol) methacrylate] films on gold surfaces without employing a backfilling process. The backfilling process plays an important role in successfully generating biopatterns; however, it has potential disadvantages in several interesting research and technical applications. To overcome the issue, a copolymer system having highly reactive functional groups and bioinert properties was introduced through a surface-initiated controlled radical polymerization with 2-aminoethyl methacrylate hydrochloride (AMA) and oligo(ethylene glycol) methacrylate (OEGMA). The prepared poly(AMA-co-OEGMA) film was fully characterized, and among the films having different thicknesses, the 35 nm-thick biotinylated, poly(AMA-co-OEGMA) film exhibited an optimum performance, such as the lowest nonspecific adsorption and the highest specific binding capability toward proteins. PMID:27252120

  20. Preparation of Novel Poly(hydroxyethyl methacrylate-co-glycidyl methacrylate-Grafted Core-Shell Magnetic Chitosan Microspheres and Immobilization of Lactase

    Directory of Open Access Journals (Sweden)

    Wendy Katiyo

    2013-06-01

    Full Text Available Poly(hydroxyethyl methacrylate-co-glycidyl methacrylate-grafted magnetic chitosan microspheres (HG-MCM were prepared using reversed-phase suspension polymerization method. The HG-MCM presented a core-shell structure and regular spherical shape with poly(hydroxyethyl methacrylate-co-glycidyl methacrylate grafted onto the chitosan layer coating the Fe3O4 cores. The average diameter of the magnetic microspheres was 10.67 μm, within a narrow size distribution of 6.6–17.4 μm. The saturation magnetization and retentivity of the magnetic microspheres were 7.0033 emu/g and 0.6273 emu/g, respectively. The application of HG-MCM in immobilization of lactase showed that the immobilized enzyme presented higher storage, pH and thermal stability compared to the free enzyme. This indicates that HG-MCM have potential applications in bio-macromolecule immobilization.

  1. Monodisperse macroporous poly(glycidyl methacrylate) microspheres coated with silica: Design, preparation and characterization

    Czech Academy of Sciences Publication Activity Database

    Grama, Silvia; Plichta, Zdeněk; Trchová, Miroslava; Kovářová, Jana; Beneš, Milan J.; Horák, Daniel

    2014-01-01

    Roč. 77, April (2014), s. 11-17. ISSN 1381-5148 R&D Projects: GA MŠk EE2.3.30.0029 Institutional support: RVO:61389013 Keywords : multistep swelling polymerization * poly(glycidyl methacrylate) * poly(2,3-dihydroxypropyl methacrylate) Subject RIV: CE - Biochemistry Impact factor: 2.515, year: 2014

  2. Blends of poly (vinylidene fluoride) with stereoregular poly (akyl methacrylate) s

    OpenAIRE

    Roerdink, Eize

    1980-01-01

    This thesis describes various aspects of polymer-polymer blends of poly (vinylidene fluoride) (PVF2) with stereoregular poly (alkyl methacrylate)s, like mutual miscibility, nature and size of the interactions between the complementary polymers, Lower Critical Solution Temperature (LCST) behaviour, complex formacion and remplate polymerization. ... Zie: Summary

  3. 21 CFR 177.2000 - Vinylidene chloride/methyl acrylate/methyl methacrylate polymers.

    Science.gov (United States)

    2010-04-01

    ... methacrylate polymers. 177.2000 Section 177.2000 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF...: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.2000 Vinylidene chloride/methyl acrylate/methyl methacrylate polymers. The vinylidene chloride/methyl...

  4. Glycol methacrylate embedding for light microscopy : Basic principles and trouble-shooting

    NARCIS (Netherlands)

    Gerrits, PO; Horobin, RW

    1996-01-01

    Acrylic resin mixtures are now widely used as embedding media for the preparation of tissue sections. Most of these mixtures are based on 2-hydroxyethyl methacrylate (glycol methacrylate, GMA). Resin embedding preserves tissue components far better than paraffin, celloidin or frozen sections. The pr

  5. Superhydrophobic terpolymer nanofibers containing perfluoroethyl alkyl methacrylate by electrospinning

    Energy Technology Data Exchange (ETDEWEB)

    Cengiz, Ugur, E-mail: ucengiz@gyte.edu.tr [Department of Chemical Engineering, Gebze Institute of Technology, Cayirova, 41400 Kocaeli (Turkey); Avci, Merih Z. [Polymer Science and Technology, Deparment of Chemistry, Istanbul Technical University, Maslak 34469, Istanbul (Turkey); Erbil, H. Yildirim [Department of Chemical Engineering, Gebze Institute of Technology, Cayirova, 41400 Kocaeli (Turkey); Sarac, A. Sezai [Polymer Science and Technology, Deparment of Chemistry, Istanbul Technical University, Maslak 34469, Istanbul (Turkey)

    2012-05-15

    A new statistical terpolymer containing perfluoroethyl alkyl methacrylate (Zonyl-TM), methyl methacrylate and butyl acrylate, poly(Zonyl-TM-ran-MMA-ran-BA) was synthesized in supercritical carbon dioxide at 200 bar and 80 Degree-Sign C using AIBN as an initiator by heterogeneous free radical copolymerization. Nanofibers of this terpolymer were produced by electrospinning from its DMF solution. The structural and thermal properties of terpolymers and electrospun poly(Zonyl-TM-MMA-BA) nanofibers were analyzed using Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy and differential scanning calorimetry. Nanofiber morphology was investigated by scanning electron microscopy. Electrospun nanofiber layer was found to be superhydrophobic with a water contact angle of 172 {+-} 1 Degree-Sign and highly oleophobic with hexadecane, glycerol and ethylene glycol contact angles of 70 {+-} 1 Degree-Sign , 167 {+-} 1 Degree-Sign and 163 {+-} 1 Degree-Sign respectively. The change of the contact angle results on the electrospun fiber layer and flat terpolymer surfaces by varying feed monomer composition were compared and discussed in the text.

  6. Sulfone-Containing Methacrylate Homopolymers: Wetting and Thermal Properties.

    Science.gov (United States)

    Fujii, Shota; McCarthy, Thomas J

    2016-01-26

    Although the sulfonyl functional group has a large dipole moment and compounds containing them (sulfones) have correspondingly high dielectric constants, this chemical structure has been neglected for use as a functional group to render surfaces hydrophilic. We have prepared three methacrylate polymers containing side chains capped with sulfolane, methylsulfone, and ethylsulfone functionality. The sulfolane-containing polymer exhibits an unusually high glass transition temperature (Tg = 188 °C) for a methacrylate polymer and slightly different thermal degradation behavior than the other two sulfone-containing polymers, likely due to the bulky structure of the sulfolane group in the polymer side chain. At macroscopic polymer film/water interfaces, the sulfone-containing side chains exposed to the interface impart hydrophilic properties as assessed by contact angle analysis. The hydrophilicities of sulfolane and methylsulfone surfaces are similar, and greater than the ethylsulfone surface. Although the chemical compositions of the sulfolane and ethylsulfone polymers are almost identical, the five-membered ring structure of sulfolane allows the sulfonyl moiety to be exposed at the interface in a manner similar to that of the methylsulfone polymer. The sulfonyl group at the ethylsulfone polymer/water interface is slightly masked by the ethyl group. Interestingly, the sulfolane surface displays a higher affinity to methylene iodide and n-hexadecane probe fluids compared to the other sulfone surfaces, suggesting that the five-membered ring structure of the sulfolane moiety can orient in a manner that shelters the sulfonyl group at hydrophobic interfaces. PMID:26716766

  7. Cobalt hexacyanoferrate-poly(methyl methacrylate) composite: Synthesis and characterization

    International Nuclear Information System (INIS)

    Graphical abstract: The preparation of cobalt hexacyanoferrate nanoparticles-poly(methyl methacrylate) (CoHCF-PMMA) composites are described together with their characterization and thermochromic properties. CoHCF nanoparticles - investigated by dynamic light scattering - were prepared by optimizing solvent composition and temperature to obtain nanoparticles with a reduced degree of aggregation. The nanoparticles were embedded in a PMMA matrix to obtain a transparent coloured composite which was studied by transmission electron microscopy. The nanoparticle chromic features, enhanced by their reduced sizes, were investigated by UV-vis and FT-IR spectroscopy. - Abstract: The preparation of cobalt hexacyanoferrate nanoparticles-poly(methyl methacrylate) (CoHCF-PMMA) composites are described together with their characterization and thermochromic properties. CoHCF nanoparticles - investigated by dynamic light scattering - were prepared by optimizing solvent composition and temperature to obtain nanoparticles with a reduced degree of aggregation. The nanoparticles were embedded in a PMMA matrix to obtain a transparent coloured composite which was studied by transmission electron microscopy. The nanoparticle chromic features, enhanced by their reduced sizes, were investigated by UV-vis and FT-IR spectroscopy.

  8. Superhydrophobic terpolymer nanofibers containing perfluoroethyl alkyl methacrylate by electrospinning

    International Nuclear Information System (INIS)

    A new statistical terpolymer containing perfluoroethyl alkyl methacrylate (Zonyl-TM), methyl methacrylate and butyl acrylate, poly(Zonyl-TM-ran-MMA-ran-BA) was synthesized in supercritical carbon dioxide at 200 bar and 80 °C using AIBN as an initiator by heterogeneous free radical copolymerization. Nanofibers of this terpolymer were produced by electrospinning from its DMF solution. The structural and thermal properties of terpolymers and electrospun poly(Zonyl-TM-MMA-BA) nanofibers were analyzed using Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy and differential scanning calorimetry. Nanofiber morphology was investigated by scanning electron microscopy. Electrospun nanofiber layer was found to be superhydrophobic with a water contact angle of 172 ± 1° and highly oleophobic with hexadecane, glycerol and ethylene glycol contact angles of 70 ± 1°, 167 ± 1° and 163 ± 1° respectively. The change of the contact angle results on the electrospun fiber layer and flat terpolymer surfaces by varying feed monomer composition were compared and discussed in the text.

  9. Graft Copolymerization Of Methyl Methacrylate Onto Agave Cellulose

    International Nuclear Information System (INIS)

    The grafting polymerization of methyl methacrylate (MMA) and Agave cellulose was prepared and the grafting reaction conditions were optimized by varying the reaction time and temperature, and ratio of monomer to cellulose. The resulting graft copolymers were characterized by Fourier transform infrared, X-ray diffraction analysis, thermogravimetric analysis, and scanning electron microscopy (SEM). The experimental results showed that the optimal conditions were at a temperature of 45 degree Celsius for 90 min with ratio monomer to cellulose at 1:1 (g/ g). An additional peak at 1738 cm-1 which was attributed to the C=O of ester stretching vibration of poly(methyl methacrylate), appeared in the spectrum of grafted Agave cellulose. A slight decrease of crystallinity index upon grafting was found from 0.74 to 0.68 for cellulose and grafted cellulose, respectively. Grafting of MMA onto cellulose enhanced its thermal stability and SEM observation further furnished evidence of grafting MMA onto Agave cellulose with increasing cellulose diameter and surface roughness. (author)

  10. Neural Network Models for Free Radical Polymerization of Methyl Methacrylate

    International Nuclear Information System (INIS)

    In this paper, a neural network modeling of the batch bulk methyl methacrylate polymerization is performed. To obtain conversion, number and weight average molecular weights, three neural networks were built. Each was a multilayer perception with one or two hidden layers. The choice of network topology, i.e. the number of hidden layers and the number of neurons in these layers, was based on achieving a compromise between precision and complexity. Thus, it was intended to have an error as small as possible at the end of back-propagation training phases, while using a network with reduced complexity. The performances of the networks were evaluated by comparing network predictions with training data, validation data (which were not uses for training), and with the results of a mechanistic model. The accurate predictions of neural networks for monomer conversion, number average molecular weight and weight average molecular weight proves that this modeling methodology gives a good representation and generalization of the batch bulk methyl methacrylate polymerization. (author)

  11. Synthesis of Methyl Methacrylate from Coal-Derived Syngas

    Energy Technology Data Exchange (ETDEWEB)

    Gerald N. Choi; James J. Spivey; Jospeh R. Zoeller; Makarand R. Gogate; Richard D. Colberg; Samuel S. Tam

    1998-04-17

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. RTI has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, RTI is currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last month, RTI has finalized the design of a fixed-bed microreactor system for DME partial oxidation reactions. RTI incorporated some design changes to the feed blending system, so as to be able to blend varying proportions of DME and oxygen. RTI has also examined the flammability limits of DME-air mixtures. Since the lower flammability limit of DME in air is 3.6 volume percent, RTI will use a nominal feed composition of 1.6 percent in air, which is less than half the lower explosion limit for DME-air mixtures. This nominal feed composition is thus considered operationally safe, for DME partial oxidation reactions. RTI is also currently developing an analytical system for DME partial oxidation reaction system.

  12. Incomplete block designs

    CERN Document Server

    Dey, Aloke

    2010-01-01

    This book presents a systematic, rigorous and comprehensive account of the theory and applications of incomplete block designs. All major aspects of incomplete block designs are considered by consolidating vast amounts of material from the literature - the classical incomplete block designs, like the balanced incomplete block (BIB) and partially balanced incomplete block (PBIB) designs. Other developments like efficiency-balanced designs, nested designs, robust designs, C-designs and alpha designs are also discussed, along with more recent developments in incomplete block designs for special t

  13. Radiation Crosslinking of a Mixture of Poly vinyle Alcohol Methacrylic acid and 2-Hydroxy ethyle Methacrylate to Removal of Pollutant Dyes from its Aqueous Solution

    International Nuclear Information System (INIS)

    Hydrogels based on poly vinyle alcohol methacrylic acid/ 2-hydroxy ethyle methacrylate [P(PVA-MAAc/HEMA)] were synthesized by gamma-radiation. The prepared hydrogels were characterized by infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and thermal gravimetric analysis (TGA). The results of the adsorption studies reveals the higher adsorption capacity of P(PVA-MAAc/ HEMA), hydrogel for the removal of methylene blue and xylenol orange dyes from aqueous solution.

  14. PEG-modified macroporous poly(glycidyl methacrylate) and poly(2-hydroxyethyl methacrylate) microspheres to reduce non-specific protein adsorption

    Czech Academy of Sciences Publication Activity Database

    Hlídková, Helena; Horák, Daniel; Proks, Vladimír; Kučerová, Z.; Pekárek, Michal; Kučka, Jan

    2013-01-01

    Roč. 13, č. 4 (2013), s. 503-511. ISSN 1616-5187 R&D Projects: GA ČR GCP207/12/J013; GA ČR GAP206/12/0381; GA MŠk 7E12053 EU Projects: European Commission(XE) 246513 - NADINE Institutional support: RVO:61389013 Keywords : coatings * glycidyl methacrylate * 2-hydroxyethyl methacrylate Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.650, year: 2013

  15. Recognition and Release of Nalidixic Acid Using Uniformly Sized -Imprinted Nanospheres: Methacrylic Acid to Methyl Methacrylate Different Mole Ratios

    Directory of Open Access Journals (Sweden)

    Mehdi Forouzani

    2013-01-01

    Full Text Available In the presence of imprinting molecules of Nalidixic acid, uniformly sized molecularly imprinted polymers (MIPs in nanometer range were synthesized. The MIPs were successfully prepared by precipitation polymerization using methacrylic acid (MAA and methyl methacrylate (MMA as functional monomers at different mole ratios. The effect of combination of MAA-to-MMA on the morphology, binding, recognition and release behaviors of the final particles were studied. The produced polymers were characterized by differential scanning calorimetry and their morphology was precisely examined by scanning electron microscopy. We obtained very uniform imprinted nanospheres with diameter of 120- 180 nm. Among the MIP nanospheres the MIPs using combination of MAA and MMA showed nanospheres with lowest mean diameter (120 nm and the highest selectivity factor (9.7. The adsorption properties of Nalidixic acid in acetonitrile for imprinted nanospheres were evaluated by equilibrium rebinding experiments. Results from binding experiments proved that MIPs exhibit specific affinity to Nalidixic acid in contrast to control polymers and this performance was affected by pH of loading solution and. Moreover, release experiments showed the controlled release of Nalidixic acid in longtime period. The loaded Nalidixic acid was released from the imprinted nanospheres within the 140 h.

  16. PROPERTIES AND MORPHOLOGY OF LIQUID CHLOROPRENE-METHACRYLIC ACID COPOLYMER MODIFIED EPOXY RESIN/POLY (BUTYL METHACRYLATE) SEMI-IPN

    Institute of Scientific and Technical Information of China (English)

    BIAN Xinsheng; HAN Xiaozu; WANG Xinren; ZHANG Qingyu

    1987-01-01

    A series of liquid chloroprene-methacrylic acid copolymer (CP-co-MAA) modified epoxy resin (ER)/poly (butyl methacrylate) (PBMA) semi-IPN were synthesised. Some physical properties were investigated. DSC diagrams showed two indistinct and inward endothermal transitions corresponding to the transitions of two networks in the semi-IPN system. By observing morphology with SEM technique it shows that there is a multiphase structure, in which CP-co-MAA's domain sizes are about 0.10-0.80μ. With increasing C/E ratio, the domain εizes are getting smaller, which is due to effect of mixing network of CP-co-MAA promoting entanglement and interpenetrating of PBMA and CP-co-MAA-ER network. In most of the semi-IPN's compositions, ER phase readily maintains its phase continuity while PBMA phase presents a hand shape structure. Consequently, crosslinking network keeps in its continuous phase more readily than uncrosslinking one, thus it influences dominantly on the physical properties.

  17. Postural heart block.

    OpenAIRE

    Seda, P E; McAnulty, J H; Anderson, C J

    1980-01-01

    A patient presented with orthostatic dizziness and syncope caused by postural heart block. When the patient was supine, atrioventricular conduction was normal and he was asymptomatic; when he was standing he developed second degree type II block and symptoms. The left bundle-branch block on his electrocardiogram and intracardiac electrophysiological study findings suggest that this heart block occurred distal to the His bundle. Orthostatic symptoms are usually presumed to be secondary to an i...

  18. Interface-enforced complexation between copolymer blocks.

    Science.gov (United States)

    Steinschulte, Alexander A; Xu, Weinan; Draber, Fabian; Hebbeker, Pascal; Jung, Andre; Bogdanovski, Dimitri; Schneider, Stefanie; Tsukruk, Vladimir V; Plamper, Felix A

    2015-05-14

    Binary diblock copolymers and corresponding ternary miktoarm stars are studied at oil-water interfaces. All polymers contain oil-soluble poly(propylene oxide) PPO, water-soluble poly(dimethylaminoethyl methacrylate) PDMAEMA and/or poly(ethylene oxide) PEO. The features of their Langmuir compression isotherms are well related to the ones of the corresponding homopolymers. Within the Langmuir-trough, PEO-b-PPO acts as the most effective amphiphile compared to the other PPO-containing copolymers. In contrast, the compression isotherms show a complexation of PPO and PDMAEMA for PPO-b-PDMAEMA and the star, reducing their overall amphiphilicity. Such complex formation between the blocks of PPO-b-PDMAEMA is prevented in bulk water but facilitated at the interface. The weakly-interacting blocks of PPO-b-PDMAEMA form a complex due to their enhanced proximity in such confined environments. Scanning force microscopy and Monte Carlo simulations with varying confinement support our results, which are regarded as compliant with the mathematical random walk theorem by Pólya. Finally, the results are expected to be of relevance for e.g. emulsion formulation and macromolecular engineering. PMID:25807174

  19. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    Energy Technology Data Exchange (ETDEWEB)

    BEN W.-L. JANG; GERALD N. CHOI; JAMES J. SPIVEY; JOSPEH R. ZOELLER; RICHARD D. COLBERG

    1999-01-20

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. The research team has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, we are currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last quarter(Oct.-Dec./98), we have investigated the condensation between methyl propionate and formaldehyde (MP/HCHO=4.5/1) at various reaction temperatures(280-360EC) over 5%, 10%, and 20% Nb O /SiO catalysts. The conversion of HCHO increases with reaction 2 5 2 temperature and niobium loading. MMA+MAA selectivity goes through a maximum with the temperature over both 10% and 20% Nb O /SiO . The selectivities to MMA+MAA are 67.2%, 2 5 2 72.3%and 58.1% at 320EC over 5%, 10%, 20% Nb O /SiO , respectively. However, the 2 5 2 conversion of formaldehyde decreases rapidly with time on stream. The results suggest that silica supported niobium catalysts are active and selective for condensation of MP with HCHO, but deactivation needs to be minimized for the consideration of commercial application. We have preliminarily investigated the partial oxidation of dimethyl ether(DME) over 5% Nb O /SiO catalyst. Reactant gas mixture of 0.1% DME, 0.1% O and balance nitrogen is 2 5 2 2 studied with temperature ranging from 200°C to 500°C. The conversion of DME first increases with temperature reaching an maximum at 400°C then decreases. The selectivity to HCHO also increases with reaction temperature first. But the selectivity to HCHO decreases at temperature above 350

  20. Nanostructured Amphiphilic Star-Hyperbranched Block Copolymers for Drug Delivery.

    Science.gov (United States)

    Seleci, Muharrem; Seleci, Didem Ag; Ciftci, Mustafa; Demirkol, Dilek Odaci; Stahl, Frank; Timur, Suna; Scheper, Thomas; Yagci, Yusuf

    2015-04-21

    A robust drug delivery system based on nanosized amphiphilic star-hyperbranched block copolymer, namely, poly(methyl methacrylate-block-poly(hydroxylethyl methacrylate) (PMMA-b-PHEMA) is described. PMMA-b-PHEMA was prepared by sequential visible light induced self-condensing vinyl polymerization (SCVP) and conventional vinyl polymerization. All of the synthesis and characterization details of the conjugates are reported. To accomplish tumor cell targeting property, initially cell-targeting (arginylglycylaspactic acid; RGD) and penetrating peptides (Cys-TAT) were binding to each other via the well-known EDC/NHS chemistry. Then, the resulting peptide was further incorporated to the surface of the amphiphilic hyperbranched copolymer via a coupling reaction between the thiol (-SH) group of the peptide and the hydroxyl group of copolymer by using N-(p-maleinimidophenyl) isocyanate as a heterolinker. The drug release property and targeting effect of the anticancer drug (doxorobucin; DOX) loaded nanostructures to two different cell lines were evaluated in vitro. U87 and MCF-7 were chosen as integrin αvβ3 receptor positive and negative cells for the comparison of the targeting efficiency, respectively. The data showed that drug-loaded copolymers exhibited enhanced cell inhibition toward U87 cells in compared to MCF-7 cells because targeting increased the cytotoxicity of drug-loaded copolymers against integrin αvβ3 receptor expressing tumor cells. PMID:25816726

  1. Generalized Block Failure

    DEFF Research Database (Denmark)

    Jönsson, Jeppe

    2015-01-01

    shows that no readily available tests with a well-defined substantial eccentricity have been performed. This paper presents theoretical and experimental work leading towards generalized block failure capacity methods. Simple combination of normal force, shear force and moment stress distributions along......Block tearing is considered in several codes as a pure block tension or a pure block shear failure mechanism. However in many situations the load acts eccentrically and involves the transfer of a substantial moment in combination with the shear force and perhaps a normal force. A literature study...... yield lines around the block leads to simple interaction formulas similar to other interaction formulas in the codes....

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

    International Nuclear Information System (INIS)

    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

  3. 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.

  4. Study of scintillation in natural and synthetic quartz and methacrylate

    CERN Document Server

    Amaré, J; Cebrián, S; Cuesta, C; Fortuño, D; García, E; Ginestra, C; Gómez, H; Herrera, D C; Martínez, M; Oliván, M A; Ortigoza, Y; de Solórzano, A Ortiz; Pobes, C; Puimedón, J; Sarsa, M L; Villar, J A; Villar, P

    2014-01-01

    Samples from different materials typically used as optical windows or light guides in scintillation detectors were studied in a very low background environment, at the Canfranc Underground Laboratory, searching for scintillation. A positive result can be confirmed for natural quartz: two distinct scintillation components have been identified, not being excited by an external gamma source. Although similar effect has not been observed neither for synthetic quartz nor for methacrylate, a fast light emission excited by intense gamma flux is evidenced for all the samples in our measurements. These results could affect the use of these materials in low energy applications of scintillation detectors requiring low radioactive background conditions, as they entail a source of background.

  5. Polymethyl Methacrylate as a Binder for Pyrotechnic Compositions

    Directory of Open Access Journals (Sweden)

    S. P. Sontakke

    1995-10-01

    Full Text Available Studies on polymethyl methacrylate (PMMA as a binder for igniter and delay compositions are reported. Igniter compositions based on magnesium and boron as fuels and potassium nitrate as oxidiser, delay compositions comprising ferrosilicon and red lead, have been investigated. These compositions were subjected to various tests, such as linear burning rate, sensitivity, calorimetric value, compatibility, pelleting properties, spark sensitivity, ignition temperatures and performance characteristics. The results indicate that the igniter compositions Mg:KNO/sub 3/:PMMA (42:50:8 and B:KNO/sub 3/:PMMA (30:70:10 as well as the delay composition comprising FeSi:Pb/sub 3/O/sub 4:PMMA (25:75:1 have improved properties and therefore could find practical applications.

  6. Copolymers Formation by Photopolymerization of (Methacrylates Containing Dissolved Polyheteroarylenes

    Directory of Open Access Journals (Sweden)

    Dmitriy A. Sapozhnikov

    2009-01-01

    Full Text Available Radical photopolymerization of (methacrylates in the presence of dissolved polyheteroarylenes has been investigated. The kinetics of radical polymerization of unsaturated monomers in the presence of polyheteroarylenes and model compounds has been studied by Differential Scanning Photocalorimetry and Infrared Spectroscopy. From the results of investigations into the kinetics and the polymer structures (Fourier Transform Infrared Spectroscopy, Nuclear Magnetic Resonance, Size-exclusion Chromatography, Thermogravimetric analysis, it has been established that radical photopolymerization of vinyl monomers in the presence of polyheteroarylenes leads to the formation of copolymers owing to chain transfer reactions and/or chain termination by the relevant condensation polymer. Using Electron Spin Resonance Spectroscopy the novel radicals upon the addition of model compounds for the polyheteroarylenes have been detected, and a mechanism of copolymer formation has been proposed.

  7. Self-sacrificial surface micromachining using poly(methyl methacrylate)

    International Nuclear Information System (INIS)

    This paper explains the idea of self-sacrificial surface micromachining. In a self-sacrificial process, there is no distinction between structural and sacrificial layers. Instead, during patterning, an in situ chemical change converts a structural material into a sacrificial material, or vice versa. This greatly increases the design space of a self-sacrificial process when compared to a traditional process with the same number of layers, as all layers can be used simultaneously for both structural and sacrificial purposes. To show the possibility of self-sacrificial surface micromachining, a concrete implementation was developed using poly(methyl methacrylate) (PMMA) as the material. Unexposed PMMA, with a high average molecular weight, was used as the structural material. Exposed PMMA, with a lower average molecular weight, was used as the sacrificial material. The in situ chemical change was caused by deep-UV irradiation at 254 nm

  8. Management of complication after breast augmentation with methacrylate

    Science.gov (United States)

    Grella, Roberto; Almadori, Aurora; D’Ari, Antonio; Romanucci, Vincenza; D’Andrea, Francesco

    2015-01-01

    Introduction Several alloplastic biomaterials are available for injection to the breast, nevertheless not all of them are approved for biomedical use. Although in North America and Western Europe experience with synthetic biomaterials for breast augmentation is very limited, migratory streams might expose physicians worldwide to manage the related complications of these procedures. The aim of this study was to share with other surgeons the case of a patient presenting complications after breast augmentation with an unknown synthetic substance containing methacrylate. Presentation of case A 33-years old Asian woman presented to our Institution with breast deformities, lumps and chest pain. The patient referred previous breast injection “with hospital fat” performed in China six years before. She was not aware about the details of the procedure, and language barriers limited communication. Clinical examination and ultrasounds revealed the irregular distribution of an unknown substance in both breasts. The material was surgically removed and replaced in the same session with polyurethane implants. Chemical analysis revealed the presence of methacrylate. Discussion With a growing demand for non-invasive cosmetic surgery, has been reported a growing population of untrained and unlicensed personnel performing cosmetic surgery in many countries where there are no laws that restrict the use of cosmetic procedures to physicians with appropriate training and with approved materials. Surgical removal of this substances can be extremely challenging and an open procedure with surgical debridement is recommended. Conclusion Breast augmentation with non-absorbable biomaterials can lead to severe complications, in particular for patients intending to breastfeed. PMID:26298244

  9. Polyglycidyl methacrylate based immunoaffinity cryogels for insulin adsorption

    International Nuclear Information System (INIS)

    Immunoaffinity chromatography (IAC) is a kind of bioaffinity chromatography which used antibodies or antibody-related molecules as the stationary phase. IAC is used by many applications for analytical, clinical and diagnostic purposes, particularly preferring in analytical purposes on one-step separation and purification of target compounds. Moreover, immunoaffinity chromatography is used in antibody enrichment and separation of cells. IAC columns are usually applied in the antibody experiments due to powerful and selective binding of antibodies and/or their target antigens. Antigen or antibody molecules could be immobilized to the solid support. Therefore, target antibody or cell is purified. Specific bioligands can be immobilized directly on glycidyl based polymeric material with simple acid–base catalyst. In this study, polyglycidyl methacrylate based therefore cryogels were prepared and anti-insulin antibodies were immobilized on porous surface of cryogels. Swelling test, Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and scanning electron microscopy (SEM) were conducted to characterize cryogels developed. To optimize separation conditions, effects of pH, initial insulin concentration, flow rate, salt concentration, contact time and temperature on insulin adsorption capacity were examined. The results indicated that the immunoaffinity cryogel developed here could be classified as good alternative with prominent properties such as high reusability and cost-friendly adsorbent and would be one of the primary reports for immunoaffinity purification of insulin molecules in not only lab-scale but also for industrial purposes. - Highlights: • Polyglycidyl methacrylate based cryogels developed as stationary phase • Immunoaffinity cryogels for reusable and cost-friendly insulin adsorption • Increase in worldwide prevalence of diabetes, type 1 or 2 • An exponential increase in the demand on insulin market • Guiding researchers for not

  10. Synthesis of acrylates and Methacrylates from Coal-Derived Syngas

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-05-12

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas, under a contract from the U.S. Department of Energy, Federal Energy Technology Center. This three-step process consists of synthesis of a propionate, its condensation with formaldehyde, and esterification of resulting methacrylic acid (MAA) with methanol to produce MMA. Eastman has focused on the propionate synthesis step. The resultant Mo catalysts work efficiently at much less severe conditions (170{degrees}C and 30 atm) than the conventional Ni catalysts (270{degrees} C and 180 atm). Bechtel has performed an extensive cost analysis which shows that Eastman`s propionate synthesis step is competitive with other technologies to produce the anhydride. Eastman and Bechtel have also compared the RTI- Eastman-Bechtel three-step methanol route to five other process routes to MMA. The results show that the product MMA can be produced at 520/lb, for a 250 Mlb/year MMA plant, and this product cost is competitive to all other process routes to MMA, except propyne carbonylation. In the second step, RTI and Eastman have developed active and stable V-SI-P tertiary metal oxide catalysts, Nb/Si0{sub 2}, and Ta/Si0{sub 2} catalysts for condensation of propionic anhydride or propionic acid with formaldehyde. RTI has demonstrated a novel correlation among the catalyst acid-base properties, condensation reaction yield, and long-term catalyst performance. Eastman and Bechtel have used the RTI experimental results of a 20 percent Nb/Si0{sub 2} catalyst, in terms of reactant conversions, MAA selectivities, and MAA yield, for their economic analysis. Recent research focuses on enhancing the condensation reaction yields, a better understanding of the acid-base property correlation and enhancing the catalyst lifetime.

  11. Polyglycidyl methacrylate based immunoaffinity cryogels for insulin adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Memmedova, Türkan; Armutcu, Canan; Uzun, Lokman, E-mail: lokman@hacettepe.edu.tr; Denizli, Adil

    2015-07-01

    Immunoaffinity chromatography (IAC) is a kind of bioaffinity chromatography which used antibodies or antibody-related molecules as the stationary phase. IAC is used by many applications for analytical, clinical and diagnostic purposes, particularly preferring in analytical purposes on one-step separation and purification of target compounds. Moreover, immunoaffinity chromatography is used in antibody enrichment and separation of cells. IAC columns are usually applied in the antibody experiments due to powerful and selective binding of antibodies and/or their target antigens. Antigen or antibody molecules could be immobilized to the solid support. Therefore, target antibody or cell is purified. Specific bioligands can be immobilized directly on glycidyl based polymeric material with simple acid–base catalyst. In this study, polyglycidyl methacrylate based therefore cryogels were prepared and anti-insulin antibodies were immobilized on porous surface of cryogels. Swelling test, Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and scanning electron microscopy (SEM) were conducted to characterize cryogels developed. To optimize separation conditions, effects of pH, initial insulin concentration, flow rate, salt concentration, contact time and temperature on insulin adsorption capacity were examined. The results indicated that the immunoaffinity cryogel developed here could be classified as good alternative with prominent properties such as high reusability and cost-friendly adsorbent and would be one of the primary reports for immunoaffinity purification of insulin molecules in not only lab-scale but also for industrial purposes. - Highlights: • Polyglycidyl methacrylate based cryogels developed as stationary phase • Immunoaffinity cryogels for reusable and cost-friendly insulin adsorption • Increase in worldwide prevalence of diabetes, type 1 or 2 • An exponential increase in the demand on insulin market • Guiding researchers for not

  12. Synthesis of Methyl Methacrylate From Coal-Derived Syngas

    Energy Technology Data Exchange (ETDEWEB)

    Ben W.-L. Jang; Gerald N. Choi; James J. Spivey; Jospeh R. Zoeller; Richard D. Colberg; Samuel S. Tam

    1998-07-27

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. RTI has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, RTI is currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last quarter(April-June, 1998), RTI has modified the reactor system including a new preheater and new temperature settings for the preheater. Continuous condensation of formaldehyde with propionic acid were carried out over 10% Nb O /SiO at 300°C without 2 5 2 interruption. Five activity and four regeneration cycles have been completed without plugging or material balance problems. The results show that 10% Nb O /SiO deactivates slowly with time 2 5 2 but can be regenerated, at least four times, to 100% of its original activity with 2% O in nitrogen 2 at 400°C. The cycles continue with consistent 90-95% of carbon balance. The reaction is scheduled to complete with 6 activity cycles and 5 regenerations. Used catalysts will be analyzed with TGA and XPS to determine bulk and surface coke content and coke properties. RTI will start the investigation of effects of propionic acid/formaldehyde ratio on reaction activity and product selectivity over 20% Nb O /SiO catalysts.

  13. Reversible switching in self-assembled monolayers of azobenzene thiolates on Au (111) probed by threshold photoemission

    International Nuclear Information System (INIS)

    Highlights: ► Photoelectron spectroscopy of liquid phase prepared SAMs of azobenzene derivative. ► Photo-induced reversible switching in densely packed SAM is monitored. ► Maximum density of switched molecules in SAM is derived from photoemission data. ► Switching reaction only enabled at defects sites within the molecular layer. - Abstract: The reversible photo- and thermally activated isomerization of the molecular switch 3-(4-(4-Hexyl-phenylazo)-phenoxy)-propane-1-thiol (ABT, short for AzoBenzeneThiol) deposited by self-assembly from solution on Au (111) was studied using laser-based photoelectron spectroscopy. Differences in the molecular dipole moment characteristic for the trans and the cis isomer of ABT were monitored via changes in the sample work function, accessible by detection of the threshold energy for photoemission. A quantitative analysis of our data shows that the fraction of molecules within the densely packed monolayer that undergoes a switching process is of the order of 1%. This result indicates the relevance of substrate and film defects required to overcome the steric or electronic hindrance of the isomerization reaction in a densely packed monolayer.

  14. Azobenzene-caged sulforhodamine dyes: a novel class of ‘turn-on’ reactive probes for hypoxic tumor cell imaging

    Science.gov (United States)

    Chevalier, Arnaud; Piao, Wen; Hanaoka, Kenjiro; Nagano, Tetsuo; Renard, Pierre-Yves; Romieu, Anthony

    2015-12-01

    New sulforhodamine-based fluorescent ‘turn-on’ probes have been developed for the direct imaging of cellular hypoxia. Rapid access to this novel class of water-soluble ‘azobenzene-caged’ fluorophores was made possible through an easily-implementable azo-coupling reaction between a fluorescent primary arylamine derived from a sulforhodamine 101 scaffold (named SR101-NaphtNH 2 ) and a tertiary aniline whose N-substituents are neutral, cationic, or zwitterionic. The detection mechanism is based on the bioreductive cleavage of the azo bond that restores strong far-red fluorescence (emission maximum at 625 nm) by regenerating the original sulforhodamine SR101-NaphtNH 2 . This valuable fluorogenic response was obtained for the three ‘smart’ probes studied in this work, as shown by an in vitro assay using rat liver microsomes placed under aerobic and then under hypoxic conditions. Most importantly, the probe namely SR101-NaphtNH 2 -Hyp-diMe was successfully applied for imaging the hypoxic status of tumor cells (A549 cells).

  15. Synthesis, optical and thermal behaviour of palladium(II) complexes with 4-(4-alkoxy-2-hydroxybenzylideneamino)azobenzene

    Indian Academy of Sciences (India)

    Boon-Teck Heng; Guan-Yeow Yeap; Daisuke Takeuchi

    2013-11-01

    A series of new Pd(II) complexes derived from the reaction of palladium acetate with 4-(4-alkoxy-2-hydroxybenzylideneamino)azobenzene having the flexible terminal chain of OCH2+1, in which n are even numbers ranging from 8 to 16, has been successfully synthesized. The physical measurement and spectroscopic techniques (FTIR and 1H-NMR) reveal that the Pd(II) complexes possess the Pd-N and Pd-O coordination modes in which the central Pd(II) adopts square-planar geometry. The observation under the polarized light shows that all the ligands and Pd(II) complexes exhibit enantiotropic mesophases. The ligands with -octyloxy and -decyloxy flexible chains exhibit the nematic (N) and smectic A (SmA) phases whilst the Pd(II) complexes show exclusive SmA phase. The SmA phase observed in Pd(II) complexes can be supported by the presence of focal conic fan-shaped texture with the presence of curved lines which are prominent during the cooling process. On the other hand, the comparison studies show that Pd(II) complexes possess exceptional higher phase transition temperatures as compared to the corresponding Cu(II) and Ni(II) complexes.

  16. Covalent functionalization of graphene by azobenzene with molecular hydrogen bonds for long-term solar thermal storage.

    Science.gov (United States)

    Feng, Yiyu; Liu, Hongpo; Luo, Wen; Liu, Enzuo; Zhao, Naiqin; Yoshino, Katsumi; Feng, Wei

    2013-01-01

    Reduced graphene oxide-azobenzene (RGO-AZO) hybrids were prepared via covalent functionalization for long-term solar thermal storage. Thermal barrier (ΔEa) of cis to tran reversion and thermal storage (ΔH) were improved by molecular hydrogen bonds (H-bonds) through ortho- or para-substitution of AZO. Intramolecular H-bonds thermally stabilized cis-ortho-AZO on RGO with a long-term half-life of 5400 h (ΔEa = 1.2 eV), which was much longer than that of RGO-para-AZO (116 h). RGO-para-AZO with one intermolecular H-bond showed a high density of thermal storage up to 269.8 kJ kg(-1) compared with RGO-ortho-AZO (149.6 kJ kg(-1)) with multiple intra- and intermolecular H-bonds of AZO according to relaxed stable structures. Thermal storage in experiment was the same order magnitude to theoretical data based on ΔH calculated by density functional theory and packing density. Photoactive RGO-AZO hybrid can be developed for high-performance solar thermal storage by optimizing molecular H-bonds. PMID:24247355

  17. Molecular structure and vibrational and chemical shift assignments of 3‧-chloro-4-dimethylamino azobenzene by DFT calculations

    Science.gov (United States)

    Toy, Mehmet; Tanak, Hasan

    2016-01-01

    In the present work, a combined experimental and theoretical study on ground state molecular structure, spectroscopic and nonlinear optical properties of azo compound 3‧-chloro-4-dimethlamino azobenzene are reported. The molecular geometry, vibrational wavenumbers and the first order hyperpolarizability of the title compound were calculated with the help of density functional theory computations. The optimized geometric parameters obtained by using DFT (B3LYP/6-311++G(d,p)) show good agreement with the experimental data. The vibrational transitions were identified based on the recorded FT-IR spectra in the range of 4000-400 cm-1 for solid state. The 1H isotropic chemical shifts with respect to TMS were also calculated using the gauge independent atomic orbital (GIAO) method and compared with the experimental data. Using the TD-DFT method, electronic absorption spectra of the title compound have been predicted, and good agreement is determined with the experimental ones. To investigate the NLO properties of the title compound, the polarizability and the first hyperpolarizability were calculated using the density functional B3LYP method with the 6-311++G(d,p) basis set. According to results, the title compound exhibits non-zero first hyperpolarizability value revealing second order NLO behavior. In addition, DFT calculations of the title compound, molecular electrostatic potential and frontier molecular orbitals were also performed at 6-311++G(d,p) level of theory.

  18. In situ investigations on the preparations of layer-by-layer films containing azobenzene and applications for LC display devices

    International Nuclear Information System (INIS)

    Preparations of alternate layer-by-layer self-assembled films of poly(diallyldimethyl ammonium chloride) (PDADMAC) and Direct Red 80 (DR80, azobenzene dye) and photo-induced surface relief gratings (SRGs) of the films have been investigated in situ using attenuated total reflection (ATR), that is, surface plasmon resonance spectroscopy (SPS) and quartz crystal microbalance (QCM) measurements. Gratings of the PDADMAC/DR80 films were fabricated by exposure to interference patterns of Ar+ laser light at 488 nm for 30 min. The formation of the gratings was observed using atomic force microscopy (AFM). The films were used for applications to liquid crystal (LC) display devices, and aligning properties of nematic liquid crystal molecules, 5CB, on the SRG in the films were also investigated in a hybrid LC cell configuration by monitoring birefringence properties of the LC cell in situ. It was estimated that the LC molecules in the cell did not align immediately after the photo-induced SRG was inscribed, but almost along the gratings after heat treatment at 40 deg. C for 1 min

  19. Blocked randomization with randomly selected block sizes.

    Science.gov (United States)

    Efird, Jimmy

    2011-01-01

    When planning a randomized clinical trial, careful consideration must be given to how participants are selected for various arms of a study. Selection and accidental bias may occur when participants are not assigned to study groups with equal probability. A simple random allocation scheme is a process by which each participant has equal likelihood of being assigned to treatment versus referent groups. However, by chance an unequal number of individuals may be assigned to each arm of the study and thus decrease the power to detect statistically significant differences between groups. Block randomization is a commonly used technique in clinical trial design to reduce bias and achieve balance in the allocation of participants to treatment arms, especially when the sample size is small. This method increases the probability that each arm will contain an equal number of individuals by sequencing participant assignments by block. Yet still, the allocation process may be predictable, for example, when the investigator is not blind and the block size is fixed. This paper provides an overview of blocked randomization and illustrates how to avoid selection bias by using random block sizes. PMID:21318011

  20. Blocked Randomization with Randomly Selected Block Sizes

    Directory of Open Access Journals (Sweden)

    Jimmy Efird

    2010-12-01

    Full Text Available When planning a randomized clinical trial, careful consideration must be given to how participants are selected for various arms of a study. Selection and accidental bias may occur when participants are not assigned to study groups with equal probability. A simple random allocation scheme is a process by which each participant has equal likelihood of being assigned to treatment versus referent groups. However, by chance an unequal number of individuals may be assigned to each arm of the study and thus decrease the power to detect statistically significant differences between groups. Block randomization is a commonly used technique in clinical trial design to reduce bias and achieve balance in the allocation of participants to treatment arms, especially when the sample size is small. This method increases the probability that each arm will contain an equal number of individuals by sequencing participant assignments by block. Yet still, the allocation process may be predictable, for example, when the investigator is not blind and the block size is fixed. This paper provides an overview of blocked randomization and illustrates how to avoid selection bias by using random block sizes.

  1. BLOCK H-MATRICES AND SPECTRUM OF BLOCK MATRICES

    Institute of Scientific and Technical Information of China (English)

    黄廷祝; 黎稳

    2002-01-01

    The block H-matrices are studied by the concept of G-functions, several concepts of block matrices are introduced. Equivalent characters of block H-matrices are obtained. Spectrum localizations claracterized by Gfunctions for block matrices are got.

  2. Theranostic Unimolecular Micelles Based on Brush-Shaped Amphiphilic Block Copolymers for Tumor-Targeted Drug Delivery and Positron Emission Tomography Imaging

    OpenAIRE

    Guo, Jintang; Hong, Hao; Chen, Guojun; Shi, Sixiang; Nayak, Tapas R.; Theuer, Charles P.; Barnhart, Todd E.; Cai, Weibo; Gong, Shaoqin

    2014-01-01

    Brush-shaped amphiphilic block copolymers were conjugated with a monoclonal antibody against CD105 (i.e., TRC105) and a macrocyclic chelator for 64Cu-labeling to generate multifunctional theranostic unimolecular micelles. The backbone of the brush-shaped amphiphilic block copolymer was poly(2-hydroxyethyl methacrylate) (PHEMA) and the side chains were poly(l-lactide)-poly(ethylene glycol) (PLLA-PEG). The doxorubicin (DOX)-loaded unimolecular micelles showed a pH-dependent drug release profile...

  3. Preparation and characterization of gelatin-poly(methacrylic acid) interpenetrating polymeric network hydrogels as a ph-sensitive delivery system for glipizide

    OpenAIRE

    Gupta N; Satish C; Shivakumar H

    2007-01-01

    In the present study, interpenetrating polymeric network hydrogels of glipizide were prepared using gelatin and methacrylic acid. Methacrylic acid was polymerized using potassium persulfate. Methacrylic acid was crosslinked with methylene bisacrylamide and gelatin was crosslinked using glutaraldehyde. Four formulations were prepared by varying the concentrations of methacrylic acid, methylene bisacrylamide and glutaraldehyde. The amounts of gelatin and potassium persulfate were kept constant ...

  4. Lesson Thirteen Trifascicular Block

    Institute of Scientific and Technical Information of China (English)

    鲁端; 王劲

    2005-01-01

    @@ A complete trifascicular block would result in complete AV block. The idio ventricular rhythm has a slower rate and a wide QRS complex because the pacemaker is located at the peripheral part of the conduction system distal to the sites of the block1. Such a rhythm may be difficult to differentiate from bifascicular or bundle branch block combined with complete block at a higher level such as the AV node or His bundle2. Besides a slower ventricular rate, a change in the morphology of the QRS complex from a previous known bifascicular pattern would be strongly suggestive of a trifascicular origin of the complete AV block3. A His bundle recording is required for a definitive diagnosis, however.

  5. Block Advertisement Protocol

    OpenAIRE

    Nemirovsky, Danil

    2015-01-01

    Bitcoin, a decentralized cryptocurrency, has attracted a lot of attention from academia, financial service industry and enthusiasts. The trade-off between transaction confirmation throughput and centralization of hash power do not allow Bitcoin to perform at the same level as modern payment systems. Block Advertisement Protocol is proposed as a step to resolve this issue. The protocol allows block mining and block relaying to happen in parallel. The protocol dictates a miner to advertise the ...

  6. Use of hydrophobically modified inulin for the preparation of polymethyl methacrylate/polybutyl acrylate latex particles using a semicontinuous reactor.

    Science.gov (United States)

    Obiols-Rabasa, M; Ramos, J; Forcada, J; Esquena, J; Solans, C; Levecke, B; Booten, K; Tadros, Tharwat F

    2010-06-01

    The seeded semicontinuous emulsion copolymerization of methyl methacrylate (MMA) and butyl acrylate (BuA) stabilized with a graft polymeric surfactant based on inulin, INUTEC SP1, as well as its mixture with sodium lauryl sulfate (SLS) is described. The mixture of SLS and Brij58 (alcohol ethoxylated) and the mixture of SLS and Pluronic P85 (block copolymer PEO-PPO-PEO) are also used as surfactant systems. The addition of methacrylic acid (MAA) or acrylic acid (AA) as comonomers is also studied. Previous results proved this inulin-derivative surfactant, INUTEC SP1, to be very effective on synthesizing latexes using a very low surfactant concentration. The kinetic features of the emulsion polymerization (instantaneous conversion and total conversion) were gravimetrically determined along the reactions. Latex dispersions were characterized by photon correlation spectroscopy (PCS) and transmission electron microscopy (TEM) to obtain the average particle size, the particle size distributions (PSDs) as well as the polydispersity index (PdI). The stability was determined by turbidimetry measurements and expressed in terms of critical coagulation concentration. The results showed that the use of the graft polymeric surfactant allowed obtaining highly stable nanoparticles, at low surfactant concentrations and high solid contents (up to 37 wt %). This is an improvement with respect to previous works, in which a mixture of the graft polymeric surfactant with another surfactant was required to obtain stable nanoparticles with low polydispersity, at high solid content. In the present work, low polydispersity was achieved using INUTEC as the only emulsifier, which was related to the absence of secondary nucleations. When a mixture of INUTEC SP1 and SLS is used, a wider PSD is obtained due to secondary nucleations. Replacing INUTEC SP1 by other nonionic surfactants such as Brij58 or Pluronic P85 leads to an increase of average particle size and wider PSD. PMID:20121169

  7. Response Of Bi-Level And Random Copolymer Brushes Based On Poly(N-Isopropylacrylamide) And Poly(Methacrylic Acid)

    International Nuclear Information System (INIS)

    Because conformations and interactions are intimately linked, the rich phase behavior exhibited by multicomponent polymer-modified interfaces, and in particular multicomponent polymer brushes, offers new opportunities for manipulating interfacial properties. Despite the widespread use of a variety of grafting to and grafting from approaches for making polymer brushes, there are few reports of synthesis and responsive behavior of stratified block copolymer brushes. In this presentation we describe our efforts to create bi-level and random copolymer brushes consisting of poly(N-isopropylacrylamide) and poly(methacrylic acid) using surface initiated, photoiniferter-mediated photopolymerization. Pre-addition of a source of deactivating radicals combined with judicious choice of photopolymerization conditions enables the formation of bi-level brushes. In situ, multi-angle ellipsometry measurements show that the blocks of the bi-level brushes actuate independently to changes in pH and temperature, but respond in concert to changes in ionic strength. Efforts to examine the nanoscale structure of these systems as a function of pH and temperature using neutron reflectometry will also be highlighted.

  8. Fabrication of 3D Microfluidic Devices by Thermal Bonding of Thin Poly(methyl methacrylate) Films

    KAUST Repository

    Perez, Paul

    2012-07-01

    The use of thin-film techniques for the fabrication of microfluidic devices has gained attention over the last decade, particularly for three-dimensional channel structures. The reasons for this include effective use of chip volume, mechanical flexibility, dead volume reduction, enhanced design capabilities, integration of passive elements, and scalability. Several fabrication techniques have been adapted for use on thin films: laser ablation and hot embossing are popular for channel fabrication, and lamination is widely used for channel enclosure. However, none of the previous studies have been able to achieve a strong bond that is reliable under moderate positive pressures. The present work aims to develop a thin-film process that provides design versatility, speed, channel profile homogeneity, and the reliability that others fail to achieve. The three building blocks of the proposed baseline were fifty-micron poly(methyl methacrylate) thin films as substrates, channel patterning by laser ablation, and device assembly by thermal-fusion bonding. Channel fabrication was characterized and tuned to produce the desired dimensions and surface roughness. Thermal bonding was performed using an adapted mechanical testing device and optimized to produce the maximum bonding strength without significant channel deformation. Bonding multilayered devices, incorporating conduction lines, and integrating various types of membranes as passive elements demonstrated the versatility of the process. Finally, this baseline was used to fabricate a droplet generator and a DNA detection chip based on micro-bead agglomeration. It was found that a combination of low laser power and scanning speed produced channel surfaces with better uniformity than those obtained with higher values. In addition, the implemented bonding technique provided the process with the most reliable bond strength reported, so far, for thin-film microfluidics. Overall, the present work proved to be versatile

  9. Magnetic hydrophilic methacrylate-based polymer microspheres designed for polymerase chain reactions applications.

    Science.gov (United States)

    Spanová, Alena; Horák, Daniel; Soudková, Eva; Rittich, Bohuslav

    2004-02-01

    Magnetic hydrophilic non-porous P(HEMA-co-EDMA), P(HEMA-co-GMA) and PGMA microspheres were prepared by dispersion (co)polymerization of 2-hydroxyethyl methacrylate (HEMA) and ethylene dimethacrylate (EDMA) or glycidyl methacrylate (GMA) in the presence of several kinds of magnetite. It was found that some components used in the preparation of magnetic carriers interfered with polymerase chain reaction (PCR). Influence of non-magnetic and magnetic microspheres, including magnetite nanoparticles and various components used in their synthesis, on the PCR course was thus investigated. DNA isolated from bacterial cells of Bifidobacterium longum was used in PCR evaluation of non-interfering magnetic microspheres. The method enabled verification of the incorporation of magnetite nanoparticles in the particular methacrylate-based polymer microspheres and evaluation of suitability of their application in PCR. Preferably, electrostatically stabilized colloidal magnetite (ferrofluid) should be used in the design of new magnetic methacrylate-based microspheres by dispersion polymerization. PMID:14698232

  10. Preparation and evaluation of poly(alkyl methacrylate-co-methacrylic acid-co-ethylene dimethacrylate) monolithic columns for separating polar small molecules by capillary liquid chromatography

    International Nuclear Information System (INIS)

    Highlights: • Methacrylic acid (MAA) was used to increase hydrophilicity of polymeric monoliths. • Fast separation of phenol derivatives was achieved in 5 min using MAA-incorporated column. • Separations of aflatoxins and phenicol antibiotics were achieved using MAA-incorporated column. - Abstract: In this study, methacrylic acid (MAA) was incorporated with alkyl methacrylates to increase the hydrophilicity of the synthesized ethylene dimethacrylate-based (EDMA-based) monoliths for separating polar small molecules by capillary LC analysis. Different alkyl methacrylate–MAA ratios were investigated to prepare a series of 30% alkyl methacrylate–MAA–EDMA monoliths in fused-silica capillaries (250-μm i.d.). The porosity, permeability, and column efficiency of the synthesized MAA-incorporated monolithic columns were characterized. A mixture of phenol derivatives is employed to evaluate the applicability of using the prepared monolithic columns for separating small molecules. Fast separation of six phenol derivatives was achieved in 5 min with gradient elution using the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column. In addition, the effect of acetonitrile content in mobile phase on retention factor and plate height as well as the plate height-flow velocity curves were also investigated to further examine the performance of the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column. Moreover, the applicability of prepared polymer-based monolithic column for potential food safety applications was also demonstrated by analyzing five aflatoxins and three phenicol antibiotics using the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column

  11. Preparation and evaluation of poly(alkyl methacrylate-co-methacrylic acid-co-ethylene dimethacrylate) monolithic columns for separating polar small molecules by capillary liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Shu-Ling; Wu, Yu-Ru; Lin, Tzuen-Yeuan; Fuh, Ming-Ren, E-mail: msfuh@scu.edu.tw

    2015-04-29

    Highlights: • Methacrylic acid (MAA) was used to increase hydrophilicity of polymeric monoliths. • Fast separation of phenol derivatives was achieved in 5 min using MAA-incorporated column. • Separations of aflatoxins and phenicol antibiotics were achieved using MAA-incorporated column. - Abstract: In this study, methacrylic acid (MAA) was incorporated with alkyl methacrylates to increase the hydrophilicity of the synthesized ethylene dimethacrylate-based (EDMA-based) monoliths for separating polar small molecules by capillary LC analysis. Different alkyl methacrylate–MAA ratios were investigated to prepare a series of 30% alkyl methacrylate–MAA–EDMA monoliths in fused-silica capillaries (250-μm i.d.). The porosity, permeability, and column efficiency of the synthesized MAA-incorporated monolithic columns were characterized. A mixture of phenol derivatives is employed to evaluate the applicability of using the prepared monolithic columns for separating small molecules. Fast separation of six phenol derivatives was achieved in 5 min with gradient elution using the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column. In addition, the effect of acetonitrile content in mobile phase on retention factor and plate height as well as the plate height-flow velocity curves were also investigated to further examine the performance of the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column. Moreover, the applicability of prepared polymer-based monolithic column for potential food safety applications was also demonstrated by analyzing five aflatoxins and three phenicol antibiotics using the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column.

  12. Radiation-induced graft polymerization of glycidyl methacrylate onto nonwoven polypropylene

    International Nuclear Information System (INIS)

    The influence of the major grafting parameters (radiation dose, reaction time, and inhibitor concentration) on graft polymerization of glycidyl methacrylate from its 10% solution in methanol onto nonwoven polypropylene upon irradiation in a 1 MeV electron beam accelerator in air was studied. It is shown that the method of preliminary irradiation of the substrate affords glycidyl methacrylate grafting at 70 deg C most efficiently when Mohr's salt in amounts of 10-2 wt.% is added to the reaction mixture

  13. Swelling characteristics of hydroxyethylmethacrylate/ methacrylic acid pH -sensitive hydrogel as a drug delivery system

    OpenAIRE

    M. Falamarzian- J. Varshosaz

    1996-01-01

    Hydroxyethyl methacrylate /methacrylic acid (HEMA/MAA) copolymer cross-linked with ethylenglycol dimethacrylate was prepared by a bulk.free radical polymerization method. The results indicate that this polymer is a pH -sensitive hydrogel which is collapsed in the acidic medium but completely swollen in the alkaline and neutral pH . it was determined that a proportion of 40% of MAA, the ionizing monomer of this hydrogel, was the best concentration among the different percentages used which sho...

  14. Effect of Nanoclay on Thermal Conductivity and Flexural Strength of Polymethyl Methacrylate Acrylic Resin

    OpenAIRE

    Tahereh Ghaffari; Ali Barzegar; Fahimeh Hamedi Rad; Elnaz Moslehifard

    2016-01-01

    Statement of the Problem: The mechanical and thermal properties of polymethyl methacrylate (PMMA) acrylic resin should be improved to counterweigh its structural deficiencies. Purpose: The aim of this study was to compare the flexural strength and thermal conductivity of conventional acrylic resin and acrylic resin loaded with nanoclay. Materials and Method: The methacrylate monomer containing the 0.5, 1 and 2 wt% of nanoclay was placed in an ultrasonic probe and mixed with the PMMA p...

  15. Grafting of Chitosan and Chitosantrimethoxylsilylpropyl Methacrylate on Single Walled Carbon Nanotubes-Synthesis and Characterization

    OpenAIRE

    Carson, Laura; Kelly-Brown, Cordella; Stewart, Melisa; Oki, Aderemi; Regisford, Gloria; Stone, Julia; Traisawatwong, Pasakorn; Durand-Rougely, Clarissa; Luo, Zhiping

    2010-01-01

    Acid functionalized single walled carbon nanotubes (CNTs) were grafted to chitosan by first reacting the oxidized CNTs with thionyl chloride to form acyl-chlorinated CNTs. This product was subsequently dispersed in chitosan and covalently grafted to form CNT-chitosan. CNT-chitosan was further grafted onto 3-trimethoxysilylpropyl methacrylate by free radical polymerization conditions, to yield CNT-g-chitosan-g-3-trimethoxysilylpropyl methacrylate (TMSPM), hereafter referred to as CNT-chitosan-...

  16. High Molecular Weight Thermally Stable Poly (Sodium Methacrylate) / Magnetites Nanocomposites Via Emulsion Polymerization

    OpenAIRE

    Rasha A. El-Ghazawya,; Atta, Ayman M.

    2014-01-01

    Core/shell type magnetite nanocomposites (MN) were synthesized using sodium methacrylate (NMA) monomer. Functionalized and bare magnetite nanoparticles were prepared by conventional co-precipitation method giving particles with 3-10 nm in diameter. Microemulsion polymerization was used for constructing core/shell structure with magnetite nanoparticles as core and poly (sodium methacrylate) as shell. Chemical structure and morphology of the synthesized PNMA/magnetite nanocompos...

  17. Syringyl Methacrylate, a Hardwood Lignin-Based Monomer for High-T g Polymeric Materials

    OpenAIRE

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

    2016-01-01

    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...

  18. Miscibility of Methylmethacrylate-co-methacrylic Acid Polymer with Magnesium, Zinc, and Manganese Sulfonated Polystyrene Ionomers

    OpenAIRE

    ALKAN, Cemil; YURTSEVEN, Nebahat; ARAS, Leyla

    2005-01-01

    The miscibility of methyl methacrylate-co-methacrylic acid polymer (MMA-MAA) with metal neutralized sulfonated polystyrene ionomers was investigated by viscometry, differential scanning calorimetry (DSC), and Fourier transform infrared radiation spectroscopy (FTIR) techniques. Polystyrene (PS) was sulfonated by acetic anhydride and sulfuric acid and the sulfonation degree was found to be 2.6 mole percent, and 2.6 mole percent sulfonated polystyrene was neutralized by Mg, Zn, and Mn sa...

  19. Synthesis of Acrylates and Methacrylates from Coal-Derived Syngas.

    Energy Technology Data Exchange (ETDEWEB)

    Gogate, M.R.; Spivey, J.J.; Zoeller, J.R.; Colberg, R.D.; Choi, G.N.; Tam, S.S.

    1997-10-17

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas, under a contract from the U.S. Department of Energy/Federal Energy Technology Center (DOE/FETC). This three-step process consists of synthesis of a propionate, its condensation with formaldehyde, and esterification of resulting methacrylic acid (MAA) with methanol to produce MMA. Over the last quarter, RTI carried out activity tests on a pure (99 percent) Nb{sub 2}O{sub 5} catalyst, received from Alfa Aesar, under the following experimental conditions: T=300 C; P=4 atm, 72:38:16:4:220 mmol/h, PA:H{sub 2}0:HCHO:CH{sub 3}0H:N{sub 2}; 5-g catalyst charge. For the pure material, the MAA yields (based on HCHO and PA) were at 8.8 and 1.5 percent, clearly inferior compared to those for a 10-percent Nb{sub 2}O{sub 5}/Si0{sub 2} catalyst (20.1 and 4.5 percent). The X-ray diffraction (XRD) patterns of pure Nb{sub 2}O{sub 5} and 20-percent Nb{sub 2}O{sub 5}/Si0{sub 2} that while pure Nb{sub 2}O{sub 5} is very highly crystalline, Si0{sub 2} support for an amorphous nature of the 20 percent Nb{sub 2}O{sub 5}/Si0{sub 2} catalyst the last quarter, RTI also began research on the use of dimethyl ether (DME), product of methanol dehydrocondensation, as an alternate feedstock in MMA synthesis. As a result, formaldehyde is generated either externally or in situ, from DME, in the process envisaged in the contract extension. The initial work on the DME extension of the contract focuses on a tradeoff analysis that will include a preliminary economic analysis of the DME and formaldehyde routes and catalyst synthesis and testing for DME partial oxidation and condensation reactions. Literature guides exist for DME partial oxidation catalysts; however, there are no precedent studies on catalyst development for DME-methyl propionate (MP) condensation reactions, thereby making DME-MP reaction studies a

  20. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    Energy Technology Data Exchange (ETDEWEB)

    BEN W.-L. JANG; GERALD N. CHOI; JAMES J. SPIVEY; JOSPEH R. ZOELLER; RICHARD D. COLBERG

    1998-10-20

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. RTI has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, RTI is currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last quarter (July-September, 1998), the project team has completed the continuous condensation of formaldehyde with propionic acid over 10% Nb{sub 2}O{sub 5}/SiO{sub 2} at 300 C. Six activity and five regeneration cycles have been completed. The results show that 10% Nb{sub 2}O{sub 5}/SiO{sub 2} deactivates slowly with time but can be regenerated to its original activity with 2% O{sub 2} in nitrogen over night at 400 C. We have investigated the effects of regeneration, propionic acid/formaldehyde ratio (PA/HCHO = 4.5/1 to 1.5/1) and reaction temperature(280-300 C) on reaction activity and product selectivity over 20% Nb{sub 2}O{sub 5}/SiO{sub 2} catalysts. The regeneration effect on 20% Nb{sub 2}O{sub 5}/SiO{sub 2} is similar to the effect on 10% Nb{sub 2}O{sub 5}/SiO{sub 2}. The regeneration can bring the deactivated catalyst to its original activity. However, the selectivity to MAA decreases with regeneration while the selectivity to DEK and CO{sub 2} increases. When PA/HCHO ratio is decreased from 4.5/1 to 2.25/1 then to 1.5/1 at 300 C the MAA yield decreases but the MAA selectivity first increases then decreases. Decreasing the reaction temperature from 300 C to 280 C decreases the MAA yield from 39.5% to 30.7% but increases the MAA selectivity from 73.7% to 82.2%. The

  1. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    Energy Technology Data Exchange (ETDEWEB)

    Makarand R. Gogate; James J. Spivey; Joseph R. Zoeller; Richard D. Colberg; Gerald N. Choi

    1999-07-19

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. The research team has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, we are currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. During the April-June quarter(04-06/99) the first in-situ formaldehyde generation from DME and condensation with methyl propionate is demonstrated and the results are summarized. The supported niobium catalyst shows better condensation activity, but supported tungsten catalyst has higher formaldehyde selectivity. The project team has also completed a 200-hour long term test of PA-HCHO condensation over 30% Nb{sub 2}O{sub 5}/SiO{sub 2}. Three activity cycles and two regeneration cycles were carried out. 30% Nb{sub 2}O{sub 5}/SiO{sub 2} showed similar MAA yields as 10% Nb{sub 2}O{sub 5}/SiO{sub 2} at 300 C. However, the deactivation appears to be slower with 30% Nb{sub 2}O{sub 5}/SiO{sub 2} than 10% Nb{sub 2}O{sub 5}/SiO{sub 2}. An detailed economic analysis of PA-HCHO condensation process for a 250 million lb/yr MMA plant is currently studied by Bechtel. Using the Amoco data-based azeotropic distillation model as the basis, an ASPEN flow sheet model was constructed to simulate the formaldehyde and propionic acid condensation processing section based on RTI's design data. The RTI MAA effluent azeotropic distillation column was found to be much more difficult to converge. The presence of non-condensible gases along with the byproduct DEK (both of which were not presented

  2. Block Scheduling Revisited.

    Science.gov (United States)

    Queen, J. Allen

    2000-01-01

    Successful block scheduling depends on provision of initial and ongoing instructional training. Teaching strategies should vary and include cooperative learning, the case method, the socratic seminar, synectics, concept attainment, the inquiry method, and simulations. Recommendations for maximizing block scheduling are outlined. (Contains 52…

  3. Phase behavior of miscible block copolymer blends and baraplastic property

    International Nuclear Information System (INIS)

    The phase behavior of the multi-component polymer systems such as blends and block copolymers (BCPs) has been studied extensively, as it determines the chemical and physical properties of the polymeric materials in practical applications. Above all, polymer baroplasticity is a desirable property for the recycling and regenerating industries, since it allows the polymers to flow at relatively mild pressure. Particularly, the compressibility issue on the enhanced miscibility with pressure has been an attractive topic, because an ordered state of the baroplastic BCPs becomes a phase-mixed state (or disordered phase) between the two dissimilar blocks upon pressurizing. This is in contrast to the incompressibility that was dictated by the enthalpic effect arising from the increased unfavorable contacts between the two blocks by increasing pressure. The phase behaviors of BCP blends composed of the weakly interacting (with no specific interaction) polystyrene-b-poly(n-butyl methacrylate) (PS-b-PnBMA) and deuterated polystyreneb- poly-(n-hexyl methacrylate) (dPS-b-PnHMA) were investigated by Small-Angle Neutron Scattering(SANS) and Depolarized Light Scattering (DPLS) measurements. Interestingly, pressure dependence of various phase transitions for the miscible BCP blends was significantly changed, in which the blends consist of a PS-b-PnBMA and a deuterated dPS-b-PnHMA. To elucidate the origin and difference in baroplasticity of weakly interacting BCP blends, the pressure dependence of transition temperatures was evaluated using enthalpic and volumetric changes at phase transitions. We also demonstrate that the entropic compressibility for the miscible BCP blends is a baroplastic indicator, which was characterized by the negative volume change on mixing (ΔVmix) at transitions.

  4. Strengthening of Poly Methyl Methacrylate (PMMA) through Electron Irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Sung Ho; Lim, Hyung San; Ha, Jun Mok; Cho, Sung Oh [KAIST, Daejeon (Korea, Republic of)

    2015-05-15

    Poly Methyl Methacrylate (PMMA) was previously known to show the deteriorating mechanical properties when irradiated with electrons. This is true for low electron irradiation does, but it was found, through experimentation, that at high irradiation dose, PMMA demonstrates improved mechanical properties. With enough electron irradiation dose, the scissions can form new links amongst one another to achieve stability that surpasses that of the PMMA in pre-irradiation treatment state. With higher irradiation dosage and beam strength, hardness of irradiated PMMA could be increased to a much greater extent. Electrons with 50keV of energy can only penetrate around 30 μm of PMMA, thus increasing the beam energy could potentially allow for hardening of not just the surface of the PMMA samples, but the whole samples themselves. Furthermore, Pencil Hardness Test is a method to roughly analyze a material's hardness and does not provide an accurate feedback on the mechanical properties of the material of interest. Hence, a more thorough and effective method of measuring data from the use of equipment such as IZOD Impact Tester, Strain-Stress Tester and Haze Meter will be utilized in the future.

  5. Radiolytic stabilization of poly(methyl methacrylate) using commercial additives

    International Nuclear Information System (INIS)

    Poly(methyl methacrylate), PMMA, Acrigel, a Brazilian polymer, is used in the manufacture of medical supplies sterelizable by ionizing radiation. However, when PMMA is gamma-irradiated it undergoes main chain scissions, which promote molecular degradation causing reduction in its mechanical properties. Therefore, radiolytic of PMMA is important for it to become commercially radiosterizable. In this work some commercial additives, originally used in photo-and thermo-oxidate stabilization of polymers, were tested. Only two additives, type HALS (Hindered Amine Light Stabilizer), denoted Scavenger, showed a good protective quality. The investigation of radiation-induced main scissions was carried out by viscosimetric method. The most effective additive, added to the polymer system at 0.3 w/w%, promotes a great molecular radioprotection of 93%. That means a reduction of G-value (scissions/100 eV) from 0.611 to 0.053. In addition, the glassy transition temperature (Tg) of PMMA (no additive) significantly changed by radiation does not change when PMMA (with additive) is irradiated. The spectroscopy analysis, FT-IR and NMR (1H), showed that the radioprotector added to the system does not change the PMMA structure. (author)

  6. Radiolytic stabilization of industrial poly(methyl methacrylate)

    International Nuclear Information System (INIS)

    Poly(methyl methacrylate), PMMA, Acrigel, a Brazilian polymer, is used in the manufacture of medical supplies sterilisable by ionizing radiation. However, when PMMA is gamma-irradiated it undergoes main chain scissions, which promote molecular degradation causing reduction in its physical properties. Therefore, radiolytic stabilization of PMMA is important for to become it commercially radio sterilisable. In this work we investigated the radiolytic stabilization of PMMA by using HALS (Hindered Amine Light Stabilizer) additive, commercially used for photo and thermo oxidative stabilization of polymers. The investigation of the radiation-induced main chain scissions was carried out by viscometric method. The additive added to the polymer system at 0.3 % w/w promotes a molecular radioprotection of 61%. That means a reduction of G value (scissions/100 eV) from 2.6 to 1.0. In addition, the glassy transition temperature (Tg) of PMMA (no additive), significantly changed by radiation, does not change when PMMA (with additive) is irradiated. TGA analysis showed that the additive promotes thermal stability to the system, increasing decomposition temperature of PMMA. Spectroscopy analysis, FT-IR and RMN (1H), showed that the radioprotector additive added to the system does not change the PMMA structure. Analysis on mechanical (tensile strength and elongation at break) and optical (yellowness index and refractive index) properties showed a good influence of the additive on polymer system. (author)

  7. Surface hardening of poly(methyl methacrylate) by electron irradiation

    International Nuclear Information System (INIS)

    Poly(methyl methacrylate) (PMMA), known as a radiation-degrading polymer, showed mechanically hardening behavior under a high-fluence electron irradiation. When the electron fluence was less than 1 x 1015 cm-2, PMMA showed normal degrading behavior. However, at electron fluence higher than 1 x 1017 cm-2, the mechanical properties of the irradiated PMMA were tremendously improved. Bulk plate PMMA samples and an electron energy of 60 keV were employed in the irradiation experiments. The surface hardness of the irradiated PMMA increased from a pristine value of 0.29 GPa up to 2.8 GPa and the elastic modulus increased from 5.6 GPa to 22.9 GPa at an electron fluence of 7.5 x 1017 cm-2. Both Raman spectra and XPS spectra showed that the surface hardening was attributed to the transformation of polymeric materials into hydrogenated amorphous carbon under the electron irradiation. Confocal Raman spectra showed that the transformation occurred from the surface to the depth of electron range

  8. Poly(methyl methacrylate) films for organic vapour sensing

    CERN Document Server

    Capan, R; Hassan, A K; Tanrisever, T

    2003-01-01

    Optical constants and fabrication parameters are investigated using surface plasmon resonance (SPR) studies on spun films of poly(methyl methacrylate) (PMMA) derivatives in contact with two different dielectric media. A value of 1.503 for the refractive index of PMMA films produced from a solution having concentration of 1 mg ml sup - sup 1 at the speed of 3000 rpm is in close agreement with the data obtained from ellipsometric measurements. The film thickness shows a power-law dependence on the spin speed but the thickness increases almost linearly with the concentration of the spreading solution. These results are in good agreement with the hydrodynamic theory for a low-viscosity and highly volatile liquid. On the basis of SPR measurements under dynamic conditions, room temperature response of PMMA films to benzene vapours is found to be fast, highly sensitive and reversible. The sensitivity of detection of toluene, ethyl benzene and m-xylene is much smaller than that of benzene.

  9. Erythrocyte membrane stabilization effect and antioxidant activity of methyl methacrylate

    International Nuclear Information System (INIS)

    Methyl methacrylate (MMK) is a synthetic product with mild impact on human health that is not well studied on cellular basis. Here, human erythrocytes were used to investigate the effects MMK exerts on acid and heat-induced hemolysis. Biphasic effect of MMK was observed for acid-induced hemolysis; i.e., protection at low (0 - 0.05% v/v) and stimulation at higher (0.1- 0.4% v/v) concentrations. The maximal protective effect was produced at 0.03% (v/v). At this concentration MMK increased the temperatures of heat denaturation of erythrocyte membrane proteins, spectrin and integral proteins, by about 20C and inhibited the heat-induced hemolysis by 20 %. This membrane stabilization effect of MMK is similar to that produced by some anti-inflammatory and antirheumatic drugs. The increased acid resistance possibly indicated anti-oxidant properties of MMK. The nonenzymatic antioxidant activity test evidenced that MMK has no superoxide dismutase-like activity but demonstrates strong catalase-like activity (about 900 kU/mmol at 0.05-0.1 mmol/l concentration). The results indicate that at low concentration MMK exerts benign effect on cellular membrane that could find therapeutic usage. (author)

  10. Anisotropic properties of aligned SWNT modified poly (methyl methacrylate) nanocomposites

    Indian Academy of Sciences (India)

    Weixue Li; Qing Wang; Jianfeng Dai

    2006-06-01

    The poly (methyl methacrylate) (PMMA)/single-walled carbon nanotube (SWNT) composites with good uniformity, dispersion and alignment of SWNT were fabricated in an improved figuration process. The semidried mixture was stretched along one direction at a drawing ratio of 50 before it was dried, and then folded along the same direction stretching repeatedly for 100 times. The transmission electron microscopic (TEM) observation demonstrated that SWNT in the PMMA/SWNT composite tends to align in the stretching direction owing to a torque exerting on it in the stretching process. The electrical and mechanical properties of PMMA/SWNT composite were studied as a function of SWNT orientation and concentration. The aligned SWNT modified PMMA/SWNT composite presented highly anisotropic properties. The experimental results showed that the electrical conductivity and mechanical properties of composite rise with the increase of SWNT concentration, and that composite films showed higher conductivity and higher mechanical draw ratios along the stretched direction than perpendicular to it. The thermogravimetric analysis (TGA) revealed that embedding the SWNTs into the PMMA matrix also improves the thermal stability of the composite.

  11. Manufacture of poly(methyl methacrylate) microspheres using membrane emulsification.

    Science.gov (United States)

    Bux, Jaiyana; Manga, Mohamed S; Hunter, Timothy N; Biggs, Simon

    2016-07-28

    Accurate control of particle size at relatively narrow polydispersity remains a key challenge in the production of synthetic polymer particles at scale. A cross-flow membrane emulsification (XME) technique was used here in the preparation of poly(methyl methacrylate) microspheres at a 1-10 l h(-1) scale, to demonstrate its application for such a manufacturing challenge. XME technology has previously been shown to provide good control over emulsion droplet sizes with careful choice of the operating conditions. We demonstrate here that, for an appropriate formulation, equivalent control can be gained for a precursor emulsion in a batch suspension polymerization process. We report here the influence of key parameters on the emulsification process; we also demonstrate the close correlation in size between the precursor emulsion and the final polymer particles. Two types of polymer particle were produced in this work: a solid microsphere and an oil-filled matrix microcapsule.This article is part of the themed issue 'Soft interfacial materials: from fundamentals to formulation'. PMID:27298430

  12. Purification of large plasmids with methacrylate monolithic columns.

    Science.gov (United States)

    Krajnc, Nika Lendero; Smrekar, Franci; Cerne, Jasmina; Raspor, Peter; Modic, Martina; Krgovic, Danijela; Strancar, Ales; Podgornik, Ales

    2009-08-01

    The rapid evolution of gene therapy and DNA vaccines results in an increasing interest in producing large quantities of pharmaceutical grade plasmid DNA. Most current clinical trials involve plasmids of 10 kb or smaller in size, however, future requirements for multigene vectors including extensive control regions may require the production of larger plasmids, e. g., 20 kb and bigger. The objective of this study was to examine certain process conditions for purification of large plasmids with the size of up to 93 kb. Since there is a lack of knowledge about production and purification of bigger plasmid DNA, cell lysis and storage conditions were investigated. The impact of chromatographic system and methacrylate monolithic column on the degradation of plasmid molecules under nonbinding conditions at different flow rates was studied. Furthermore, capacity measurements varying salt concentration in loading buffer were performed and the capacities up to 13 mg of plasmid per mL of the monolithic column were obtained. The capacity flow independence in the range from 130 to 370 cm/h was observed. Using high resolution monolithic column the separation of linear and supercoiled isoforms of large plasmids was obtained. Last but not least, since the baseline separation of RNA and pDNA was achieved, the one step purification on larger CIM DEAE 8 mL tube monolithic column was performed and the fractions were analyzed by CIM analytical monolithic columns. PMID:19598166

  13. Insulin Release Dynamics from Poly(diethylaminoethyl methacrylate) Hydrogel Systems.

    Science.gov (United States)

    Marek, Steve R; Peppas, Nicholas A

    2013-10-01

    Novel glucose-sensitive systems for the release of insulin from poly(diethylaminoethyl methacrylate) (PDEAEM) micro-particles and nanoparticles decorated with glucose oxidase and catalase enzymes have been developed. The effect of polymer composition and loading conditions on the insulin loading efficiency and release was studied. The optimal conditions for loading insulin into PDEAEM microparticles were found to be at a loading pH of 5.6, particle to insulin mass ratio of 7:1, a concentration of 1.0 mg/mL insulin, and a collapsing pH of approximately 9.5. Microparticles exhibited a responsive (pH) or intelligent (glucose) release of insulin from a stimulus. Microparticles that had a nominal crosslinking ratio of 10% released a third of the insulin payload after a single stimulus, compared to nearly 70% for microparticles with a 3% crosslinking ratio. PDEAEM micro particles of 150 µm diameter showed promise as components of a system of automated, intelligent delivery method for insulin to type I diabetics. PMID:24634515

  14. Well-defined inorganic/organic nanocomposite by nano silica core-poly(methyl methacrylate/butylacrylate/trifluoroethyl methacrylate) shell.

    Science.gov (United States)

    Chang, Gang; He, Ling; Zheng, Wei; Pan, Aizhao; Liu, Jing; Li, Yingjun; Cao, Ruijun

    2013-04-15

    The novel inorganic/organic core-shell SiO2/P(MMA/BA/3FMA) nanocomposite for coating application is synthesized in this paper by seed emulsion polymerization, in which the inorganic phase is composed of nano-SiO2 modified by vinyl-trimethoxysilane (VMS) or γ-methacryloxy propyl trimethoxylsilane (MPMS), and the organic phase is made of terpolymer by 2,2,2-trifluoroethyl methacrylate (3FMA), methyl methacrylate (MMA), and n-butyl acrylate (BA). The chemical structure of SiO2/P(MMA/BA/3FMA) is characterized by FTIR. The effect of surfactant polyvinylpyrrolidone (PVP), sodium dodecyl sulfate (SDS)/octyl phenyl polyoxyethylene ether (TX-10), sodium dodecyl benzene sulfonate (SDBS)/TX-10 and sodium hexametaphosphate (SHMP) on the grafting ratio (GR) of VMS and MPMS, the dispersion of nano-SiO2 particles and the film properties of SiO2/P(MMA/BA/3FMA) are investigated by TGA, DLS, TEM, SEM, and XPS. The morphology variation and the particle size distributions of SiO2/P(MMA/BA/3FMA) with the content of surfactant and P(MMA/BA/3FMA) are characterized. It is found that MPMS is more effective than VMS in improving GR and the dispersion of nano-SiO2 particles. The surfactants are favor of gaining the higher GR in the multilayer grafted nano-SiO2, especially SDS/TX-10 for 17.6% GR. The morphology of SiO2/P(MMA/BA/3FMA) is controlled by the amount of SDS/TX-10 and P(MMA/BA/3FMA) as the core-shell particles, the stacked pomegranate seed with multicore and the multicore-single shell structure when w(MMA)/w(BA)/w(3FMA)=1.3/1/1. Among the different surfactants, SDBS/TX-10 and PVP could give the monodispersing nano-SiO2 in the terpolymer matrix of the films, but SDS/TX-10 and SDBS/TX-10 could perform the fluorine-rich surface. PMID:23403111

  15. Metal Nanoparticle/Block Copolymer Composite Assembly and Disassembly.

    Science.gov (United States)

    Li, Zihui; Sai, Hiroaki; Warren, Scott C; Kamperman, Marleen; Arora, Hitesh; Gruner, Sol M; Wiesner, Ulrich

    2009-01-01

    Ligand-stabilized platinum nanoparticles (Pt NPs) were self-assembled with poly(isoprene-block-dimethylaminoethyl methacrylate) (PI-b-PDMAEMA) block copolymers to generate organic-inorganic hybrid materials. High loadings of NPs in hybrids were achieved through usage of N,N-di-(2-(allyloxy)ethyl)-N-3-mercaptopropyl-N-3-methylammonium chloride as the ligand, which provided high solubility of NPs in various solvents as well as high affinity to PDMAEMA. From NP synthesis, existence of sub-1 nm Pt NPs was confirmed by high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) images. Estimations of the Pt NP ligand head group density based on HAADF-STEM images and thermogravimetric analysis (TGA) data yielded results comparable to what has been found for alkanethiol self-assembled monolayers (SAMs) on flat Pt {111} surfaces. Changing the volume fraction of Pt NPs in block copolymer-NP composites yielded hybrids with spherical micellar, wormlike micellar, lamellar and inverse hexagonal morphologies. Disassembly of hybrids with spherical, wormlike micellar, and lamellar morphologies generated isolated metal-NP based nano-spheres, cylinders and sheets, respectively. Results suggest the existence of powerful design criteria for the formation of metal-based nanostructures from designer blocked macromolecules. PMID:21103025

  16. Fast assembly of ordered block copolymer nanostructures through microwave annealing.

    Science.gov (United States)

    Zhang, Xiaojiang; Harris, Kenneth D; Wu, Nathanael L Y; Murphy, Jeffrey N; Buriak, Jillian M

    2010-11-23

    Block copolymer self-assembly is an innovative technology capable of patterning technologically relevant substrates with nanoscale precision for a range of applications from integrated circuit fabrication to tissue interfacing, for example. In this article, we demonstrate a microwave-based method of rapidly inducing order in block copolymer structures. The technique involves the usage of a commercial microwave reactor to anneal block copolymer films in the presence of appropriate solvents, and we explore the effect of various parameters over the polymer assembly speed and defect density. The approach is applied to the commonly used poly(styrene)-b-poly(methyl methacrylate) (PS-b-PMMA) and poly(styrene)-b-poly(2-vinylpyridine) (PS-b-P2VP) families of block copolymers, and it is found that the substrate resistivity, solvent environment, and anneal temperature all critically influence the self-assembly process. For selected systems, highly ordered patterns were achieved in less than 3 min. In addition, we establish the compatibility of the technique with directed assembly by graphoepitaxy. PMID:20964379

  17. Synthesis of Stimuli-responsive, Water-soluble Poly[2-(dimethylaminoethyl methacrylate/styrene] Statistical Copolymers by Nitroxide Mediated Polymerization

    Directory of Open Access Journals (Sweden)

    Milan Maric

    2011-08-01

    Full Text Available 2-(Dimethylaminoethyl methacrylate/styrene statistical copolymers (poly(DMAEMA-stat-styrene with feed compositions fDMAEMA = 80–95 mol%, (number average molecular weights Mn = 9.5–11.2 kg mol−1 were synthesized using succinimidyl ester-functionalized BlocBuilder alkoxyamine initiator at 80 °C in bulk. Polymerization rate increased three-fold on increasing fDMAEMA = 80 to 95 mol%. Linear Mn increases with conversion were observed up to about 50% conversion and obtained copolymers possessed monomodal, relatively narrow molecular weight distributions (polydispersity = 1.32–1.59. Copolymers with fDMAEMA = 80 and 90 mol% were also cleanly chain-extended with DMAEMA/styrene mixtures of 95 and 90 mol% DMAEMA, respectively, confirming the livingness of the copolymers. Copolymer phase behavior in aqueous solutions was examined by dynamic light scattering and UV-Vis spectroscopy. All copolymers exhibited lower critical solution temperature (LCST-type behavior. LCST decreased with increasing styrene content in the copolymer and with increasing solution concentration. All copolymers were completely water-soluble and temperature insensitive at pH 4 but were more hydrophobic at pH 10, particularly copolymers with fDMAEMA = 80 and 85 mol%, which were water-insoluble. At pH 10, LCST of copolymers with fDMAEMA = 90 and 95 mol% were more than 10 °C lower compared to their solutions in neutral, de-ionized water. Block copolymers with two statistical blocks with different DMAEMA compositions exhibited a single LCST, suggesting the block segments were not distinct enough to exhibit separate LCSTs in water.

  18. Predictability of blocking

    International Nuclear Information System (INIS)

    Tibaldi and Molteni (1990, hereafter referred to as TM) had previously investigated operational blocking predictability by the ECMWF model and the possible relationships between model systematic error and blocking in the winter season of the Northern Hemisphere, using seven years of ECMWF operational archives of analyses and day 1 to 10 forecasts. They showed that fewer blocking episodes than in the real atmosphere were generally simulated by the model, and that this deficiency increased with increasing forecast time. As a consequence of this, a major contribution to the systematic error in the winter season was shown to derive from the inability of the model to properly forecast blocking. In this study, the analysis performed in TM for the first seven winter seasons of the ECMWF operational model is extended to the subsequent five winters, during which model development, reflecting both resolution increases and parametrisation modifications, continued unabated. In addition the objective blocking index developed by TM has been applied to the observed data to study the natural low frequency variability of blocking. The ability to simulate blocking of some climate models has also been tested

  19. Control of Protein Affinity of Bioactive Nanocellulose and Passivation Using Engineered Block and Random Copolymers.

    Science.gov (United States)

    Vuoriluoto, Maija; Orelma, Hannes; Zhu, Baolei; Johansson, Leena-Sisko; Rojas, Orlando J

    2016-03-01

    We passivated TEMPO-oxidized cellulose nanofibrils (TOCNF) toward human immunoglobulin G (hIgG) by modification with block and random copolymers of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA). The block copolymers reversibly adsorbed on TOCNF and were highly effective in preventing nonspecific interactions with hIgG, especially if short PDMAEMA blocks were used. In such cases, total protein rejection was achieved. This is in contrast to typical blocking agents, which performed poorly. When an anti-human IgG biointerface was installed onto the passivated TOCNF, remarkably high affinity antibody-antigen interactions were observed (0.90 ± 0.09 mg/m(2)). This is in contrast to the nonpassivated biointerface, which resulted in a significant false response. In addition, regeneration of the biointerface was possible by low pH aqueous wash. Protein A from Staphylococcus aureus was also utilized to successfully increase the sensitivity for human IgG recognition (1.28 ± 0.11 mg/m(2)). Overall, the developed system based on TOCNF modified with multifunctional polymers can be easily deployed as bioactive material with minimum fouling and excellent selectivity. PMID:26844956

  20. Composition and solution properties of fluorinated block copolymers and their surface structures in the solid state

    Institute of Scientific and Technical Information of China (English)

    NI HuaGang; XUE DongWu; WANG XiaoFang; ZHANG Wei; WANG XinPing; SHEN ZhiQuan

    2009-01-01

    A series of diblock copolymers composed of methyl methacrylate and 2-perfluorooctylethyl methacry-late (PMMA144-b-PFMAn) with various PFMA block lengths were prepared by atom transfer radical po-lymerization (ATRP). The surface structures and properties of these polymers in the solid state and in solution were investigated using contact angle measurement, X-ray photoelectron spectroscopy (XPS), sum frequency generation (SFG) vibrational spectroscopy, surface tension and dynamic laser light scattering (DLS). It was found that with increasing PFMA block length, water and oil repellency de-creased, the ratio of F/C increased with increasing film depth, and the degree of ordered packing of the perfluoroalkyl side chains at the surface decreased. When the number of PFMA block units reached 10, PMMA segments were detected at the copolymer surface, which was attributed to the PFMA block length affecting molecular aggregation structure of the copolymer in the solution and the interfacial structure at the air/liquid interface, which in turn affects surface structure formation during solution solidification. The results suggest that copolymer solution properties play an important role in struc-ture formation on the solid surface.

  1. Block Cipher Analysis

    DEFF Research Database (Denmark)

    Miolane, Charlotte Vikkelsø

    ensurethat no attack violatesthe securitybounds specifiedbygeneric attack namely exhaustivekey search and table lookup attacks. This thesis contains a general introduction to cryptography with focus on block ciphers and important block cipher designs, in particular the Advanced Encryption Standard......(AES).Wedescribe the mostgeneraltypes ofblock cipher cryptanalysis but concentrate on the algebraic attacks. While the algebraic techniques have been successful oncertainstreamcipherstheirapplicationtoblock ciphershasnot shown any significant results so far. This thesis contributes to the field of algebraic attacks on...... algebraic results on small scale variants of AES. In the final part of the thesis we present a new block cipher proposal Present and examine its security against algebraic and differential cryptanalysis in particular....

  2. Polymerization of oligo(ethylene glycol) methacrylate from monodisperse poly(glycidyl methacrylate) microsphers to reduce non-specific protein adsorption

    Czech Academy of Sciences Publication Activity Database

    Grama, Silvia; Heuts, H.; Horák, Daniel

    Riva del Garda : Elsevier, 2015. P2.010. [International Symposium Frontiers in Polymer Science /4./ - POLY 2015. 20.05.2015-22.05.2015, Riva del Garda] R&D Projects: GA MŠk(CZ) EE2.3.30.0029 Institutional support: RVO:61389013 Keywords : microspheres * poly(glycidyl methacrylate) * atom transfer radical polymerization Subject RIV: CE - Biochemistry

  3. 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.

  4. 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)

    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, 13C, 29Si 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

  5. Effect of trans-cis photoisomerization on phase equilibria and phase transition of liquid-crystalline azobenzene chromophore and its blends with reactive mesogenic diacrylate.

    Science.gov (United States)

    Kim, Namil; Li, Quan; Kyu, Thein

    2011-03-01

    Photoisomerization-induced phase transition of neat liquid-crystalline azobenzene chromophore (LCAC) and its effect on phase diagrams of its mixtures with reactive mesogenic diacrylate monomer (RM257) have been investigated experimentally and theoretically. Upon irradiation with ultraviolet light, the nematic phase of LCAC transformed to isotropic, while the crystal phase showed corrugated textures on the surface (i.e., ripples). The phase-transition temperatures and corresponding morphologies of the blends have been investigated by means of differential scanning calorimetry and optical microscopy. A theoretical phase diagram of a binary nematic and crystalline system was constructed by self-consistently solving the combined free energies of Flory-Huggins, Maier-Saupe, and phase-field theory. The calculation revealed various coexistence regions such as nematic + liquid (N₁ + L₂), crystal + liquid (Cr₁ + L₂), crystal + nematic (Cr₁ + N₂), and crystal + crystal (Cr₁ + Cr₂) over a broad range of compositions including the single-phase nematic (N₁, N₂) of the corresponding constituents. The calculated liquidus lines were in good accord with the depressed mesophase-isotropic transition points. The present paper demonstrates the effect of trans-cis photoisomerization on the mesophase transitions of neat LCAC and the phase diagram of LCAC-RM257 as well as on the ripple formation (i.e., periodic undulation) on the azobenzene crystals. PMID:21517513

  6. Modeling of a Buss-Kneader as a Polymerization Reactor for Acrylates. Part II: Methyl Methacrylate Based Resins

    OpenAIRE

    Janssen, L.P.B.M.; Dierendonck, L.L. van; Troelstra, E. J.; Renken, A.

    2002-01-01

    The Buss-Kneader has proven to be a suitable reactor for the polymerization of acrylates. In this second part, the polymerization of methyl methacrylate and the ter- polymerization of methyl methacrylate (MMA), hydroxyethyl methacrylate and n-butylmethacrylate is carried out in a pilot Buss-Kneader. The reactor had to be pressurized up to about 10 bars to avoid evaporation of MMA. Instabilities in output rate and temperature profiles were observed as a result of fluctuating the pressures. Bec...

  7. 偶氮苯聚氨酯基抗皱功能高分子染料制备及性能%Synthesis and properties of azobenzene-polyurethane based anti-wrinkle polymeric dye

    Institute of Scientific and Technical Information of China (English)

    冒海燕; 张淼; 强思雨; 杨小祥; 王潮霞; 殷允杰

    2016-01-01

    为同步实现纺织品着色与功能整理并改善低分子染料的耐热迁移性,通过共价键合方式将N, N-二羟乙基偶氮苯发色体引入聚氨酯分子链,制备具有抗皱功能的偶氮苯聚氨酯基高分子染料.结果表明,偶氮苯发色体的反应率为87.81%,占聚氨酯链的3.53%,偶氮苯聚氨酯基高分子染料色光未发生变化,且涂层织物色泽鲜艳饱满,K/S值从1.50提高到4.61,急弹折皱回复角从110º增加到183º,缓弹折皱回复角从136º提高到227º,且热迁移率下降至5%,因此,偶氮苯聚氨酯基高分子染料不仅具有良好的抗皱性及耐热迁移性,而且为缩短纺织品生产工艺流程提供了一条新途径.%Azobenzene-polyurethane based polymeric dye with anti-wrinkle property was prepared by covalently bonding N,N-di(2-hydroxyethyl) azobenzene with polyurethane chain to synchronously realize coloring and functional finishing and enhance the thermal migration. Results showed that reaction rate of azobenzene and its content in polyurethane chain were 87. 81% and 3. 53%, respectively. The color remained unchanged after the azobenzene was introduced into polyurethane. The coated cotton fabric with the azobenzene-polyurethane polymeric dye presented more vivid and richer shade than that with azobenzene physically mixed polyurethane, and the K/S value increased from 1. 50 to 4. 61. The fast and delayed elastic recovery angles of the coated fabric were improved from 110 º to 183 º and 136 º to 227 º , respectively. The thermal migration rate was dramatically reduced to 5%. Consequently, the azobenzene-polyurethane polymeric dye exhibited outstanding anti-wrinkle property and thermal migration property, which provided a novel route for shortening the textile technological process.

  8. Block copolymer battery separator

    Energy Technology Data Exchange (ETDEWEB)

    Wong, David; Balsara, Nitash Pervez

    2016-04-26

    The invention herein described is the use of a block copolymer/homopolymer blend for creating nanoporous materials for transport applications. Specifically, this is demonstrated by using the block copolymer poly(styrene-block-ethylene-block-styrene) (SES) and blending it with homopolymer polystyrene (PS). After blending the polymers, a film is cast, and the film is submerged in tetrahydrofuran, which removes the PS. This creates a nanoporous polymer film, whereby the holes are lined with PS. Control of morphology of the system is achieved by manipulating the amount of PS added and the relative size of the PS added. The porous nature of these films was demonstrated by measuring the ionic conductivity in a traditional battery electrolyte, 1M LiPF.sub.6 in EC/DEC (1:1 v/v) using AC impedance spectroscopy and comparing these results to commercially available battery separators.

  9. Low Molecular Weight pDMAEMA-block-pHEMA Block-Copolymers Synthesized via RAFT-Polymerization: Potential Non-Viral Gene Delivery Agents?

    Directory of Open Access Journals (Sweden)

    Thomas Kissel

    2011-03-01

    Full Text Available The aim of this study was to investigate non-viral pDNA carriers based on diblock-copolymers consisting of poly(2-(dimethyl aminoethyl methacrylate (pDMAEMA and poly(2-hydroxyethyl methacrylate (pHEMA. Specifically the block-lengths and molecular weights were varied to determine the minimal requirements for transfection. Such vectors should allow better transfection at acceptable toxicity levels and the entire diblock-copolymer should be suitable for renal clearance. For this purpose, a library of linear poly(2-(dimethyl aminoethyl methacrylate-block-poly(2-hydroxyl methacrylate (pDMAEMA-block-pHEMA copolymers was synthesized via RAFT (reversible addition-fragmentation chain transfer polymerization in a molecular weight (Mw range of 17–35.7 kDa and analyzed using 1H and 13C NMR (nuclear magnetic resonance, ATR (attenuated total reflectance, GPC (gel permeation chromatography and DSC (differential scanning calorimetry. Copolymers possessing short pDMAEMA-polycation chains were 1.4–9.7 times less toxic in vitro than polyethylenimine (PEI 25 kDa, and complexed DNA into polyplexes of 100–170 nm, favorable for cellular uptake. The DNA-binding affinity and polyplex stability against competing polyanions was comparable with PEI 25 kDa. The zeta-potential of polyplexes of pDMAEMA-grafted copolymers remained positive (+15–30 mV. In comparison with earlier reported low molecular weight homo pDMAEMA vectors, these diblock-copolymers showed enhanced transfection efficacy under in vitro conditions due to their lower cytotoxicity, efficient cellular uptake and DNA packaging. The homo pDMAEMA115 (18.3 kDa self-assembled with DNA into small positively charged polyplexes, but was not able to transfect cells. The grafting of 6 and 57 repeating units of pHEMA (0.8 and 7.4 kDa to pDMAEMA115 increased the transfection efficacy significantly, implying a crucial impact of pHEMA on vector-cell interactions. The intracellular trafficking, in vivo transfection

  10. Novel architecture design of ultra low-fouling block copolymers of oligo ethylene glycol methyl ether methacrylate and carboxybetaine acrylamide

    Czech Academy of Sciences Publication Activity Database

    Rodriguez-Emmenegger, Cesar; Hasan, B.; Brynda, Eduard; Houska, Milan; Sedláková, Zdeňka; Bologna Alles, A.; Gautrot, J.; Huck, W.

    Praha : Ústav makromolekulární chemie AV ČR, 2009. L5. ISBN 978-80-85009-60-6. [Workshop: Career in Polymers. 10.07.2009-11.07.2009, Prague] R&D Projects: GA AV ČR KAN200670701 Institutional research plan: CEZ:AV0Z40500505 Subject RIV: CD - Macromolecular Chemistry

  11. Blocking in Category Learning

    OpenAIRE

    Bott, Lewis; Hoffman, Aaron B.; Murphy, Gregory L.

    2007-01-01

    Many theories of category learning assume that learning is driven by a need to minimize classification error. When there is no classification error, therefore, learning of individual features should be negligible. We tested this hypothesis by conducting three category learning experiments adapted from an associative learning blocking paradigm. Contrary to an error-driven account of learning, participants learned a wide range of information when they learned about categories, and blocking effe...

  12. Concord Housing Blocks

    OpenAIRE

    Kumaraswamy, Mohan

    2002-01-01

    One element of the CIVCAL project Web-based resources containing images, tables, texts and associated data on the construction of Concord type Housing Blocks. A high rise public housing project using prefabriction and advanced formwork systems. Both Harmony and Concord Blocks are designed on the basis of standard modular flats which permit the use of factory produced components and a construction sequence which makes extensive use of advanced formwork systems.

  13. Efficient Block Truncation Coding

    Directory of Open Access Journals (Sweden)

    K.Somasundaram,

    2010-09-01

    Full Text Available Block Truncation Coding (BTC is one of the lossy image compression techniques. The computational complexity involved in this method is very simple. In the proposed method, the feature of inter-pixel correlation is exploited to further reduce the requirement of bits to store a block. The proposed method gives very good performance in terms of bit-rate and PSNR values when compared to the conventional BTC.

  14. Gelation of photopolymerized hyaluronic acid grafted with glycidyl methacrylate

    Energy Technology Data Exchange (ETDEWEB)

    Prado, S.S.; Weaver, J.M.; Love, B.J., E-mail: bjlove@umich.edu

    2011-12-01

    Experiments have tracked the ambient gelation of a series of hydrophilic hyaluronic acid (HA) resins grafted with glycidyl methacrylate (GM) and photopolymerized as a function of dose. The resin mixtures range in GMHA concentration between 0.5 and 1.5% w/w in phosphate buffered saline (PBS). Illuminated at 20 mW/cm{sup 2}, the dynamic viscosity ({eta}(t)) has been tracked and characterized using the Boltzmann log-sigmoidal model. A gelled viscosity of {approx} 10 Pa s was determined at 0.5% w/w which rose to {approx} 50 Pa s at or above 1% w/w. More curing agent marginally increased the gel viscosity at each concentration. Time constants associated with viscosity advancement were shortest at [GMHA] = 1.0%; higher concentrations are attributed with lower quantum efficiency when illuminated. Subsequent frequency sweeps replicated already published work using similar GHMA concentrations in PBS. G' values ranged from 100 to 500 Pa over the formulation range with expected sensitivity to GMHA and curing agent concentration. Overall, the sigmoidal model represented this advancing viscosity data well, and further analysis of the physical significance of these model parameters may help in understanding photopolymerization of this complicated formulation more broadly. Highlights: {yields} The ambient dynamic viscosity of photopolymerized GMHA gels has been measured. {yields} 2 physical parameters and two time constants were extracted from the sigmoidal model. {yields} Higher crosslinker content for a fixed GMHA concentration led to higher gel viscosity. {yields} The time to toggle between the initial and final viscosity ranged between 5 and 10 s. {yields} Dynamic frequency sweep tests on cured gels also revealed G' values between 100 and 500 Pa.

  15. Gelation of photopolymerized hyaluronic acid grafted with glycidyl methacrylate

    International Nuclear Information System (INIS)

    Experiments have tracked the ambient gelation of a series of hydrophilic hyaluronic acid (HA) resins grafted with glycidyl methacrylate (GM) and photopolymerized as a function of dose. The resin mixtures range in GMHA concentration between 0.5 and 1.5% w/w in phosphate buffered saline (PBS). Illuminated at 20 mW/cm2, the dynamic viscosity (η(t)) has been tracked and characterized using the Boltzmann log-sigmoidal model. A gelled viscosity of ∼ 10 Pa s was determined at 0.5% w/w which rose to ∼ 50 Pa s at or above 1% w/w. More curing agent marginally increased the gel viscosity at each concentration. Time constants associated with viscosity advancement were shortest at [GMHA] = 1.0%; higher concentrations are attributed with lower quantum efficiency when illuminated. Subsequent frequency sweeps replicated already published work using similar GHMA concentrations in PBS. G' values ranged from 100 to 500 Pa over the formulation range with expected sensitivity to GMHA and curing agent concentration. Overall, the sigmoidal model represented this advancing viscosity data well, and further analysis of the physical significance of these model parameters may help in understanding photopolymerization of this complicated formulation more broadly. Highlights: → The ambient dynamic viscosity of photopolymerized GMHA gels has been measured. → 2 physical parameters and two time constants were extracted from the sigmoidal model. → Higher crosslinker content for a fixed GMHA concentration led to higher gel viscosity. → The time to toggle between the initial and final viscosity ranged between 5 and 10 s. → Dynamic frequency sweep tests on cured gels also revealed G' values between 100 and 500 Pa.

  16. Dual-functional electrospun poly(2-hydroxyethyl methacrylate).

    Science.gov (United States)

    Zhang, Bo; Lalani, Reza; Cheng, Fang; Liu, Qingsheng; Liu, Lingyun

    2011-12-01

    Poly(2-hydroxyethyl methacrylate) (pHEMA) has been widely used in many biomedical applications due to its well-known biocompatibility. For tissue engineering applications, porous scaffolds that mimic fibrous structures of natural extracellular matrix and possess high surface-area-to-volume ratios are highly desirable. So far, a systematic approach to control diameter and morphology of pHEMA fibers has not been reported and potential applications of pHEMA fibers have barely been explored. In this work, pHEMA was synthesized and processed into fibrous scaffolds using an electrospinning approach. Fiber diameters from 270 nm to 3.6 μm were achieved by controlling polymer solution concentration and electrospinning flow rate. Post-electrospinning thermal treatment significantly improves integrity of the electrospun membranes in water. The pHEMA microfibrous membranes exhibited water absorption up to 280% (w/w), whereas the pHEMA hydrogel only absorbed 70% water. Fibrinogen adsorption experiments demonstrate that the electrospun pHEMA fibers highly resist nonspecific protein adsorption. Hydroxyl groups on electrospun pHEMA fibers were further activated for protein immobilization. A bovine serum albumin (BSA) binding capacity as high as 120 mg BSA/g membrane was realized at an intermediate fiber diameter. The pHEMA fibrous scaffolds functionalized with collagen I significantly promoted fibroblast adhesion, spreading, and proliferation. We conclude that the electrospun pHEMA fibers are dual functional, that is, they resist nonspecific protein adsorption meanwhile abundant hydroxyl groups on fibers allow effective conjugation of biomolecules in a nonfouling background. High water absorption and dual functionality of the electrospun pHEMA fibers may lead to a number of potential applications such as wound dressings, tissue scaffolds, and affinity membranes. PMID:21887741

  17. Assessment of methyl methacrylate genotoxicity by the micronucleus test

    Directory of Open Access Journals (Sweden)

    Amarildo Mariano de Araújo

    2013-02-01

    Full Text Available The aim of this study was to evaluate the genotoxic potential of methyl methacrylate (MMA vapor by simulating standard occupational exposure of 8 hours per day and using the micronucleus test. We used 32 adult male Wistar rats divided into three groups: A - 16 rats exposed to MMA for 8 hours a day, B - Eight rats receiving single subcutaneous doses of cyclophosphamide on the first day of the experiment (positive control, C - Eight rats receiving only water and food ad libitum (negative control. Eight rats from group A and all of the rats from groups B and C were sacrificed 24 hours after beginning the experiment (acute exposure in group A. The remaining animals in group A were sacrificed 5 days after the experiment began (repeated exposure assessment in group A, simulating occupational exposure 40 hours/week. Femoral bone marrow was collected from each rat at the time of sacrifice for use in the micronucleus test. Two slides were completed per animal and were stained with Giemsa staining. Two thousand polychromatic erythrocytes were counted per animal. The Kruskal-Wallis test followed by a multiple comparisons test (Dunn test was used for statistical analysis. The median number of micronuclei was 7.00 in the group exposed to MMA for 1 day, 2.00 in the group exposed to MMA for 5 days, 9.00 in the group exposed to cyclophosphamide (positive control and 0.756 in the negative control group (p < 0.0001. MMA was genotoxic when measured after 1 day of exposure but was not evidently genotoxic after 5 days.

  18. Efficient Condensation of DNA into Environmentally Responsive Polyplexes Produced from Block Catiomers Carrying Amine or Diamine Groups.

    Science.gov (United States)

    Albuquerque, Lindomar J C; Annes, Kelly; Milazzotto, Marcella P; Mattei, Bruno; Riske, Karin A; Jäger, Eliézer; Pánek, Jiří; Štěpánek, Petr; Kapusta, Peter; Muraro, Paulo I R; De Freitas, Augusto G O; Schmidt, Vanessa; Giacomelli, Cristiano; Bonvent, Jean-Jacques; Giacomelli, Fernando C

    2016-01-19

    The intracellular delivery of nucleic acids requires a vector system as they cannot diffuse across lipid membranes. Although polymeric transfecting agents have been extensively investigated, none of the proposed gene delivery vehicles fulfill all of the requirements needed for an effective therapy, namely, the ability to bind and compact DNA into polyplexes, stability in the serum environment, endosome-disrupting capacity, efficient intracellular DNA release, and low toxicity. The challenges are mainly attributed to conflicting properties such as stability vs efficient DNA release and toxicity vs efficient endosome-disrupting capacity. Accordingly, investigations aimed at safe and efficient therapies are still essential to achieving gene therapy clinical success. Taking into account the mentioned issues, herein we have evaluated the DNA condensation ability of poly(ethylene oxide)113-b-poly[2-(diisopropylamino)ethyl methacrylate]50 (PEO113-b-PDPA50), poly(ethylene oxide)113-b-poly[2-(diethylamino)ethyl methacrylate]50 (PEO113-b-PDEA50), poly[oligo(ethylene glycol)methyl ether methacrylate]70-b-poly[oligo(ethylene glycol)methyl ether methacrylate10-co-2-(diethylamino)ethyl methacrylate47-co-2-(diisopropylamino)ethyl methacrylate47] (POEGMA70-b-P(OEGMA10-co-DEA47-co-DPA47), and poly[oligo(ethylene glycol)methyl ether methacrylate]70-b-poly{oligo(ethylene glycol)methyl ether methacrylate10-co-2-methylacrylic acid 2-[(2-(dimethylamino)ethyl)methylamino]ethyl ester44} (POEGMA70-b-P(OEGMA10-co-DAMA44). Block copolymers PEO113-b-PDEA50 and POEGMA70-b-P(OEGMA10-co-DEA47-co-DPA47) were evidenced to properly condense DNA into particles with a desirable size for cellular uptake via endocytic pathways (R(H) ≈ 65-85 nm). The structure of the polyplexes was characterized in detail by scattering techniques and atomic force microscopy. The isothermal titration calorimetric data revealed that the polymer/DNA binding is endothermic; therefore, the process in entropically driven

  19. Dispersion of luminescent nanoparticles in different derivatives of poly(ethyl methacrylate).

    Science.gov (United States)

    Davion, B; Delhorbe, V; Péralta, S P; Goubard, F; Vidal, F

    2011-04-01

    Gd2O3:Tb(5%) nanoparticles were prepared via the polyol route and dispersed without any stabilizer in several ethyl methacrylate derivatives matrices such as poly(ethyl methacrylate), poly(2-methoxyethyl methacrylate) and poly(2-hydroxyethyl methacrylate) (PHEMA). Nanocomposites were obtained via free-radical polymerization of methacrylic monomers with ethylene glycol dimethacrylate as crosslinker and colloidal solution of Gd2O3:Tb(5%) nanoparticles. Best results are obtained with PHEMA in which the dispersed Gd2O3:Tb(5%) nanoparticles are spherical with a mean diameter of 15 nm, as measured by TEM. The obtained solid Gd2O3:Tb(5%)/PHEMA nanocomposites are highly transparent (in the visible spectral range) and exhibit characteristic photoluminescence of Tb3+ 5D4-7F(J) (J = 6-3), with 5D4-7F5 strong green emission at 536 nm upon UV excitation. The nanoparticles and nanocomposites have been well characterized by high-resolution transmission electron microscope (TEM), UV/Vis transmission spectra, photoluminescence excitation, and emission spectra. PMID:21776688

  20. Mechanical Properties of Surface-Charged Poly(Methyl Methacrylate as Denture Resins

    Directory of Open Access Journals (Sweden)

    Sang E. Park

    2009-01-01

    Full Text Available The aim of this study was to examine the mechanical properties of a new surface-modified denture resin for its suitability as denture base material. This experimental resin is made by copolymerization of methacrylic acid (MA to poly(methyl methacrylate (PMMA to produce a negative charge. Four experimental groups consisted of Orthodontic Dental Resin (DENTSPLY Caulk as a control and three groups of modified PMMA (mPMMA produced at differing ratios of methacrylic acid (5 : 95, 10 : 90, and 20 : 80 MA : MMA. A 3-point flexural test using the Instron Universal Testing Machine (Instron Corp. measured force-deflection curves and a complete stress versus strain history to calculate the transverse strength, transverse deflection, flexural strength, and modulus of elasticity. Analysis of Variance and Scheffe Post-test were performed on the data. Resins with increased methacrylic acid content exhibited lower strength values for the measured physical properties. The most significant decrease occurred as the methacrylic acid content was increased to 20% mPMMA. No significant differences at P<.05 were found in all parameters tested between the Control and 5% mPMMA.

  1. Micelle-like nanoparticles of block copolymer poly(ethylene oxide)-block-poly(methacrylic acid) incorporating fluorescently substituted metallacarboranes designed as HIV protease inhibitor interaction probes

    Czech Academy of Sciences Publication Activity Database

    Uchman, M.; Cígler, Petr; Grüner, Bohumír; Procházka, K.; Matějíček, P.

    2010-01-01

    Roč. 348, č. 1 (2010), s. 129-136. ISSN 0021-9797 R&D Projects: GA MŠk LC523; GA AV ČR IAAX00320901 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40320502 Keywords : metallacarboranes * micelles * drug delivery Subject RIV: CC - Organic Chemistry Impact factor: 3.068, year: 2010

  2. Impression block with orientator

    International Nuclear Information System (INIS)

    Tool review, namely the impression block, applied to check the shape and size of the top of fish as well as to determine the appropriate tool for fishing operation was realized. For multiple application and obtaining of the impress depth of 3 cm and more, the standard volumetric impression blocks with fix rods are used. However, the registered impress of fish is not oriented in space and the rods during fishing are in the extended position. This leads to rods deformation and sinking due to accidental impacts of impression block over the borehole irregularity and finally results in faulty detection of the top end of fishing object in hole. The impression blocks with copy rods and fixed magnetic needle allow estimating the object configuration and fix the position of magnetic needle determining the position of the top end of object in hole. However, the magnetic needle fixation is realized in staged and the rods are in extended position during fishing operations as well as it is in standard design. The most efficient tool is the impression block with copy rods which directs the examined object in the borehole during readings of magnetic needles data from azimuth plate and averaging of readings. This significantly increases the accuracy of fishing toll direction. The rods during fishing are located in the body and extended only when they reach the top of fishing object

  3. Uniaxial backfill block compaction

    International Nuclear Information System (INIS)

    The main parts of the project were: to make a literature survey of the previous uniaxial compaction experiments; do uniaxial compaction tests in laboratory scale; and do industrial scale production tests. Object of the project was to sort out the different factors affecting the quality assurance chain of the backfill block uniaxial production and solve a material sticking to mould problem which appeared during manufacturing the blocks of bentonite and cruched rock mixture. The effect of mineralogical and chemical composition on the long term functionality of the backfill was excluded from the project. However, the used smectite-rich clays have been tested for mineralogical consistency. These tests were done in B and Tech OY according their SOPs. The objective of the Laboratory scale tests was to find right material- and compaction parameters for the industrial scale tests. Direct comparison between the laboratory scale tests and industrial scale tests is not possible because the mould geometry and compaction speed has a big influence for the compaction process. For this reason the selected material parameters were also affected by the previous compaction experiments. The industrial scale tests were done in summer of 2010 in southern Sweden. Blocks were done with uniaxial compaction. A 40 tons of the mixture of bentonite and crushed rock blocks and almost 50 tons of Friedland-clay blocks were compacted. (orig.)

  4. Block diagonal and schur complement preconditioners for block-toeplitz systems with small size blocks

    OpenAIRE

    Ching, WK; Ng, MK; Wen, YW

    2007-01-01

    In this paper we consider the solution of Hermitian positive definite block-Toeplitz systems with small size blocks. We propose and study block diagonal and Schur complement preconditioners for such block-Toeplitz matrices. We show that for some block-Toeplitz matrices, the spectra of the preconditioned matrices are uniformly bounded except for a fixed number of outliers where this fixed number depends only on the size of the block. Hence, conjugate gradient type methods, when applied to solv...

  5. Synthesis and characterization of methacrylate matrix resin bearing o-nitrobenzyl group

    Institute of Scientific and Technical Information of China (English)

    郭玲香; 管婧; 林保平; 杨洪

    2015-01-01

    The matrix polymer PTBCHNB bearing o-nitrobenzyl group was successfully synthesized by copolymerization of tertiary-butyl methacrylate (TBMA), cyclohexyl methacrylate (CHMA) and o-nitrobenzyl methacrylate (NBMA) via reversible addition fragmentation chain transfer (RAFT) polymerization method. PTBCHNB was characterized by FTIR, 1HNMR, GPC and DSC. After UV irradiation, the o-nitrobenzyl groups of PTBCHNB were photocleaved and the resulting carboxyl groups were highly alkali soluble, and PTBCHNB was converted to PCHIBMA bearing carboxyl groups. So, the matrix polymer could be etched by mild alkali solution with no requirements of photoacid generators and other diverse additives. The photocleavable behaviors of PTBCHNB were determined by FTIR, 1H NMR and TGA analysis. The resist formulated with PTBCHNB and cast in THF solution showed square pattern of 10 μm×10 μm using a mercury-xenon lamp in a contact printing mode and tetramethyl-ammonium hydroxide aqueous solution as a developer.

  6. Nymble Blocking System

    Directory of Open Access Journals (Sweden)

    Anand Joshi

    2012-05-01

    Full Text Available In order to allow users to access Internet services privately, anonymizing networks like Tor uses a series of routers to hide the client’s IP address from the server. These networks, however, have been marred by users employing this anonymity for abusive purposes such as defacing popular web sites. Usually, web site administrators rely on IP-address blocking in order to disable access to misbehaving users, but it is impractical if the abuser routes through an anonymizing network. In order to avoid this, administrators bar all known exit nodes of the anonymizing network, thereby denying anonymous access to all the users(whether misbehaving or not. To solve this issue, we introduce Nymble, a system where servers blacklist misbehaving users, thereby blocking users without affecting their anonymity. Nymble is thus agnostic to varied definitions of misbehavior. Servers can block users for any reason, and the privacy of blacklisted users is not affected in any case.

  7. Mutagenicity assessment of acrylate and methacrylate compounds and implications for regulatory toxicology requirements.

    Science.gov (United States)

    Johannsen, F R; Vogt, Barbara; Waite, Maureen; Deskin, Randy

    2008-04-01

    Esters of acrylic acid and methacrylic acid, more commonly known as acrylates and methacrylates, respectively, are key raw materials in the coatings and printing industry, with several of its chemical class used in food packaging. The results of over 200 short-term in vitro and in vivo mutagenicity studies available in the open literature have been evaluated. Despite differences in acrylate or methacrylate functionality or in the number of functional groups, a consistent pattern of test response was seen in a typical regulatory battery of mutagenicity tests. No evidence of point mutations was observed when acrylic acid or over 60 acrylates and methacrylates were investigated in Salmonella bacterial tests or in hprt mutation tests mammalian cells, and no evidence of a mutagenic effect was seen when tested in whole animal clastogenicity and/or aneuploidy (chromosomal aberration/micronucleus) studies. Consistent with the in vivo testing results, acrylic acid exhibited no evidence of carcinogenicity in chronic rodent cancer bioassays. In contrast, acrylic acid and the entire acrylate and methacrylate chemical class produced a consistently positive response when tested in the mouse lymphoma assay and/or other in vitro mammalian cell assays designed to detect clastogenicity. The biological relevance of this in vitro response is questioned based on the non-concordance of in vitro results with those of in vivo studies addressing the same mutagenic endpoint (clastogenicity). Thus, in short-term mutagenicity tests, the acrylates and methacrylates behave as a single chemical category, and genotoxicity behavior of a similar chemical can be predicted with confidence by inclusion within this chemical class, thus avoiding unnecessary testing. PMID:18346829

  8. Bactericidal block copolymer micelles.

    Science.gov (United States)

    Vyhnalkova, Renata; Eisenberg, Adi; van de Ven, Theo

    2011-05-12

    Block copolymer micelles with bactericidal properties were designed to deactivate pathogens such as E. coli bacteria. The micelles of PS-b-PAA and PS-b-P4VP block copolymers were loaded with biocides TCMTB or TCN up to 20 or 30 wt.-%, depending on the type of antibacterial agent. Bacteria were exposed to loaded micelles and bacterial deactivation was evaluated. The micelles loaded with TCN are bactericidal; bacteria are killed in less than two minutes of exposure. The most likely interpretation of the data is that the biocide is transferred to the bacteria by repeated micelle/bacteria contacts, and not via the solution. PMID:21275041

  9. E-Block: A Tangible Programming Tool with Graphical Blocks

    OpenAIRE

    Danli Wang; Yang Zhang; Shengyong Chen

    2013-01-01

    This paper designs a tangible programming tool, E-Block, for children aged 5 to 9 to experience the preliminary understanding of programming by building blocks. With embedded artificial intelligence, the tool defines the programming blocks with the sensors as the input and enables children to write programs to complete the tasks in the computer. The symbol on the programming block's surface is used to help children understanding the function of each block. The sequence information is transfer...

  10. Simultaneous Photoinduced ATRP and CuAAC Reactions for the Synthesis of Block Copolymers.

    Science.gov (United States)

    Murtezi, Eljesa; Yagci, Yusuf

    2014-09-01

    Atom transfer radical polymerization (ATRP) and copper-catalyzed azide-alkyne cycloaddition (CuAAC) reactions, both utilizing copper(I) (Cu(I)) complexes, make a tremendous progress in synthetic polymer chemistry. Independently or in combination with other polymerization processes, they give access to the synthesis of polymers with well-defined structures, desired molecular architectures, and a wide variety of functionalities. Here, a novel in situ photoinduced formation of block copolymers is described by simultaneous ATRP and CuAAC processes. This approach relies on the direct reduction of initially charged copper(II) complexes to Cu(I) complexes to trigger both ATRP and CuAAC reactions coinciding under UV light at ambient temperature in one pot. Its synthetic utility is demonstrated on a model block copolymerization process by photoinduced ATRP of methyl methacrylate (MMA) using an initiator possessing acetylene functionality and concomitant click reaction between thus formed α-acetylene-poly(methyl methacrylate) (Ac-PMMA) and independently prepared azide functional polystyrene (PS-N3 ). Successful formation of PS-b-PMMA block copolymer is confirmed by FT-IR and (1) H NMR spectral analysis and gel permeation chromatography (GPC) measurements. PMID:25200624

  11. Block copolymer modified surfaces for conjugation of biomacromolecules with control of quantity and activity.

    Science.gov (United States)

    Li, Xin; Wang, Mengmeng; Wang, Lei; Shi, Xiujuan; Xu, Yajun; Song, Bo; Chen, Hong

    2013-01-29

    Polymer brush layers based on block copolymers of poly(oligo(ethylene glycol) methacrylate) (POEGMA) and poly(glycidyl methacrylate) (PGMA) were formed on silicon wafers by activators generated by electron transfer atom transfer radical polymerization (AGET ATRP). Different types of biomolecule can be conjugated to these brush layers by reaction of PGMA epoxide groups with amino groups in the biomolecule, while POEGMA, which resists nonspecific protein adsorption, provides an antifouling environment. Surfaces were characterized by water contact angle, ellipsometry, and Fourier transform infrared spectroscopy (FTIR) to confirm the modification reactions. Phase segregation of the copolymer blocks in the layers was observed by AFM. The effect of surface properties on protein conjugation was investigated using radiolabeling methods. It was shown that surfaces with POEGMA layers were protein resistant, while the quantity of protein conjugated to the diblock copolymer modified surfaces increased with increasing PGMA layer thickness. The activity of lysozyme conjugated on the surface could also be controlled by varying the thickness of the copolymer layer. When biotin was conjugated to the block copolymer grafts, the surface remained resistant to nonspecific protein adsorption but showed specific binding of avidin. These properties, that is, well-controlled quantity and activity of conjugated biomolecules and specificity of interaction with target biomolecules may be exploited for the improvement of signal-to-noise ratio in sensor applications. More generally, such surfaces may be useful as biological recognition elements of high specificity for functional biomaterials. PMID:23265296

  12. Macroporous poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) resins-Versatile immobilization supports for biocatalysts

    NARCIS (Netherlands)

    Miletic, Nemanja; Vukovic, Zorica; Nastasovic, Aleksandra; Loos, Katja; Miletić, Nemanja; Vuković, Zorica; Nastasović, Aleksandra

    2009-01-01

    Crosslinked macroporous hydrophilic poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate)s [abbreviated poly(GMA-co-EGDMA)] with identical chemical structure (60% of glycidyl methacrylate) but with varied average pore sizes (from 30 to 560 nm), specific surface areas (from 13.2 to 106.0 m(2)

  13. Perfluoroalkylated diblock-alkyl methacrylate monomers for biomedical applications. Wetability of their copolymers with HEMA and DEGMA

    Czech Academy of Sciences Publication Activity Database

    Kaplánek, R.; Paleta, O.; Michálek, Jiří; Přádný, Martin

    2005-01-01

    Roč. 126, č. 4 (2005), s. 593-598. ISSN 0022-1139 R&D Projects: GA ČR GA106/00/1296 Institutional research plan: CEZ:AV0Z40500505 Keywords : epoxide ring opening * perfuoroalkylated methacrylates * double-tail methacrylates Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.185, year: 2005

  14. Modification of polyethylene films by radiation grafting of glycidyl methacrylate and immobilization of β-cyclodextrin

    International Nuclear Information System (INIS)

    Glycidyl methacrylate was grafted onto polyethylene films using a preirradiation method with γ rays. The effect of absorbed dose, monomer concentration, and reaction time on the degree of grafting was determined. The grafted samples were verified by FTIR-ATR spectroscopy. β-Cyclodextrin was immobilized onto polypropylene modified with glycidyl methacrylate, and the ability of the cavities of β-cyclodextrin to form inclusion complexes was demonstrated using the typically organic compound approach with m-toluic acid (3-MBA) as a probe

  15. Penetration of 3H-glycerol trinitrate through silicone-hydroxyethyl methacrylate matrices

    International Nuclear Information System (INIS)

    The possibility of use of a powder-like polymeric hydrogel of 2-hydroxyethyl methacrylate with 33 wt. % methacrylic acid as potential pharmaceutical adjuvant in the form of a composite powdered material, with silicone rubber in the form of matrices for transdermal therapeutic system has been studied. The effect of solvents and the content of composite hydrogel in matrices on the rate of permeation of an antianginic drug, radioactive labeled glycerol trinitrate (GTN) was evaluated. The results show that hydrogel copolymers are prospective adjuvants for transdermal therapeutic systems. (author). 9 refs., 5 figs., 1 tab

  16. Influence of cyclodextrin on the solubility and the polymerization of (methacrylated Triton® X-100

    Directory of Open Access Journals (Sweden)

    Melanie Kemnitz

    2012-12-01

    Full Text Available Triton® X-100 (poly(ethylene glycol tert-octylphenyl ether was (methacrylated and polymerized in the absence and presence of randomly methylated β-cyclodextrin (RAMEB-CD. Triton®-polymers that were polymerized with RAMEB-CD in water were compared with polymers that were synthesized in organic solvents after the addition of RAMEB-CD. The polymers were characterized by 1H NMR and FTIR spectroscopy, matrix-assisted laser desorption ionization mass spectrometry (MALDI-TOF MS, dynamic light scattering (DLS, gel-permeation chromatography (GPC and turbidity measurements. Additionally, the viscosity change of the methacrylic homopolymer with RAMEB-CD was evaluated.

  17. Comparative examination of radiation polymerization in a thin layer of acrylic and methacrylic esters

    International Nuclear Information System (INIS)

    Some features of radiation polymerization of acrylic esters CH2 double-bond CH-COOR (AE) and their methacrylic analogs CH2 double-bond C(CH3)-COOR (ME) in a thin layer have not been explained within the framework of concepts of the radical mechanism of radiation polymerization. To determine the causes of the anomalies, the authors comparatively studied polymerization of a series of AE and ME in a thin layer under the effect of accelerated electrons, butyl acrylate and butyl methacrylate, ethylene glycol diacrylate and ethylene glycol dimethacrylate and diethylene glycol diacrylate and diethylene glycol dimethacrylate

  18. A new polymer gel dosimeter composed of methacrylic acid, agarose gel and THPC with gelatin

    International Nuclear Information System (INIS)

    In this paper, a new type of methacrylic acid based gel dosimeter is presented. This gel contains both agarose and gelatin with deferent roles respectively. The agarose conducts itself as a gelling agent, while the gelatin relates to the graft reaction of methacrylic acid. This new type of gel excels in the long-term stability of R2 after irradiation. The characteristics of this gel were studied by the measurements of R2 with MRI and the direct measurements of temperature in the gel during the irradiation.

  19. Investigation of nanocomposites made with poly(methacrylic acid-co-methyl methacrylate)/poly(N-vinyl-2-pyrrolidone)/multi-walled carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Guoqin, Liu; Wei, Miao [College of Material Science and Engineering, Henan University of Technology (China); Lin-Jian, Shangguan, E-mail: mikepolymer@126.com [School of Mechanical Engineering, North China University of Water Conservancy and Electric Power (China)

    2014-06-01

    Poly(methacrylic acid-co-methyl methacrylate) (P(MAA-co-MMA)) was prepared in the presence of poly(N-vinyl-2-pyrrolidone) (PVP) and multi-walled carbon nanotubes (MWNTs) via ultrasonic assisted solution free radical polymerization, i.e., P(MAA-co-MMA)/PVP/MWNTs nanocomposites. The morphology, glassy-state storage modulus, thermal behavior and swelling characteristics of P(MAA-co-MMA)/PVP/MWNTs nanocomposites were investigated. Scanning electron micrographs (SEM) revealed that MWNTs at low concentration could be uniformly dispersed into P(MAA-co-MMA)/PVP blends. With increasing MWNTs weight fraction, the average glassy-state modulus, glass transition temperatures and decomposition temperature of the nanocomposites increased, but their swelling characteristics decreased. (author)

  20. Investigation of nanocomposites made with poly(methacrylic acid-co-methyl methacrylate/poly(N-vinyl-2-pyrrolidone/multi-walled carbon nanotubes

    Directory of Open Access Journals (Sweden)

    Liu Guoqin

    2014-01-01

    Full Text Available Poly(methacrylic acid-co-methyl methacrylate (P(MAA-co-MMA was prepared in the presence of poly(N-vinyl-2-pyrrolidone (PVP and multiwalled carbon nanotubes (MWNTs via ultrasonic assisted solution free radical polymerization, i.e., P(MAA-co-MMA/PVP/MWNTs nanocomposites. The morphology, glassy-state storage modulus, thermal behavior and swelling characteristics of P(MAA-co-MMA/PVP/MWNTs nanocomposites were investigated. Scanning electron micrographs (SEM revealed that MWNTs at low concentration could be uniformly dispersed into P(MAA-co-MMA/PVP blends. With increasing MWNTs weight fraction, the average glassy-state modulus, glass transition temperatures and decomposition temperature of the nanocomposites increased, but their swelling characteristics decreased.

  1. Interactions between plasma and block copolymers used in directed self-assembly patterning

    Science.gov (United States)

    Sirard, Stephen; Azarnouche, Laurent; Gurer, Emir; Durand, William; Maher, Michael; Mori, Kazunori; Blachut, Gregory; Janes, Dustin; Asano, Yusuke; Someya, Yasunobu; Hymes, Diane; Graves, David; Ellison, Christopher J.; Willson, C. Grant

    2016-03-01

    The directed self-assembly (DSA) of block copolymers offers a promising route for scaling feature sizes below 20 nm. At these small dimensions, plasmas are often used to define the initial patterns. It is imperative to understand how plasmas interact with each block in order to design processes with sufficient etch contrast and pattern fidelity. Symmetric lamella forming block copolymers including, polystyrene-b-poly(methyl methacrylate) and several high-χ silicon-containing and tin-containing block copolymers were synthesized, along with homopolymers of each block, and exposed to various oxidizing, reducing, and fluorine-based plasma processes. Etch rate kinetics were measured, and plasma modifications of the materials were characterized using XPS, AES, and FTIR. Mechanisms for achieving etch contrast were elucidated and were highly dependent on the block copolymer architecture. For several of the polymers, plasma photoemissions were observed to play an important role in modifying the materials and forming etch-resistant protective layers. Furthermore, it was observed for the silicon- and tin-containing polymers that an initial transient state exists, where the polymers exhibit an enhanced etch rate, prior to the formation of the etch-resistant protective layer. Plasma developed patterns were demonstrated for the differing block copolymer materials with feature sizes ranging from 20 nm down to approximately 5 nm.

  2. Fabrication of Bioactive Surfaces by Functionalization of Electroactive and Surface-Active Block Copolymers

    Directory of Open Access Journals (Sweden)

    Omotunde Olubi

    2014-08-01

    Full Text Available Biofunctional block copolymers are becoming increasingly attractive materials as active components in biosensors and other nanoscale electronic devices. We have described two different classes of block copolymers with biofuctional properties. Biofunctionality for block copolymers is achieved through functionalization with appropriate biospecific ligands. We have synthesized block copolymers of electroactive poly(3-decylthiophene and 2-hydroxyethyl methacrylate by atom transfer radical polymerization. The block copolymers were functionalized with the dinitrophenyl (DNP groups, which are capable of binding to Immunoglobulin E (IgE on cell surfaces. The block copolymers were shown to be redox active. Additionally, the triblock copolymer of α, ω-bi-biotin (poly(ethylene oxide-b-poly (styrene-b-poly(ethylene oxide was also synthesized to study their capacity to bind fluorescently tagged avidin. The surface-active property of the poly(ethylene oxide block improved the availability of the biotin functional groups on the polymer surfaces. Fluorescence microscopy observations confirm the specific binding of biotin with avidin.

  3. 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.

  4. pH-responsive layer-by-layer films of zwitterionic block copolymer micelles

    OpenAIRE

    Demirel, Adem Levent; Yusan, Pelin; Tuncel, İrem; Bütün, Vural; Erel-Goktepe, İrem

    2014-01-01

    We report a strategy to incorporate micelles of poly[3-dimethyl (methacryloyloxyethyl) ammonium propane sulfonate]-block-poly[2-(diisopropylamino) ethyl methacrylate] (beta PDMA-b-PDPA) into electrostatic layer-by-layer (LbL) films. We obtained micelles with pH-responsive PDPA-cores and zwitterionic bPDMA-coronae at pH 8.5 through pH-induced self-assembly of bPDMA-b-PDPA in aqueous solution. To incorporate bPDMA-b-PDPA micelles into LbL films, we first obtained a net electrical charge on bPDM...

  5. Effects of Block Scheduling

    Directory of Open Access Journals (Sweden)

    William R. Veal

    1999-09-01

    Full Text Available This study examined the effects of a tri-schedule on the academic achievement of students in a high school. The tri-schedule consists of traditional, 4x4 block, and hybrid schedules running at the same time in the same high school. Effectiveness of the schedules was determined from the state mandated test of basic skills in reading, language, and mathematics. Students who were in a particular schedule their freshman year were tested at the beginning of their sophomore year. A statistical ANCOVA test was performed using the schedule types as independent variables and cognitive skill index and GPA as covariates. For reading and language, there was no statistically significant difference in test results. There was a statistical difference mathematics-computation. Block mathematics is an ideal format for obtaining more credits in mathematics, but the block format does little for mathematics achievement and conceptual understanding. The results have content specific implications for schools, administrations, and school boards who are considering block scheduling adoption.

  6. Spice Blocks Melanoma Growth

    Science.gov (United States)

    Science Teacher, 2005

    2005-01-01

    Curcumin, the pungent yellow spice found in both turmeric and curry powders, blocks a key biological pathway needed for development of melanoma and other cancers, according to a study that appears in the journal Cancer. Researchers from The University of Texas M. D. Anderson Cancer Center demonstrate how curcumin stops laboratory strains of…

  7. Contaminated soil concrete blocks

    NARCIS (Netherlands)

    Korte, de A.C.J.; Brouwers, H.J.H.; Limbachiya, Mukesh C.; Kew, Hsein Y.

    2009-01-01

    According to Dutch law the contaminated soil needs to be remediated or immobilised. The main focus in this article is the design of concrete blocks, containing contaminated soil, that are suitable for large production, financial feasible and meets all technical and environmental requirements. In ord

  8. Using click chemistry to modify block copolymers and their morphologies

    Science.gov (United States)

    Wollbold, Johannes

    Microphase separated block copolymers (BCPs) are emerging as promising templates and scaffolds for the fabrication of nanostructured materials. To achieve the desired nanostructures, it is necessary to establish convenient approaches to control the morphology of BCPs. It remains challenging to induce morphological transitions of BCPs via external fields. Click chemistry, especially alkyne/azide click chemistry, has been widely used to synthesize novel functionalized materials. Here, we demonstrate that alkyne/azide click chemistry can be used as an efficient approach to chemically modify BCPs and therefore induce morphological transitions. Alkyne-functionalized diblock copolymers (di-BCPs) poly(ethylene oxide)- block-poly(n-butyl methacrylate-random-propargyl methacrylate) (PEO-b-P(nBMA-r-PgMA)) have been successfully synthesized. When the di-BCP is blended with an azide additive Rhodamine B azide and annealed at elevated temperatures, click reaction occurs between the two components. With the Rhodamine B structure attached to the polymer backbone, the di-BCP shows dramatic change in the interactions between the two blocks and the volume fraction of each block. As a result, morphological transitions, such as disorder-to-order transitions (DOTs) and order-to-order transitions (OOTs), are observed. The reaction kinetics and morphology evolution during the click chemistry induced DOTs have been investigated by in-situ and ex-situ characterizations, and fast kinetics properties are observed. Microphase separated morphologies after the DOTs or OOTs are dictated by the composition of neat di-BCPs and the mole ratio between the alkyne and azide groups. The DOTs of PEO-b-P(nBMA-r-PgMA) di-BCPs induced by alkyne/azide click chemistry have also been achieved in thin film geometries, with comparable kinetics to bulk samples. The orientation of the microdomains is dependent on the grafting density of Rhodamine B structure as well as film thickness. At higher grafting densities

  9. Luminescence and Magnetic Properties of Two Three-Dimensional Terbium and Dysprosium MOFs Based on Azobenzene-4,4′-Dicarboxylic Linker

    Directory of Open Access Journals (Sweden)

    Belén Fernández

    2016-02-01

    Full Text Available We report the in situ formation of two novel metal-organic frameworks based on terbium and dysprosium ions using azobenzene-4,4′-dicarboxylic acid (H2abd as ligand, synthesized by soft hydrothermal routes. Both materials show isostructural three-dimensional networks with channels along a axis and display intense photoluminescence properties in the solid state at room temperature. Textural properties of the metal-organic frameworks (MOFs have been fully characterized although no appreciable porosity was obtained. Magnetic properties of these materials were studied, highlighting the dysprosium material displays slightly frequency-dependent out of phase signals when measured under zero external field and under an applied field of 1000 Oe.

  10. Edit Distance with Block Deletions

    OpenAIRE

    Dana Shapira; Storer, James A.

    2011-01-01

    Several variants of the edit distance problem with block deletions are considered. Polynomial time optimal algorithms are presented for the edit distance with block deletions allowing character insertions and character moves, but without block moves. We show that the edit distance with block moves and block deletions is NP-complete (Nondeterministic Polynomial time problems in which any given solution to such problem can be verified in polynomial time, and any NP problem can be converted into...

  11. Fermion-Scalar Conformal Blocks

    CERN Document Server

    Iliesiu, Luca; Poland, David; Pufu, Silviu S; Simmons-Duffin, David; Yacoby, Ran

    2015-01-01

    We compute the conformal blocks associated with scalar-scalar-fermion-fermion 4-point functions in 3D CFTs. Together with the known scalar conformal blocks, our result completes the task of determining the so-called `seed blocks' in three dimensions. Conformal blocks associated with 4-point functions of operators with arbitrary spins can now be determined from these seed blocks by using known differential operators.

  12. Spectral Characteristics of Bent-Core Azobenzen Monomers%含偶氮基团的弯曲型分子的光谱特性研究

    Institute of Scientific and Technical Information of China (English)

    董寅; 沈冬; 郑致刚

    2012-01-01

    The azo (-N =N-) linkage has the particular thermochemistry and actinoche-mistry behavior, the azobenzene group can undergo reversible cis-trans isomerization under light irradiation and its nonlinear optical properties possess the potential applications in the aspects of molecular design, photofixation, photochromics, thermochromism, etc. The UV-Vis absorbance of sixteen bent-core or linear monomers containing azobenzene as side arms and substituted para/m-aminobenzoic acid as central units was studied. The angle of the bent-core molecules was simulated. The trans-form of azo compounds showed a strong band in the UV region (330~370 nm) and a weak band at 440~450 nm. It was found that it has a close relationship between the angle of the molecules and the UV-Vis absorption.%偶氮连接基团(-N=N-)有着特殊的热化学和光化学行为,在适当波长光的照射下,能发生可逆的顺反异构反应,从而发生吸收波长的变化.在分子设计、光定位、光致变色和热致变色等方面,偶氮连接基团的非线性光化学性质都有着潜在的应用价值.文章以含有偶氮基作为侧翼的弯曲型分子作为研究对象,比较了弯曲型和直线型分子的吸收光谱;并用计算机模拟计算了弯曲型分子的角度,发现分子弯曲角和紫外可见吸收光谱存在着密切的关系.

  13. Development of mesalazine pellets coated with methacrylic-derived polymer

    Directory of Open Access Journals (Sweden)

    Simone Cristina Déo

    2011-03-01

    Full Text Available Mesalazine (5-ASA is the standard drug for the treatment of inflammatory bowel disease (IBD due to its local effect on intestinal and colonic mucosa. The effective and safe treatment of this disease requires more efficient delivery of the active substance to its site of action. The focus of this study was the use of multiparticulate systems, a modified release form in which the drug is divided into several functional subunits of release in the form of granules or pellets. When these forms are administered, they are rapidly disintegrated, distributing their content throughout the gastrointestinal tract. The aim of this study was to develop and evaluate a multiparticulate system consisting of pellets coated with polymer for pH-dependent release, derived from methacrylic acid and incorporated into the tablet dosage form of mesalazine as a model drug. The extrusion-spheronisation technique was used, resulting in smooth and spherical pellets with uniform size distribution, which were coated in fluidized bed using Opadry® Enteric 94K28327 containing Eudragit® S100 as the agent regulating drug release. The dissolution profile of coated pellets showed good control of drug release from the polymer at the two levels of coating evaluated (8% and 10%, but only the 10% coated pellets were statistically similar to Asalit® 400 mg.A mesalazina (5-ASA tem se apresentado como fármaco padrão para o tratamento da doença inflamatória intestinal (DII devido ao seu efeito local na mucosa intestinal e colônica. A terapia efetiva e segura desta doença requer a chegada da substância ativa ao seu local de ação com maior eficiência. Nessa busca, tem se destacado o uso de Sistemas Multiparticulados, forma farmacêutica de liberação modificada, em que o fármaco está dividido em várias subunidades funcionais de liberação, sob a forma de grânulos ou péletes, que quando administrados, são rapidamente desintegrados distribuindo seu conteúdo por todo trato

  14. Thionine-modified poly(glycidyl methacrylate) nanospheres as labels of antibodies for biosensing applications

    Czech Academy of Sciences Publication Activity Database

    Zasońska, Beata Anna; Čadková, M.; Kovářová, A.; Bílková, Z.; Korecká, L.; Horák, Daniel

    2015-01-01

    Roč. 7, č. 44 (2015), s. 24926-24931. ISSN 1944-8244 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0109 Institutional support: RVO:61389013 Keywords : glycidyl methacrylate * nanospheres * thionine Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 6.723, year: 2014

  15. 78 FR 55644 - Styrene, Copolymers with Acrylic Acid and/or Methacrylic Acid; Tolerance Exemption

    Science.gov (United States)

    2013-09-11

    ... number average molecular weight (in amu), 1,200 when used as an inert ingredient in a pesticide chemical... number average molecular weight (in amu), 1,200 to include the monomer lauryl methacrylate. That notice... exemption. 6. The polymer is not a water absorbing polymer with a number average molecular weight...

  16. Radiation immobilization of α-amylase on poly methyl methacrylate Pt. 2

    International Nuclear Information System (INIS)

    Bacterial α-amylase Bacillus substilis has been immobilized by the method of emulsion polymerization of methyl methacrylate initiated with γ60Co radiation; a product of high activity and stability has been obtained. Optimum process parameters have been established. (author)

  17. Controlled Degradation of Poly(Ethyl Cyanoacrylate-Co-Methyl Methacrylate)(PECA-Co-PMMA) Copolymers

    Science.gov (United States)

    This paper describes a method for modifying poly(ethyl cyanoacrylate) in order to control the degradation and the stability as well as the glass transition temperatures. Copolymers of poly(ethyl cyanoacrylate-co-methyl methacrylate) (PECA-co-PMMA) with various compositions were synthesized by free ...

  18. Preparation and characterization of monodisperse silica-coated poly(glycidyl methacrylate) micropsheres

    Czech Academy of Sciences Publication Activity Database

    Grama, Silvia; Plichta, Zdeněk; Horák, Daniel

    Pisa : European Polymer Federation, 2013. P3-54. [European Polymer Congress - EPF 2013. 16.06.2013-21.06.2013, Pisa] R&D Projects: GA MŠk EE2.3.30.0029 Institutional support: RVO:61389013 Keywords : poly(glycidyl methacrylate) * microspheres * silica Subject RIV: CE - Biochemistry

  19. Crystallization and melt behaviour of isotactic poly((4-alpha,alpha-dimethyl-benzyl)phenyl methacrylate)

    NARCIS (Netherlands)

    vanEkenstein, GORA; Tan, YY

    1997-01-01

    The crystallization and melting behaviour of practically 100% isotactic poly((4-alpha,alpha-dimethylbenzyl) phenyl methacrylate) has been studied by d.s.c. and light microscopy. Crystallization from the melt seemed to be non-spherulitic. The maximum crystallization rate, which could only be determin

  20. Phase continuity and inversion in polystyrene/poly(methyl methacrylate) blends

    DEFF Research Database (Denmark)

    Chuai, Chengzhi; Almdal, K.; Lyngaae-Jørgensen, Jørgen

    2003-01-01

    Dual-phase continuity and phase inversion of polystyrene (PS)/poly(methyl methacrylate) (PMMA) blends processed in a twin-screw extruder was investigated using a selective extraction technique and scanning electron microscopy. Emphasis was placed on investigating the effects of viscosity ratio...

  1. Gamma radiation-induced grafting of glycidyl methacrylate (GMA) onto water hyacinth fibers

    Science.gov (United States)

    Madrid, Jordan F.; Nuesca, Guillermo M.; Abad, Lucille V.

    2013-04-01

    Water hyacinth fibers (Eichhornia crassipes) were functionalized using radiation-induced graft polymerization of glycidyl methacrylate by γ-rays from 60Co source. The simultaneous grafting technique was employed wherein the water hyacinth fibers were irradiated in nitrogen atmosphere in the presence of glycidyl methacrylate dissolved in water/methanol solvent. The effects of different grafting parameters to the grafting yield were evaluated. The optimal values of solvent, absorbed dose, dose rate, and concentration of monomer were found to be 1:3 (volume/volume) water-methanol solvent, 10 kGy, 8 kGy h-1 dose rate and 5% volume/volume glycidyl methacrylate, respectively. Using the optimum conditions, degree of grafting of approximately 58% was achieved. The grafted water hyacinth fibers were characterized using Attenuated Total Reflectance-Fourier Transformed Infrared Spectroscopy (ATR-FTIR), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDX). The results of these tests confirmed the successful grafting of glycidyl methacrylate onto water hyacinth fibers.

  2. Methacrylic acid obtaining in the presence of vanadium-containing catalysts in gas phase

    OpenAIRE

    Івасів, Володимир Васильович

    2012-01-01

    In the article regularities of methacrylic acid obtaining by the aldol condensation of propionic acid with formaldehyde in the presence of B2O3 – P2O5 – V2O5 catalysts in gas phase have been investigated

  3. Versatility of Alkyne-Modified Poly(Glycidyl Methacrylate) Layers for Click Reactions

    International Nuclear Information System (INIS)

    Functional soft interfaces are of interest for a variety of technologies. We describe three methods for preparing substrates with alkyne groups, which show versatility for 'click' chemistry reactions. Two of the methods have the same root: formation of thin, covalently attached, reactive interfacial layers of poly(glycidyl methacrylate) (PGMA) via spin coating onto silicon wafers followed by reactive modification with either propargylamine or 5-hexynoic acid. The amine or the carboxylic acid moieties react with the epoxy groups of PGMA, creating interfacial polymer layers decorated with alkyne groups. The third method consists of using copolymers comprising glycidyl methacrylate and propargyl methacrylate (pGP). The pGP copolymers are spin coated and covalently attached on silicon wafers. For each method, we investigate the factors that control film thickness and content of alkyne groups using ellipsometry, and study the nanophase structure of the films using neutron reflectometry. Azide-terminated polymers of methacrylic acid and 2-vinyl-4,4-dimethylazlactone synthesized via reversible addition-fragmentation chain transfer polymerization were attached to the alkyne-modified substrates using 'click' chemistry, and grafting densities in the range of 0.007-0.95 chains nm-2 were attained. The maximum density of alkyne groups attained by functionalization of PGMA with propargylamine or 5-hexynoic acid was approximately 2 alkynes nm-3. The alkyne content obtained by the three decorating approaches was sufficiently high that it was not the limiting factor for the click reaction of azide-capped polymers.

  4. Anionic polymerization of (meth)acrylate monomers with the ligated systems, metalloporphyrin and lanthanocene initiators

    Czech Academy of Sciences Publication Activity Database

    Vlček, Petr

    New York: Nova Science Publishers, Inc, 2006 - (Jagur-Grodzinski, J.), s. 289-342 ISBN 1-59454-330-5 Institutional research plan: CEZ:AV0Z40500505 Keywords : anionic polymerization * copolymers * (meth)acrylates Subject RIV: CD - Macromolecular Chemistry

  5. Graft Copolymerization of Methyl Methacrylate Monomer onto Starch and Natural Rubber Latex Initiated by Gamma Irradiation

    Directory of Open Access Journals (Sweden)

    S. Iskandar

    2011-04-01

    Full Text Available To obtain the degradable plastic, the graft copolymerization of methyl methacrylate onto starch and natural rubber latex was conducted by a simultaneous irradiation technique. Gamma-ray from cobalt-60 source was used as the initiator. The grafted copolymer of starch-polymethyl methacrylate and the grafted copolymer of natural rubber-polymethyl methacrylate were mixed in the blender, and dried it in the oven. The dried grafted copolymer mixture was then molded using hydraulic press machine. The effect of irradiation dose, composition of the grafted copolymer mixture, film forming condition and recycle effect was evaluated. The parameters observed were tensile strength, gel fraction and soil burial degradability of grafted copolymer mixture. It was found that the tensile strength of grafted copolymer mixture increased by -ray irradiation. Increasing of the grafted copolymer of natural rubber-polymethyl methacrylate content, the gel fraction and tensile strength of the grafted copolymer mixture increased. The tensile strength of the grafted copolymer mixture was increased from 18 MPa to 23 MPa after recycled (film forming reprocessed 3 times. The grafted copolymer mixture was degraded completely after soil buried for 6 months

  6. Biocompatible monodisperse poly(glycidyl methacrylate) microspheres intended for biological applications

    Czech Academy of Sciences Publication Activity Database

    Grama, Silvia; Stoika, R.; Heuts, H.; Horák, Daniel

    Cancún : Zing Conferences, 2014. [Zing Polymer Chemistry Conference /4./. 10.12.2014-13.12.2014, Cancún] R&D Projects: GA MŠk(CZ) EE2.3.30.0029 Institutional support: RVO:61389013 Keywords : poly(glycidyl methacrylate) * microspheres * silica Subject RIV: CE - Biochemistry

  7. Copolymers Formation by Photopolymerization of (Meth)acrylates Containing Dissolved Polyheteroarylenes

    OpenAIRE

    Dmitriy A. Sapozhnikov; Tat'yana V. Volkova; Sakharova, Antonina A.; Gasanov, Rashid G.; Vanda Yu. Voytekunas; Abadie, Marc J. M.; Jean-Yves Sanchez; Vygodskii, Yakov S.

    2009-01-01

    Radical photopolymerization of (meth)acrylates in the presence of dissolved polyheteroarylenes has been investigated. The kinetics of radical polymerization of unsaturated monomers in the presence of polyheteroarylenes and model compounds has been studied by Differential Scanning Photocalorimetry and Infrared Spectroscopy. From the results of investigations into the kinetics and the polymer structures (Fourier Transform Infrared Spectroscopy, Nuclear Magnetic Resonance, Size-exclusion Chromat...

  8. Thick Methacrylate Sections Devoid of Lost Caps Simplify Stereological Quantifications Based on the Optical Fractionator Design

    DEFF Research Database (Denmark)

    Hasselholt, Stine; Lykkesfeldt, Jens; Overgaard Larsen, Jytte

    2015-01-01

    methacrylate) sections were inspected for lost caps to evaluate the possibility of whole section thickness counting with the optical fractionator technique and hippocampal granular cell nucleoli density differences along the z-axis were assessed with a z-axis analysis. No lost caps were found in the examined...

  9. Zwitterion-grafted monodisperse poly(glycidyl methacrylate) microspheres to minimize nonspecific protein adsorption

    Czech Academy of Sciences Publication Activity Database

    Horák, Daniel; Koubková, Jana; Proks, Vladimír; Trchová, Miroslava

    Riva del Garda : Elsevier, 2015. P1.006. [International Symposium Frontiers in Polymer Science /4./ - POLY 2015. 20.05.2015-22.05.2015, Riva del Garda] R&D Projects: GA MŠk(CZ) EE2.3.30.0029 Institutional support: RVO:61389013 Keywords : microspheres * poly(glycidyl methacrylate) * zwitterion Subject RIV: CE - Biochemistry

  10. Macroporous hydrogels based on 2-hydroxyethyl methacrylate. Part 3. Hydrogels as carriers for immobilization of proteins

    Czech Academy of Sciences Publication Activity Database

    Michálek, Jiří; Přádný, Martin; Artyukhov, A.; Šlouf, Miroslav; Smetana Jr., K.

    2005-01-01

    Roč. 16, č. 8 (2005), s. 783-786. ISSN 0957-4530 R&D Projects: GA ČR GA203/01/0737; GA AV ČR IBS4050005; GA MŠk LN00A065 Keywords : macroporous hydrogels * hydroxyethyl methacrylate * crosslinked copolymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.248, year: 2005

  11. Polymorphism and polymerisation of acrylic and methacrylic acid at high pressure

    DEFF Research Database (Denmark)

    Oswald, Iain D. H.; Urquhart, Andrew J.

    2011-01-01

    The polymorphism and polymerisation of two related acids have been investigated under high pressure conditions. Acrylic acid crystallises as a new polymorph at 0.65 GPa whilst methacrylic acid crystallises in a new polymorph at a higher pressure of 1.5 GPa. Both these new polymorphs exhibit similar...

  12. A novel epoxy methacrylate resin containing phthalazinone moiety for UV coatings

    Institute of Scientific and Technical Information of China (English)

    Yan Kou; Jin Yan Wang; Xi Gao Jian

    2007-01-01

    A novel phthalazinone modified epoxy acrylate resin for the high temperature resistant ultravioet (UV) curable coating was synthesized. The methacrylated epoxy resins obtained were utilized to UV radiation curing by taking 2.5% (wt%) of photoinitiator in combination with 20% (wt%) of diluent, and generated the interpenetraring polymer networks. The cured film had good thermal and chemical stability.

  13. Monitor of Polymerization of Inverse Microemulsions Containing Methyl Methacrylate and Acrylic Acid

    Institute of Scientific and Technical Information of China (English)

    Xiao LI; Sheng Ping XIA; Wei Jie ZENG; Wei Ying ZHANG; Sheng Xiong DONG

    2006-01-01

    The polymerization of the inverse microemulsions composed of methyl methacrylate,acrylic acid, sodium dodecyl sulfate and water was monitored by refractometer, conductometer and time-resolved light scattering device. The results showed that refractive index, conductivity or intensity distribution of scattered light changed along with polymerization, and different processes of polymerization could be identified.

  14. NCCN Evidence Blocks.

    Science.gov (United States)

    Carlson, Robert W; Jonasch, Eric

    2016-05-01

    NCCN has developed a series of Evidence Blocks: graphics that provide ratings for each recommended treatment regimen in terms of efficacy, toxicity, quality and consistency of the supporting data, and affordability. The NCCN Evidence Blocks are currently available in 10 tumor types within the NCCN Clinical Practice Guidelines in Oncology (NCCN Guidelines). At a glance, patients and providers can understand how a given treatment was assessed by the NCCN Guidelines Panel and get a sense of how a given treatment may match individual needs and preferences. Robert W. Carlson, MD, CEO of NCCN, described the reasoning behind this new feature and how the tool is used, and Eric Jonasch, MD, Professor of Genitourinary Medical Oncology at The University of Texas MD Anderson Cancer Center, and Vice Chair of the NCCN Kidney Cancer Panel, described its applicability in the management of metastatic renal cell carcinoma. PMID:27226499

  15. Right bundle branch block

    DEFF Research Database (Denmark)

    Bussink, Barbara E; Holst, Anders Gaarsdal; Jespersen, Lasse;

    2013-01-01

    AimsTo determine the prevalence, predictors of newly acquired, and the prognostic value of right bundle branch block (RBBB) and incomplete RBBB (IRBBB) on a resting 12-lead electrocardiogram in men and women from the general population.Methods and resultsWe followed 18 441 participants included in...... men vs. 0.5%/2.3% in women, P <0.001). Significant predictors of newly acquired RBBB were male gender, increasing age, high systolic blood pressure, and presence of IRBBB, whereas predictors of newly acquired IRBBB were male gender, increasing age, and low BMI. Right bundle branch block was associated...... with significantly increased all-cause and cardiovascular mortality in both genders with age-adjusted hazard ratios (HR) of 1.31 [95% confidence interval (CI), 1.11-1.54] and 1.87 (95% CI, 1.48-2.36) in the gender pooled analysis with little attenuation after multiple adjustment. Right bundle branch...

  16. SNUPPS power block modelling

    International Nuclear Information System (INIS)

    A series of models is being built and used as tools in the design of the SNUPPS Standard Power Block. The modelling programme includes both preliminary and final design models, a construction sequence mode, and additional models used to study various features of the design. The design of a standard power block unit has necessitated design definition which is more detailed than that customarily used in the design of nuclear power stations. One innovation is the use of engineering models as a primary design tool in the layout of process piping, preparation of isometric drawings, design of small components which are customarily designed in the field during construction. Development of a standard construction sequence and construction work plan is another innovation. (author)

  17. SUPERFICIAL CERVICAL PLEXUS BLOCK

    Directory of Open Access Journals (Sweden)

    Komang Mega Puspadisari

    2014-01-01

    Full Text Available Superficial cervical plexus block is one of the regional anesthesia in  neck were limited to thesuperficial fascia. Anesthesia is used to relieve pain caused either during or after the surgery iscompleted. This technique can be done by landmark or with ultrasound guiding. The midpointof posterior border of the Sternocleidomastoid was identified and the prosedure done on thatplace or on the level of cartilage cricoid.

  18. Growth, Endlessness, Blocks

    OpenAIRE

    Nabata, Avery Misuzu

    2014-01-01

    Growth, Endlessness, Blocks is a sculptural installation comprised of a series of wood structures of various scales. Large sections of drywall function as extensions of the gallery walls. Each structure balances a number of different physical characteristics that are tied to the act of making. Balance and presence combine in a disconcerting way giving the viewer a sense of uneasiness and a moment finely tuned by the artist. The artist seeks to embody the role of the factory fabricator as a me...

  19. E-Block: A Tangible Programming Tool with Graphical Blocks

    Directory of Open Access Journals (Sweden)

    Danli Wang

    2013-01-01

    Full Text Available This paper designs a tangible programming tool, E-Block, for children aged 5 to 9 to experience the preliminary understanding of programming by building blocks. With embedded artificial intelligence, the tool defines the programming blocks with the sensors as the input and enables children to write programs to complete the tasks in the computer. The symbol on the programming block's surface is used to help children understanding the function of each block. The sequence information is transferred to computer by microcomputers and then translated into semantic information. The system applies wireless and infrared technologies and provides user with feedbacks on both screen and programming blocks. Preliminary user studies using observation and user interview methods are shown for E-Block's prototype. The test results prove that E-Block is attractive to children and easy to learn and use. The project also highlights potential advantages of using single chip microcomputer (SCM technology to develop tangible programming tools for children.

  20. Development of methacrylate/silorane hybrid monomer system: Relationship between photopolymerization behavior and dynamic mechanical properties.

    Science.gov (United States)

    Song, Linyong; Ye, Qiang; Ge, Xueping; Singh, Viraj; Misra, Anil; Laurence, Jennifer S; Berrie, Cindy L; Spencer, Paulette

    2016-07-01

    Resin chemistries for dental composite are evolving as noted by the introduction of silorane-based composites in 2007. This shift in the landscape from methacrylate-based composites has fueled the quest for versatile methacrylate-silorane adhesives. The objective of this study was to evaluate the polymerization behavior and structure/property relationships of methacrylate-silorane hybrid systems. Amine compound ethyl-4-(dimethylamino) benzoate (EDMAB) or silane compound tris(trimethylsilyl) silane (TTMSS) was selected as coinitiators. The mechanical properties of the copolymer were improved significantly at low concentrations (15, 25, or 35 wt %) of silorane when EDMAB was used as coinitiator. The rubbery moduli of these experimental copolymers were increased by up to 260%, compared with that of the control (30.8 ± 1.9 MPa). Visible phase separation appeared in these formulations if the silorane concentrations in the formulations were 50-75 wt %. The use of TTMSS as coinitiator decreased the phase separation, but there was a concomitant decrease in mechanical properties. In the neat methacrylate formulations, the maximum rates of free-radical polymerization with EDMAB or TTMSS were 0.28 or 0.06 s(-1) , respectively. In the neat silorane resin, the maximum rates of cationic ring-opening polymerization with EDMAB or TTMSS were 0.056 or 0.087 s(-1) , respectively. The phase separation phenomenon may be attributed to differences in the rates of free-radical polymerization of methacrylates and cationic ring-opening polymerization of silorane. In the hybrid systems, free-radical polymerization initiated with EDMAB led to higher crosslink density and better mechanical properties under dry/wet conditions. These beneficial effects were, however, associated with an increase in heterogeneity in the network structure. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 841-852, 2016. PMID:25953619

  1. A approximate non-isothermal method to study kinetic processes controlled by a distribution of rate constants: the case of a photochromic azobenzene derivative dissolved in a polymer matrix

    Czech Academy of Sciences Publication Activity Database

    Janus, K.; Koshets, I. A.; Sworakowski, J.; Nešpůrek, Stanislav

    2002-01-01

    Roč. 12, č. 6 (2002), s. 1657-1663. ISSN 0959-9428 R&D Projects: GA AV ČR IAA1050901; GA ČR GA202/01/0518 Institutional research plan: CEZ:AV0Z4050913 Keywords : photochromism * bleaching kinetics * azobenzene Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 2.683, year: 2002

  2. Controlled release of cortisone drugs from block copolymers synthetized by ATRP

    Science.gov (United States)

    Valenti, G.; La Carta, S.; Mazzotti, G.; Rapisarda, M.; Perna, S.; Di Gesù, R.; Giorgini, L.; Carbone, D.; Recca, G.; Rizzarelli, P.

    2016-05-01

    Diseases affecting posterior eye segment, like macular edema, infection and neovascularization, may cause visual impairment. Traditional treatments, such as steroidal-drugs intravitreal injections, involve chronic course of therapy usually over a period of years. Moreover, they can require frequent administrations of drug in order to have an adequately disease control. This dramatically reduce patient's compliance. Efforts have been made to develop implantable devices that offer an alternative therapeutic approach to bypass many challenges of conventional type of therapy. Implantable drug delivery systems (DDS) have been developed to optimize therapeutic properties of drugs and ensure their slow release in the specific site. Polymeric materials can play an essential role in modulating drug delivery and their use in such field has become indispensable. During last decades, acrylic polymers have obtained growing interest. Biocompatibility and chemical properties make them extremely versatile, allowing their use in many field such as biomedical. In particular, block methacrylate copolymer with a balance of hydrophilic and hydrophobic properties can be suitable for prolonged DDS in biomedical devices. In this work, we focused on the realization of a system for controlled and long term release of betamethasone 17,21-dipropionate (BDP), a cortisone drug, from methacrylic block copolymers, to be tested in the treatment of the posterior eye's diseases. Different series of methyl methacrylate/hydroxyethyl methacrylate (MMA/HEMA) block and random copolymers, with different monomer compositions (10-60% HEMA), were synthetized by Atom Transfer Radical Polymerization (ATRP) to find the best hydrophilic/hydrophobic ratio, able to ensure optimal kinetic release. Copolymer samples were characterized by NMR spectroscopy (1H-NMR, 13C-NMR, CosY), SEC, TGA and DSC. Monitoring of drug release from films loaded with BDP was carried out by HPLC analysis. Evaluation of different kinetic

  3. Demographic Data - MDC_Block

    Data.gov (United States)

    NSGIC GIS Inventory (aka Ramona) — A polygon feature class of Miami-Dade Census 2000 Blocks. Census blocks are areas bounded on all sides by visible and/or invisible features shown on a map prepared...

  4. Ear - blocked at high altitudes

    Science.gov (United States)

    High altitudes and blocked ears; Flying and blocked ears; Eustachian tube dysfunction - high altitude ... you are going up or coming down from high altitudes. Chewing gum the entire time you are changing ...

  5. THE COMPATIBILITY OF BLENDS OF POLY(VINYL CHLORIDE) OR CHLORINATED POLY(VINYL CHLORIDE) WITH POLY(METHYL METHACRYLATE)

    Institute of Scientific and Technical Information of China (English)

    WANG Qingguo; CHENG Rongshi

    1988-01-01

    IR spectral shifts of carbonyl vibrational absorption for ethyl acetate, which acts analogically as the structural unit of poly(methyl methacrylate), in cyclohexane, chloroform, chlorinated paraffins, poly(vinyl chloride) and chlorinated poly(vinyl chloride) were measured. The results suggest that there are specific interactions between the carbonyl groups and the chlorinated hydrocarbons which could be responsible for the apparent compatibility of poly(vinyl chloride) -poly(methyl methacrylate) and chlorinated poly(vinyl chloride) -poly(methyl methacrylate) blends. Additionally, the effects of the preparation mode of blend films on phase separation and observed compatibility are discussed.

  6. Porous block nanofiber composite filters

    Energy Technology Data Exchange (ETDEWEB)

    Ginley, David S.; Curtis, Calvin J.; Miedaner, Alexander; Weiss, Alan J.; Paddock, Arnold

    2016-08-09

    Porous block nano-fiber composite (110), a filtration system (10) and methods of using the same are disclosed. An exemplary porous block nano-fiber composite (110) includes a porous block (100) having one or more pores (200). The porous block nano-fiber composite (110) also includes a plurality of inorganic nano-fibers (211) formed within at least one of the pores (200).

  7. Preparation and icephobic properties of polymethyltrifluoropropylsiloxane–polyacrylate block copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiaohui; Zhao, Yunhui [School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072 (China); Li, Hui [School of Chemistry and Chemical Engineering, Shandong Key Laboratory of Fluorine Chemistry and Chemical Engineering Materials, University of Jinan, Jinan 250022 (China); Yuan, Xiaoyan, E-mail: xyuan28@yahoo.com [School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072 (China)

    2014-10-15

    Highlights: • PMTFPS–b-polyacrylate copolymers in five different compositions were synthesized. • Enrichment of PMTFPS amounts at the surface made high F/Si value. • Icing delay time was related to the surface roughness. • Ice shear strength was decreased by the synergistic effect of silicone and fluorine. - Abstract: Five polymethyltrifluoropropylsiloxane (PMTFPS)–polyacrylate block copolymers (PMTFPS–b-polyacrylate) were synthesized by free radical polymerization of methyl methacrylate, n-butyl acrylate and hydroxyethyl methacrylate using PMTFPS macroazoinitiator (PMTFPS-MAI) in range of 10–50 mass percentages. The morphology, surface chemical composition and wettability of the prepared copolymer films were investigated by transmission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and water contact angle measurement. Delayed icing time and ice shear strength of the films were also detected for the icephobic purpose. The surface morphologies of the copolymers were different from those of the bulk because of the migration of the PMTFPS segments to the air interface during the film formation. Maximal delayed icing time (186 s at −15 °C) and reduction of the ice shear strength (301 ± 10 kPa) which was significantly lower than that of polyacrylates (804 ± 37 kPa) were achieved when the content of PMTFPS-MAI was 20 wt%. The icephobicity of the copolymers was attributed primarily to the enrichment of PMTFPS on the film surface and synergistic effect of both silicone and fluorine. Thus, the results show that the PMTFPS–b-polyacrylate copolymer can be used as icephobic coating materials potentially.

  8. Surface Modification of Block Copolymer Through Sulfur Containing Plasma Treatment.

    Science.gov (United States)

    Choi, Sang Wook; Shin, Jae Hee; Jeon, Min Hwan; Mun, Jeong Ho; Kim, Sang Ouk; Yeom, Geun Young; Kim, Kyong Nam

    2015-10-01

    Some of the important issues of block copolymer (BCP) as an application to the potential low cost next generation lithography are thermal stability and deformation during pattern transfer process in addition to defect density, line edge/width roughness, etc. In this study, sulfur containing plasma treatment was used to modify the BCP and the effects of the plasma on the properties of plasma treated BCP were investigated. The polystyrene hole pattern obtained from polystyrene polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) was initially degraded when the polystyrene hole was annealed at 190 °C for 15 min. However, when the hole pattern was treated using sulfur containing plasmas using H2S or SF6 up to 2 min, possibly due to the sulfurization of the polystyrene hole surface, no change in the hole pattern was observed after the annealing even though there is a slight change in hole shapes during the plasma treatment. The optimized plasma treated polystyrene pattern showed the superior characteristics as the mask layer by showing better thermal stability, higher chemical inertness, and higher etch selectivity during plasma etching. PMID:26726468

  9. Synthesis and Characterization of Poly(hydroxyethyl methacrylate-co-methacrylic acid) Cross Linked Polymeric Network for the Delivery of Analgesic Agent

    International Nuclear Information System (INIS)

    Objective of the study was to synthesize a chemically cross-linked poly(hydroxyethylmethacrylate-co-methacrylic acid) hydrogel (p(HEMA-co-MAA hydrogel)) for pH-responsive, controlled drug delivery of Flurbiprofen. pH-sensitive hydrogel drug delivery system was synthesized with the help of poly hydroxyethyl methacrylate (HEMA) and methacrylic acid (MAA) by using ethylene glycol dimethacrylate (EGDMA) as crosslinker. The monomers (HEMA and MAA) were successfully cross linked through free radical polymerization process, initiated by benzoyl peroxide in an aqueous medium. All formulations were loaded with Flurbiprofen as a model drug and evaluated at pH 1.2 and pH 7.4 to investigate pH-responsive nature of the system. Fourier transform infrared spectroscopy (FTIR) was performed to confirm the cross-linking of copolymer while thermo gravimetric analysis (TGA) and differential scanning calorimetry (DSC) were performed to evaluate the thermal stability of the system. Swelling studies and in-vitro release studies were carried out to evaluate pH-responsive nature of the hydrogels. FTIR confirmed that monomers were successfully cross-linked to form a copolymer. Hydrogel system showed less swelling at lower pH while at higher pH, it showed higher swelling, releasing drug in the same fashion. It was concluded that a stable hydrogel network was chemically cross-linked showing pH-responsive nature and thus, synthesized p(HEMA-co-MAA) hydrogels can be successfully employed as potential candidate for controlled drug delivery. (author)

  10. Synthesis of PMMA-b-PU-b-PMMA tri-block copolymers through ARGET ATRP in the presence of air

    Directory of Open Access Journals (Sweden)

    P. Krol

    2013-03-01

    Full Text Available ARGET (activators regenerated by electron transfer ATRP (atom transfer radical polymerization has been successfully performed (in flasks fitted with rubber septa without the need for use of Schlenk line in the presence of limited amount of air and with a very small (370 ppm amount of copper catalyst together with an appropriate reducing agent Cu(0. Novelty of this work is that the poly(methyl methacrylate-block-polyurethane-block-poly(methyl methacrylate triblock copolymers were synthesized for the first time through ARGET ATRP, by using tertiary bromine-terminated polyurethane as a macroinitiator (MBP-PU-MBP, CuBr2 or CuCl2 as a catalyst and N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA or 2,2'-bipyridine (Bpy as a complexing agent. As the polymerization time increases, both the monomer conversion and ln([M]0/[M] increased and the molecular weight of copolymer increases linearly with increasing conversion. Theoretical number-average molecular weight (Mn, th of the tri-block copolymers was found to be comparable with number-average molecular weight determined by GPC analyses (Mn, GPC. These results indicate that the formation of the tri-block copolymers was through atom transfer radical polymerization mechanism. 1H and 13C NMR spectral methods were employed to confirm chemical structures of synthesized macroinitiator and tri-block copolymers. Mole percentage of PMMA in the tri-block copolymers was calculated using 1H NMR spectroscopy and was found to be comparable with the GPC results. Additionally, the studies of surface properties (confocal microscopy and SFE of tri-block copolymer coatings confirmed the presence of MMA segments.

  11. Block copolymer assembly on nanoscale patterns of polymer brushes formed by electrohydrodynamic jet printing.

    Science.gov (United States)

    Onses, M Serdar; Ramírez-Hernández, Abelardo; Hur, Su-Mi; Sutanto, Erick; Williamson, Lance; Alleyne, Andrew G; Nealey, Paul F; de Pablo, Juan J; Rogers, John A

    2014-07-22

    Fundamental understanding of the self-assembly of domains in block copolymers (BCPs) and capabilities in control of these processes are important for their use as nanoscale templates in various applications. This paper focuses on the self-assembly of spin-cast and printed poly(styrene-block-methyl methacrylate) BCPs on patterned surface wetting layers formed by electrohydrodynamic jet printing of random copolymer brushes. Here, end-grafted brushes that present groups of styrene and methyl methacrylate in geometries with nanoscale resolution deterministically define the morphologies of BCP nanostructures. The materials and methods can also be integrated with lithographically defined templates for directed self-assembly of BCPs at multiple length scales. The results provide not only engineering routes to controlled formation of complex patterns but also vehicles for experimental and simulation studies of the effects of chemical transitions on the processes of self-assembly. In particular, we show that the methodology developed here provides the means to explore exotic phenomena displayed by the wetting behavior of BCPs, where 3-D soft confinement, chain elasticity, interfacial energies, and substrate's surface energy cooperate to yield nonclassical wetting behavior. PMID:24882265

  12. Fabrication of a sub-10 nm silicon nanowire based ethanol sensor using block copolymer lithography.

    Science.gov (United States)

    Rasappa, Sozaraj; Borah, Dipu; Faulkner, Colm C; Lutz, Tarek; Shaw, Matthew T; Holmes, Justin D; Morris, Michael A

    2013-02-15

    This paper details the fabrication of ultrathin silicon nanowires (SiNWs) on a silicon-on-insulator (SOI) substrate as an electrode for the electro-oxidation and sensing of ethanol. The nanowire surfaces were prepared by a block copolymer (BCP) nanolithographic technique using low molecular weight symmetric poly(styrene)-block-poly(methyl methacrylate) (PS-b-PMMA) to create a nanopattern which was transferred to the substrate using plasma etching. The BCP orientation was controlled using a hydroxyl-terminated random polymer brush of poly(styrene)-random-poly(methyl methacrylate) (HO-PS-r-PMMA). TEM cross-sections of the resultant SiNWs indicate an anisotropic etch process with nanowires of sub-10 nm feature size. The SiNWs obtained by etching show high crystallinity and there is no evidence of defect inclusion or amorphous region production as a result of the pattern transfer process. The high density of SiNWs at the substrate surface allowed the fabrication of a sensor for cyclic voltammetric detection of ethanol. The sensor shows better sensitivity to ethanol and a faster response time compared to widely used polymer nanocomposite based sensors. PMID:23340158

  13. A new drug carrier: Magnetite nanoparticles coated with amphiphilic block copolymer

    Institute of Scientific and Technical Information of China (English)

    CHANG Yu; BAI YunPeng; TENG Bao; Li ZhaoLong

    2009-01-01

    This paper reports on the synthesis and characterization of 4 nm magnetite nanoparticles coated with amphiphilic block copolymers of poly(ethyl methacrylate)-b-poly(2-hydroxyethyl methacrylate) (PEMA-b-PHEMA) by surface-initiated atom transfer radical polymerization (ATRP), which can act as new po-tential carriers for hydrophobic targeted drug delivery. Vibrating sample magnetometer analysis indi-cated that the magnetite nanoparticles were superparamagnetic at room temperature. Thermogravim-etric analysis (TGA) was applied to studying the property of surface of magnetite nanoparticles, and the surface density of macromolecules was calculated. The grafting density of oleic acid, BrMPA and PEMA was 5.8, 3.9, 0.16 chain/nm2 respectively, which indicates that the initiation efficiency decreases due to the influence of large space of oleic acid molecules. In vitro progesterone and (-)-isoproterenol hy-drochloride release in phosphate buffered saline (PBS) at pH 7.0 and 37℃ was conducted in order to demonstrate the function of drug loading and release. The results showed that the amount of drug carried into the core-shell Fe3O4@PEMA-b-PHEMA depends on the length of hydrophobic segment of block copolymer. The release of progesterone (37% after 22 h in our previous work) was compared with the release of (-)-isoproterenol hydrochloride (80% after 50 min), demonstrating that the strong hy-drophobic interaction between hydrophobic segment and drug can effectively control the release of hydrophobic drugs.

  14. Enhanced Lateral Ordering in Cylinder Forming PS-b-PMMA Block Copolymers Exploiting the Entrapped Solvent.

    Science.gov (United States)

    Seguini, Gabriele; Zanenga, Fabio; Giammaria, Tommaso J; Ceresoli, Monica; Sparnacci, Katia; Antonioli, Diego; Gianotti, Valentina; Laus, Michele; Perego, Michele

    2016-03-30

    The self-assembly of block copolymer (BCP) thin films produces dense and ordered nanostructures. Their exploitation as templates for nanolithography requires the capability to control the lateral order of the nanodomains. Among a multiplicity of polymers, the widely studied all-organic polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) BCP can easily form nanodomains perpendicularly oriented with respect to the substrate, since the weakly unbalanced surface interactions are effectively neutralized by grafting to the substrate an appropriate poly(styrene-random-methyl methacrylate) P(S-r-MMA) random copolymer (RCP). This benefit along with the selective etching of the PMMA component and the chemical similarity with the standard photoresist materials deserved for PS-b-PMMA the role of BCP of choice for the technological implementation in nanolithography. This work demonstrates that the synergic effect of thermal annealing with the initial solvent naturally trapped in the basic RCP + BCP system after the deposition process can be exploited to enhance the lateral order. The solvent content embedded in the total RCP + BCP system can be tuned by changing the molecular weight and thus the thickness of the grafted RCP brush layer, without introducing external reservoirs or dedicated setup and/or systems. The appropriate supply of solvent supports a grain coarsening kinetics following a power law with a 1/3 growth exponent for standing hexagonally ordered cylinders. PMID:26959626

  15. A standard graphite block

    International Nuclear Information System (INIS)

    A graphite block was calibrated for the thermal neutron flux of the Ra-Be source using indium foils as detectors. Experimental values of the thermal neutron flux along the central vertical axis of the system were corrected for the self-shielding effect and depression of flux in the detector. The experimental values obtained were compared with the values calculated on the basis of solving the conservation neutron equation by the continuous slowing-down theory. In this theoretical calculation of the flux the Ra-Be source was divided into three resonance energy regions. The measurement of the thermal neutron diffusion length in the standard graphite block is described. The measurements were performed in the thermal neutron region of the system. The experimental results were interpreted by the diffusion theory for point thermal neutron source in the finite system. The thermal neutron diffusion length was calculated to be L= 50.9 ±3.1 cm for the following graphite characteristics: density = 1.7 g/cm3; boron content = 0.1 ppm; absorption cross section = 3.7 mb

  16. Synthesis of carboxylic block copolymers via reversible addition fragmentation transfer polymerization for tooth erosion prevention.

    Science.gov (United States)

    Lei, Y; Wang, T; Mitchell, J W; Qiu, J; Kilpatrick-Liverman, L

    2014-12-01

    Dental professionals are seeing a growing population of patients with visible signs of dental erosion. The approach currently being used to address the problem typically leverages the enamel protection benefits of fluoride. In this report, an alternative new block copolymer with a hydrophilic polyacrylic acid (PAA) block and a hydrophobic poly(methyl methacrylate) (PMMA) block was developed to similarly reduce the mineral loss from enamel under acidic conditions. This series of PMMA-b-PAA block copolymers was synthesized by reversible addition fragmentation transfer (RAFT) polymerization. Their structures were characterized by gel permeation chromatography (GPC) and (1)H nuclear magnetic resonance (NMR) spectra. The molar fractions of acrylic acid (AA) in the final block copolymer were finely controlled from 0.25 to 0.94, and the molecular weight (Mn) of PMMA-b-PAA was controlled from 10 kDa to 90 kDa. The binding capability of the block copolymer with hydroxyapatite (HAP) was investigated by ultraviolet-visible spectroscopy (UV-Vis) and Fourier transform infrared (FTIR) spectroscopy. FTIR spectra confirmed that the PMMA-b-PAA block copolymer could bind to HAP via bridging bidentate bonds. Both UV-Vis and FTIR spectra additionally indicated that a high polymer concentration and low solution pH favored the polymer binding to HAP. The erosion-preventing efficacy of the PMMA-b-PAA block copolymer in inhibiting HAP mineral loss was quantitatively evaluated by atomic absorption spectroscopy (AAS). Based on the results, polymer treatment reduced the amount of calcium released by 27% to 30% in comparison with the unprotected samples. Scanning electron microscope (SEM) observations indicated that PMMA-b-PAA polymer treatment protected enamel from acid erosion. This new amphiphilic block copolymer has significant potential to be integrated into dentifrices or mouthrinses as an alternative non-fluoride ingredient to reduce tooth erosion. PMID:25248611

  17. Negative-tone block copolymer lithography by in situ surface chemical modification.

    Science.gov (United States)

    Kim, Bong Hoon; Byeon, Kyeong-Jae; Kim, Ju Young; Kim, Jinseung; Jin, Hyeong Min; Cho, Joong-Yeon; Jeong, Seong-Jun; Shin, Jonghwa; Lee, Heon; Kim, Sang Ouk

    2014-10-29

    Negative-tone block copolymer (BCP) lithography based on in situ surface chemical modification is introduced as a highly efficient, versatile self-assembled nanopatterning. BCP blends films consisting of end-functionalized low molecular weight poly(styrene-ran-methyl methacrylate) and polystyrene-block-Poly(methyl methacylate) can produce surface vertical BCP nanodomains on various substrates without prior surface chemical treatment. Simple oxygen plasma treatment is employed to activate surface functional group formation at various substrates, where the end-functionalized polymers can be covalently bonded during the thermal annealing of BCP thin films. The covalently bonded brush layer mediates neutral interfacial condition for vertical BCP nanodomain alignment. This straightforward approach for high aspect ratio, vertical self-assembled nanodomain formation facilitates single step, site-specific BCP nanopatterning widely useful for various substrates. Moreover, this approach is compatible with directed self-assembly approaches to produce device oriented laterally ordered nanopatterns. PMID:24912807

  18. One-Block CYRCA: an automated procedure for identifying multiple-block alignments from single block queries

    OpenAIRE

    Frenkel-Morgenstern, Milana; Singer, Alice; Bronfeld, Hagit; Pietrokovski, Shmuel

    2005-01-01

    One-Block CYRCA is an automated procedure for identifying multiple-block alignments from single block queries (). It is based on the LAMA and CYRCA block-to-block alignment methods. The procedure identifies whether the query blocks can form new multiple-block alignments (block sets) with blocks from a database or join pre-existing database block sets. Using pre-computed LAMA block alignments and CYRCA sets from the Blocks database reduces the computation time. LAMA and CYRCA are highly sensit...

  19. Evaluation of pH-sensitive poly(2-hydroxyethyl methacrylate-co-2-(diisopropylamino)ethyl methacrylate) copolymers as drug delivery systems for potential applications in ophthalmic therapies/ocular delivery of drugs

    OpenAIRE

    P. A. Faccia; F. M. Pardini; J. I. Amalvy

    2015-01-01

    Smart polymers like pH sensitive systems can improve different pharmacological treatment. In this work the behavior of copolymers containing 2-hydroxyethyl methacrylate (HEMA) with different proportions of 2-(diisopropylamino) ethyl methacrylate (DPA) and different amounts of cross-linker agent, ethylene glycol dimethacrylate (EGDMA) are evaluated as pH-sensitive drug delivery systems for potential application in ophthalmic therapies. A detailed characterization of the pH-responsive behavior ...

  20. Photochemical Synthesis and Versatile Functionalization Method of a Robust Porous Poly(ethylene glycol methacrylate-co-allyl methacrylate) Monolith Dedicated to Radiochemical Separation in a Centrifugal Microfluidic Platform

    OpenAIRE

    Marion Losno; Ivan Ferrante; René Brennetot; Jérôme Varlet; Cécile Blanc; Bernard Grenut; Etienne Amblard; Stéphanie Descroix; Clarisse Mariet

    2016-01-01

    The use of a centrifugal microfluidic platform is an alternative to classical chromatographic procedures for radiochemistry. An ion-exchange support with respect to the in situ light-addressable process of elaboration is specifically designed to be incorporated as a radiochemical sample preparation module in centrifugal microsystem devices. This paper presents a systematic study of the synthesis of the polymeric porous monolith poly(ethylene glycol methacrylate-co-allyl methacrylate) used as ...

  1. Effect of cyclic loading on microleakage of silorane based composite compared with low shrinkage methacrylate-based composites

    Directory of Open Access Journals (Sweden)

    Hamid Kermanshah

    2016-01-01

    Conclusion: Silorane did not provide better marginal seal than the low shrinkage methacrylate-based composites (except Aelite. In addition, cyclic loading did not affect the marginal microleakage of evaluated composite restorations .

  2. Studies on acrylated epoxydised triglyceride resin-co-butyl methacrylate towards the development of biodegradable pressure sensitive adhesives.

    Science.gov (United States)

    David, S Begila; Sathiyalekshmi, K; Gnana Raj, G Allen

    2009-12-01

    The potential chemical utility of Soya bean oil for the preparation of novel biodegradable polymeric pressure sensitive adhesive has been investigated. Epoxy resin was prepared through in situ epoxidation of Soya bean oil under controlled reaction conditions. Acrylated epoxidised triglyceride resin (AET resin) and copolymer of AET resin with butyl methacrylate were prepared and evaluated. Higher the concentration of butyl methacrylate higher is the degree of copolymerization of AET resin with butyl methacrylate. An optimum concentration of AET resin with butyl methacrylate (100 : 0.40) yields favourable shear holding time and peel strength to qualify as pressure sensitive adhesive. The candidate PSA formulation is biodegradable with antimicrobial activity against gram positive S. aureus ATCC 25923. PMID:18584126

  3. Methacrylic-based nanogels for the pH-sensitive delivery of 5-Fluorouracil in the colon

    OpenAIRE

    Ashwanikumar N; Kumar NA; Nair SA; Kumar GS

    2012-01-01

    N Ashwanikumar,1,* Nisha Asok Kumar,2,* S Asha Nair,2 GS Vinod Kumar11Chemical Biology, 2Cancer Research Programme, Rajiv Gandhi Center for Biotechnology, Poojappura, Thiruvananthapuram, Kerala, India *These authors contributed equally to this workAbstract: Methacrylic-based copolymers in drug-delivery systems demonstrate a pH-sensitive drug-releasing behavior in the colon. In this study, copolymers of methacrylic acid and 2-ethyl hexyl acrylate were prepared using a microemulsion polymerizat...

  4. Influence of Methacrylic-Acrylic Copolymer Composition on Plasticiser-free Optode Films for pH Sensors

    OpenAIRE

    Musa Ahmad; Loh Han Chern; Teh Huey Fang; Lee Yook Heng

    2003-01-01

    In this work we have examined the use of plasticiser-free polymeric films incorporating a proton selective chromoionophore for optical pH sensor. Four types of methacrylic-acrylic copolymers containing different compositions of n-butyl acrylate (nBA) and methyl methacrylate (MMA) were synthesised for use as optical sensor films. The copolymers were mixed with appropriate amounts of chromoionophore (ETH5294) and a lipophilic salt before spin coated on glass slides to form films for the evaluat...

  5. Use of polyester resins and methyl methacrylate in the process of a radiation modification of alder wood. Pt. 1

    International Nuclear Information System (INIS)

    The possibility of alder wood modification by the radiation cross-linking of unsaturated polyester resins and methyl methacrylate was considered. The dependence of cross-linking density of resins and degree of conversion of methyl methacrylate on gamma or electron irradiation doses was determined. Using Polimal unsaturated polyester resins to improve alder wood properties appeared to be most profitable. It was found, that radiation-thermal method enabled to decrease the irradiation dose that was necessary to cure polyester resins. (author)

  6. Stress relaxation via addition-fragmentation chain transfer in high Tg, high conversion methacrylate-based systems

    OpenAIRE

    Park, Hee Young; Kloxin, Christopher J.; Abuelyaman, Ahmed S.; Oxman, Joe D.; Bowman, Christopher N.

    2012-01-01

    To reduce shrinkage stress which arises during the polymerization of crosslinked polymers, allyl sulfide functional groups were incorporated into methacrylate polymerizations to determine their effect on stress relaxation via addition-fragmentation chain transfer (AFCT). Additionally, stoichiometrically balanced thiol and allyl sulfide-containing norbornene monomers were incorporated into the methacrylate resin to maximize the overall functional group conversion and promote AFCT while also en...

  7. Preparation of poly (methyl methacrylate)/nanometer calcium carbonate composite by in-situ emulsion polymerization

    Institute of Scientific and Technical Information of China (English)

    史建明; 包永忠; 黄志明; 翁志学

    2004-01-01

    Methyl methacrylate (MMA) emulsion polymerization in the presence of nanometer calcium carbonate (nano-CaCO3) surface modified with (-methacryloxypropyltrimethoxysilane (MPTMS) was carried out to prepare poly (methyl methacrylate) (PMMA)/nano-CaCO3 composite. The reaction between nano-CaCO3 and MPTMS, and the grafting of PMMA onto nano-CaCO3 were confirmed by infrared spectrum. The grafting ratio and grafting efficiency of PMMA on nano-CaCO3 modified with MPTMS were much higher than that on nano-CaCO3 modified with stearic acid. The grafting ratio of PMMA increased as the weight ratio between MMA and nano-CaCO3 increased, while the grafting efficiency of PMMA decreased. Transmission electron micrograph showed that nano-CaCO3 covered with PMMA was formed by in-situ emulsion polymerization.

  8. Preparation and surface modification of magnetic poly(methyl methacrylate) microspheres

    Institute of Scientific and Technical Information of China (English)

    YANG Chengli; GUAN Yueping; XING Jianmin; LIU Junguo; AN Zhentao; LIU Huizhou

    2004-01-01

    A novel method for preparation of magnetic polymer microspheres by spraying suspension polymerization (SSP) was developed. Relatively uniform magnetic poly(methyl methacrylate) microspheres were prepared by the spraying suspension polymerization (SSP)using methyl methacrylate (MMA) as monomer, divinylbenzene (DVB) as cross-linking agent,benzoyl peroxide (BPO) as initiator and polyvinyl alcohol (PVA) as stabilizer in the presence of hydrophobic Fe3O4 magnetic fluid. The microspheres prepared were modified by surface chemical reaction. The magnetic properties and morphology of the microspheres were examined by SEM and VSM respectively. The active functional groups of microspheres were examined by infrared spectra. The results showed that microspheres with saturation magnetization of 16.8emu/g showed distinct superparamagnetic characteristics and the magnetic microspheres with a size of 10 μm were relatively uniform.

  9. Stable Poly(methacrylic acid Brush Decorated Silica Nano-Particles by ARGET ATRP for Bioconjugation

    Directory of Open Access Journals (Sweden)

    Marcello Iacono

    2015-08-01

    Full Text Available The synthesis of polymer brush decorated silica nano-particles is demonstrated by activator regeneration by electron transfer atom transfer radical polymerization (ARGET ATRP grafting of poly(tert-butyl methacrylate. ATRP initiator decorated silica nano-particles were obtained using a novel trimethylsiloxane derivatised ATRP initiator obtained by click chemistry. Comparison of de-grafted polymers with polymer obtained from a sacrificial initiator demonstrated good agreement up to 55% monomer conversion. Subsequent mild deprotection of the tert-butyl ester groups using phosphoric acid yielded highly colloidal and pH stable hydrophilic nano-particles comprising approximately 50% methacrylic acid groups. The successful bio-conjugation was achieved by immobilization of Horseradish Peroxidase to the polymer brush decorated nano-particles and the enzyme activity demonstrated in a conversion of o-phenylene diamine dihydrochloride assay.

  10. Rapid preparation and characterization of methacrylate-based monoliths for chromatographic and electrophoretic separation.

    Science.gov (United States)

    Fan, Li-Qun; Zhang, Yu-Ping; Gong, Wen-Jun; Qu, Ling-Bo; Lee, Kwang-Pill

    2010-01-01

    Butyl-methacrylate-based porous monoliths were rapidly prepared in the fused-silica capillary with a 10-cm stripe of polyimide removed from its exterior. The photopolymerization could be carried out in 150 s using ethylene glycol dimethacrylate as a cross-linking agent; 1-propanol, 1,4-butanediol, and water as tri-porogenic solvents; and Irgacure 1800 as a photo-initiator. The effect of different morphologies on the efficiency and retention properties was investigated using pressure-assisted CEC (p-CEC), CEC, and low pressure-assisted liquid chromatography modes (LPLC). Baseline separation of the model analytes was respectively achieved including thiourea, toluene, naphthalene, and biphenyl with the lowest theoretical height up to 8.0 microm for thiourea in the mode of p-CEC. Furthermore, the influence of the tri-porogenic solvents on the morphology of methacrylate-based monoliths was systematically studied with mercury intrusion porosimetry and scanning electron microscopy. PMID:20515536

  11. Effect of epoxidation on 30% poly(methyl methacrylate)-grafted natural rubber polymer electrolytes

    International Nuclear Information System (INIS)

    Epoxidized 30% poly(methyl methacrylate)-grafted natural rubber (EMG 30) as a polymer host in solid polymer electrolytes (SPEs) has been investigated. EMG30 was synthesized via performicepoxidation method onto 30% poly(methyl methacrylate)-grafted natural rubber (MG30) and the formations of epoxy group were discussed. The EMG30 were characterized by proton nuclear magnetic resonance (1HNMR) to investigate their chemical structure and differential scanning calorimeter to determine their crystallinity. A new peak in 1HNMR spectra (2.71 ppm) confirmed the appearance of epoxy group. SPE based on EMG30 doped with 40 wt% LiCF3SO3 show the highest conductivity. The complexation between EMG30 and LiCF3SO3 were confirmed by attenuated total reflection Fourier transform infrared (ATR-FTIR)

  12. Radioisotope investigations on the stratigraphic distribution of poly(methyl methacrylate) grafted onto leather

    International Nuclear Information System (INIS)

    Investigations on the stratigraphic distribution of poly(methyl methacrylate) in leather follow our earlier experiments on radiation grafting of vinyl monomers in situ. Polymer distribution was determined for pigskins and cattlehides tanned with basic sulphates of chromium (III). 14C-labelled methyl methacrylate was used in present experiments. Precision slicing technique was employed to cut consecutive slices parallel to the grain surface of the radiation modified leather. Quantitative analysis of polymer distribution in leather was based on radioactivity measurements. Each layer was burned in Oxymat apparatus and resulting 14CO2 was analysed by liquid scintillation method. On the basis of radioactivity measurements and visual observations with light microscope conclusion on desirable distribution of polymer was reached. In the midcorium part of leather polymer is evenly distributed and its content is much higher than for outer layers next to surface and flesh. Mechanism of relevant processes as well as formation and role played by peroxide compounds are discussed. (author)

  13. Radioisotope investigations on the stratigraphic distribution of poly/methyl methacrylate/grafted onto leather

    International Nuclear Information System (INIS)

    Investigations on the stratigraphic distribution of poly/methyl methacrylate/ in leather follow our earlier experiments on radiation grafting of vinyl monomers in situ. Polymer distribution was determined for pigskins and cattlehides tanned with basic sulphates of chromium/III/. 14C-labelled methyl methacrylate was used in present experiments. Precision slicing technique was employed to cut consecutive slices parallel to the grain surface of the radiation modified leather. Quantative analysis of polymer distribution in leather was based on radioactivity measurements. Each layer was burned in Oxymat apparatus and resulting 14CO2 was analysed by liquid scintillation method. On the basis of radioactivity measurements and visual observations with light microscope conclusion on desirable distribution of polymer was reached. In the midcorium part of leather polymer is evenly distributed and its content is much higher than for outer layers next to surface and flesh. Mechanism of relevant processes as well as formation and role played by peroxide compounds is discussed

  14. Synthesis and characterization of in situ prepared poly (methyl methacrylate) nanocomposites

    Indian Academy of Sciences (India)

    Shahzada Ahmad; Sharif Ahmad; S A Agnihotry

    2007-02-01

    Hybrid materials, which consist of organic–inorganic materials, are of profound interest owing to their unexpected synergistically derived properties. These hybrid materials replaced the pristine polymers due to their higher strength and stiffness in the recent years. In the present work, studies concerning the preparation of poly (methyl methacrylate) (PMMA), PMMA/SiO2, and PMMA/TiO2 nanocomposites are reported. These nanocomposite polymers were synthesized by means of free radical polymerization of methyl methacrylate using benzoyl peroxide as an initiator in a water medium. Further `sol–gel’ transformation based hydrolysis and condensation of Ti and Si alkoxides were used to prepare the inorganic phase during the polymerization process of MMA.

  15. High Molecular Weight Thermally Stable Poly (Sodium Methacrylate / Magnetites Nanocomposites Via Emulsion Polymerization

    Directory of Open Access Journals (Sweden)

    Rasha A. El-Ghazawya,

    2014-04-01

    Full Text Available Core/shell type magnetite nanocomposites (MN were synthesized using sodium methacrylate (NMA monomer. Functionalized and bare magnetite nanoparticles were prepared by conventional co-precipitation method giving particles with 3-10 nm in diameter. Microemulsion polymerization was used for constructing core/shell structure with magnetite nanoparticles as core and poly (sodium methacrylate as shell. Chemical structure and morphology of the synthesized PNMA/magnetite nanocomposites were investigated using FTIR and TEM, respectively. The synthesized nanocomposites show effective encapsulation of different treated magnetite nanoparticles in the polymer matrix and exhibited good thermal stability. Such magnetite nanocomposites with high molecular weight and thermal stability have potential application in enhanced oil recovery application.

  16. Synthesis and characterization of hydrolysed starch-g-poly(methacrylic acid) composite.

    Science.gov (United States)

    Zahran, Magdy K; Ahmed, Enas M; El-Rafie, Mohamed H

    2016-06-01

    A novel method for the synthesis of starch-g-poly(methacrylic acid) composite was adopted by graft polymerization of hydrolysed starch (HS) and methacrylic acid (MAA) in aqueous medium using an efficient sodium perborate (SPB)-thiourea (TU) redox initiation system. The parameters influencing the redox system efficiency and thence the polymerization method were considered. These parameters comprehended the concentrations of MAA, SPB, TU and SPB/TU molar ratio as well as the polymerization temperature. The polymerization reaction was scrutinized through calculation of the MAA total conversion percent (TC%). The resultant poly(MAA-HS) composite was assessed by evaluating the polymer criteria (the graft yield, GY%; the grafting efficiency, GE%; the homopolymer, HP%; and the total conversion). The comportment of the apparent viscosity of the cooked poly(MAA)-starch composite paste, obtained under diverse polymerization conditions, was examined. Tentative mechanisms, which depict all occasions that happen amid the entire course of the polymerization reaction, have been proffered. PMID:26968925

  17. PREPARATION OF POLY(METHYL METHACRYLATE)/LAYERED DOUBLE HYDROXIDES NANOCOMPOSITES via in situ SOLUTION POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    An exfoliated layered double hydroxides/poly(methyl methacrylate) (LDHs/PMMA) nanocomposite was prepared by in situ solution polymerization of methyl methacrylate (MMA) in the presence of 4-vinylbenzenesulfonate intercalated LDHs(MgAl-VBS LDHs). MgAl-VBS LDHs was prepared by the ion exchange method, and the structure and composition of the MgAl-VBS LDHs were determined by X-ray diffraction (XRD), infrared spectroscopy and elemental analysis. XRD and transmission electron microscopy (TEM) were employed to examine the structure of LDHs/PMMA nanocomposite. It was indicated that the LDHs layers were well exfoliated and dispersed in the PMMA matrix. The grafting of PMMA onto LDHs was confirmed by the extraction result and the weight fraction of grafted PMMA increased as the weight fraction of LDHs in the nanocomposites increased.

  18. Chemical structure of chromium(III) crosslinked collagen-poly(methyl methacrylate) copolymers in radiation grafting

    International Nuclear Information System (INIS)

    Upon γ-irradiation of aqueous emulsions of methyl methacrylate embedded into chrome tanned skin, the formation of graft copolymers is observed. The number-average molecular weight of the grafted poly(methyl methacrylate) side chains was in the range of 430000 (for a dose of 10 kGy) and practically independent of grafting degree. However, the number of branches per graft copolymer molecule increases from 0.3 to 0.8 when the degree of grafting increases from 32% to 88%. Similarly, the radiation yield, i.e. the number of branches formed per 100 eV of energy absorbed in the substrate polymer increases from 0.75 to 1.94. The value and meaning of molecular weight of graft copolymer is discussed along with the mechanism of polymer chain termination. (author) 14 refs.; 3 figs.; 4 tabs

  19. Preparation and characterization of poly(isobutyl methacrylate) microbeads with grafted amidoxime groups

    Science.gov (United States)

    Çaykara, Tuncer; Alaslan, Şerife Şirin; Gürü, Metin; Bodugöz, Hatice; Güven, Olgun

    2007-10-01

    Poly(isobutyl methacrylate) (PiBMA) microspheres with a 800- to 1500-μm diameter range synthesized by suspension polymerization technique were used as the trunk polymer in the preparation of a highly efficient new adsorbent. Glycidyl methacrylate (GMA) was grafted onto the trunk polymer by pre-irradiation grafting technique. Grafting conditions were optimized, and GMA grafted PiBMA beads were modified with iminodiacetonitrile (IDAN) in ethanol at 80 °C. The nitrile groups were then amidoximated by using 6% (m/v) hydroxylamine hydrochloride in methanol solution. The IDAN modification and the conversion of the nitrile groups to amidoxime were followed by FT-IR spectroscopy. The surface morphology and thermal behavior of the PiBMA and its modificated forms were also characterized by scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques further confirming modification and amidoximation.

  20. Preparation and characterization of poly(isobutyl methacrylate) microbeads with grafted amidoxime groups

    International Nuclear Information System (INIS)

    Poly(isobutyl methacrylate) (PiBMA) microspheres with a 800- to 1500-μm diameter range synthesized by suspension polymerization technique were used as the trunk polymer in the preparation of a highly efficient new adsorbent. Glycidyl methacrylate (GMA) was grafted onto the trunk polymer by pre-irradiation grafting technique. Grafting conditions were optimized, and GMA grafted PiBMA beads were modified with iminodiacetonitrile (IDAN) in ethanol at 80 deg. C. The nitrile groups were then amidoximated by using 6% (m/v) hydroxylamine hydrochloride in methanol solution. The IDAN modification and the conversion of the nitrile groups to amidoxime were followed by FT-IR spectroscopy. The surface morphology and thermal behavior of the PiBMA and its modificated forms were also characterized by scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques further confirming modification and amidoximation