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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. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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...

  13. Polystyrene-Poly(sodium methacrylate) Amphiphilic Block Copolymers by ATRP : Effect of Structure, pH, and Ionic Strength on Rheology of Aqueous Solutions

    NARCIS (Netherlands)

    Raffa, Patrizio; Brandenburg, Piter; Wever, Diego A. Z.; Broekhuis, Antonius A.; Picchioni, Francesco

    2013-01-01

    Three well-defined polystyrene-poly(sodium methacrylate) amphiphilic block copolymers characterized by different molecular architecture (diblock, triblock, and four-arm star) have been synthesized by ATRP. The rheology of their water solutions has been evaluated by measuring dynamic moduli and shear

  14. 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.

  15. 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.

  16. Investigation of cross-linking poly(methyl methacrylate) as a guiding material in block copolymer directed self-assembly

    Science.gov (United States)

    Seidel, Robert; Rincon Delgadillo, Paulina; Ramirez-Hernandez, Abelardo; Wu, Hengpeng; Her, Youngjun; Yin, Jian; Nealey, Paul; de Pablo, Juan; Gronheid, Roel

    2014-03-01

    Directed self-assembly (DDSA) of block copolymers ((BCP) is attracting a growing amount of interest as a techhnique to expand traditional lithography beyond its current limits. It has reecently been demonstrated that chemoepitaxy can be used to successfully ddirect BCP assembly to form large arrays off high-density features. The imec DSA LiNe flow uses lithography and trim-etch to produce a "prepattern" of cross-linked polystyrene (PS) stripes, which in turn guide the formation of assembled BCPP structures. Thhe entire process is predicated on the preferential interaction of the respective BCP domains with particular regionss of the underlying prepattern. The use of polystyrene as the guiding material is not uniquely required, however, and in fact may not even be preferable. This study investigates an alternate chemistry -- crosslinked poly(methyl methacrylate), X-PMMA, -- as the underlying polymer mat, providing a route to higher auto-affinity and therefore a stronger guiding ability. In addition to tthe advantages of the chemistry under investigation, this study explores the broader theme of extending BCP DSA to other materials.

  17. 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

  18. Amphiphilic poly(D- or L-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) block copolymers: controlled synthesis, characterization, and stereocomplex formation.

    Science.gov (United States)

    Spasova, Mariya; Mespouille, Laetitia; Coulembier, Olivier; Paneva, Dilyana; Manolova, Nevena; Rashkov, Iliya; Dubois, Philippe

    2009-05-11

    Novel well-defined amphiphilic poly(D-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) (PDLA-b-PDMAEMA) and poly(L-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) (PLLA-b-PDMAEMA) copolymers were obtained. The synthesis strategy consisted of a three-step procedure: (i) controlled ring-opening polymerization (ROP) of (D- or L-)lactide initiated by Al(O(i)Pr)(3), followed by (ii) quantitative conversion of the polylactide (PLA) hydroxyl end-groups with bromoisobutyryl bromide and (iii) atom transfer radical polymerization (ATRP) of DMAEMA. The PLA block molecular weight was kept below 5000 g/mol. The macromolecular parameters of the (co)polymers were determined by (1)H NMR spectroscopy and size exclusion chromatography (SEC). The stereocomplexes of PDLA-b-PDMAEMA/PLLA-b-PDMAEMA diblock copolymers were prepared via solvent casting. The stereocomplex formation was evidenced by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses. The obtained stereocomplexes had melting temperature of about 65 degrees C above that of the individual copolymers and exhibited diffraction patterns assigned to the stereocomplex crystallites. In addition, for the first time it was shown that the replacement of one of the PLA partners with high molecular weight PLLA or PDLA did not hamper the stereocomplex formation. The presence of PDMAEMA blocks proved to impart hydrophilicity of the synthesized copolymers and related stereocomplexes, as determined by static water contact angle measurements. PMID:19331403

  19. Can ionic liquid additives be used to extend the scope of poly(styrene)-block-poly(methyl methacrylate) for directed self-assembly?

    Science.gov (United States)

    Bennett, Thomas M.; Pei, Kevin; Cheng, Han-Hao; Thurecht, Kristofer J.; Jack, Kevin S.; Blakey, Idriss

    2014-07-01

    Directed self-assembly (DSA) is a promising approach for extending conventional lithographic techniques by being able to print features with critical dimensions under 10 nm. The most widely studied block copolymer system is polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA). This system is well understood in terms of its synthesis, properties, and performance in DSA. However, PS-b-PMMA also has a number of limitations that impact on its performance and hence scope of application. The primary limitation is the low Flory-Huggins polymer-polymer interaction parameter (χ), which limits the size of features that can be printed. Another issue with block copolymers in general is that specific molecular weights need to be synthesized to achieve desired morphologies and feature sizes. Here we explore blending ionic liquid (IL) additives with PS-b-PMMA to increase the χ parameter. ILs have a number of useful properties that include negligible vapor pressure, tunable solvent strength, thermal stability, and chemical stability. The blends of PS-b-PMMA with an IL selective for the PMMA block allowed the resolution of the block copolymer to be improved. Depending on the amount of additive, it is also possible to tune the domain size and the morphology of the systems. These findings may expand the scope of PS-b-PMMA for DSA.

  20. Laterally Mounted Azobenzenes on Platforms.

    Science.gov (United States)

    Hammerich, Melanie; Herges, Rainer

    2015-11-20

    Triazatriangulenium ions have previously been used as platforms to prepare self-assembled monolayers of functional molecules such as azobenzenes with vertical orientation and that are free-standing on gold surfaces. We have now prepared azobenzenes that are spanned between two posts which are attached on two platforms. Absorbed on a gold surface, the azobenzene should be laterally oriented at a distance of more than 4 Å above and thus electronically decoupled from the surface, and the system should perform a muscle-type movement upon isomerization. PMID:26551306

  1. 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...

  2. 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

  3. 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

  4. Unusual photoanisotropic alignment in amorphous azobenzene polymers

    DEFF Research Database (Denmark)

    Ramanujam, P.S.

    2015-01-01

    It is well known that irradiation of azobenzene polymer films between 490 and 530nm results in alignment of molecules perpendicular to the polarization of the incident beam. I have recently found that irradiation of amorphous azobenzene polymers with linearly polarized light at wavelengths between...

  5. 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.

  6. 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;

    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 ...

  7. 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...

  8. SYNTHESIS AND CHARACTERIZATION OF FOUR-ARMED BLOCK POLY(STYRENE-b-p-NITRO PHENYL METHACRYLATE) PREPARED BY THE ATRP METHOD

    Institute of Scientific and Technical Information of China (English)

    Cai-yuan Pan; Lei Tao; Ye Liu

    2002-01-01

    A novel tetrafunctional initiator, C[CH2O(CH2)3OOCCH(Br)CH3]4 (1), was synthesized through the reaction oftetraol with α-bromopropionyl chloride, and then was used as initiator of atom transfer radical polymerization (ATRP) in thepreparation of 4-armed polystyrene (PSt) with narrow polydispersity. The structure, molecular weight and molecular weightdistribution (MWD) of each arm were studied by 1H-NMR and GPC data of hydrolyzed products of the 4-armed PSt. TheATRP of St using 1/CuBr/bpy as initiator system is of "living" character based on the following evidence: narrow MWD,constant concentration of chain radical during the polymerization, control of molecular weight by the molar ratio of monomerconsumed to 1. The 4-armed poly(St-b-p-nitrophenyl methacrylate) [poly(St-b-NPMA)] was prepared by the ATRP ofNPMA using 4-armed PSt with terminal bromine as the initiator, and characterized by FT-IR, 1H-NMR spectra and GPCcurves. The micelles with PSt as core, and PNPMA as shell were formed by dropping DMSO into a solution of 4-armedpoly(St-b-NPMA) in DMF, as proved by laser light scatter (LLS) method.

  9. Incorporation of cyclic azobenzene into oligodeoxynucleotides for the photo-regulation of DNA hybridization.

    Science.gov (United States)

    Eljabu, Fatma; Dhruval, Joshi; Yan, Hongbin

    2015-12-01

    Cyclic azobenzene carboxylic acid was synthesized using a shortened route. After reaction with D-threolinol, the resulting cyclic azobenzene-D-threolinol (cAB-Thr) building block was transformed into the corresponding DMTr-protected phosphoramidite, and incorporated into oligodeoxynucleotides at various positions and frequencies by solid phase synthesis. The melting temperatures of these modified oligonucleotides were determined by UV spectrometry. Photo-regulation of cAB-Thr-modified oligonucleotides with their complementary sequence was evaluated by Fluorescence Resonance Energy Transfer experiments using a fluorescein-Black Hole Quencher pair. Results suggest that while cis-cAB destabilizes DNA duplexes, trans-cAB can be accommodated in double stranded DNA.

  10. 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.

  11. 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.

  12. 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

  13. 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

    2016-05-01

    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.

  14. 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 ...... Institute of Physics....

  15. 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

  16. 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...

  17. 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.

  18. 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

  19. Azobenzene-derived tris-β-diketonate lanthanide complexes: reversible trans-to-cis photoisomerization in solution and solid state.

    Science.gov (United States)

    Lin, Li-Rong; Wang, Xuan; Wei, Gao-Ning; Tang, Hui-Hui; Zhang, Hui; Ma, Li-Hua

    2016-10-14

    Novel azobenzene-derived β-diketonates (4,4,5,5,6,6,6-heptafluoro-1-azobenzene-1,3-hexanedione (LA), 4,4,5,5,6,6,6-heptafluoro-1-(4-dimethylamino)azobenzene-1,3-hexanedione (LB)) were designed and their complexes with lanthanide cations (La(3+), Eu(3+), Gd(3+), Yb(3+)) were prepared and characterized by (1)H NMR, FT-IR, and elemental analysis. Three of the complexes were crystallized successfully and identified by X-ray diffraction. It was significant to find that LA showed remarkably reversible trans-to-cis isomerization properties, however, LB, bearing an electron donor compared with LA, slowed down the isomerization to an extent. The presence of Ln(iii) enhanced the reversible trans-to-cis isomerization properties of both LA and LB a little upon photoirradiation in organic solvents, and amazingly increased the fatigue resistance. In addition, the complexes doped in polymethyl methacrylate (PMMA) films produced a similar phenomenon as well as when in solution. Theoretical calculations based on time dependent density functional theory (TD-DFT) were performed for geometry optimization and to determine the excitation energies of LA and LB to gain further insight into the electronic structure of the complexes, and the data were consistent with the experimental results. The excellent reversible photoisomerization properties of the newly designed Ln(iii) complexes can offer important advantages that will help with the further study of these materials to reach their full potential in applications such as molecular switching devices.

  20. Dynamics of Azobenzene Dimer Photoisomerization: Electronic and Steric Effects.

    Science.gov (United States)

    Titov, Evgenii; Granucci, Giovanni; Götze, Jan Philipp; Persico, Maurizio; Saalfrank, Peter

    2016-09-15

    While azobenzenes readily photoswitch in solution, their photoisomerization in densely packed self-assembled monolayers (SAMs) can be suppressed. Reasons for this can be steric hindrance and/or electronic quenching, e.g., by exciton coupling. We address these possibilities by means of nonadiabatic molecular dynamics with trajectory surface hopping calculations, investigating the trans → cis isomerization of azobenzene after excitation into the ππ* absorption band. We consider a free monomer, an isolated dimer and a dimer embedded in a SAM-like environment of additional azobenzene molecules, imitating in this way the gradual transition from an unconstrained over an electronically coupled to an electronically coupled and sterically hindered, molecular switch. Our simulations reveal that in comparison to the single molecule the quantum yield of the trans → cis photoisomerization is similar for the isolated dimer, but greatly reduced in the sterically constrained situation. Other implications of dimerization and steric constraints are also discussed. PMID:27542538

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

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Sanchez, Carlos; Alcalá, Rafael

    2009-01-01

    Volume holographic data storage is one of the most promising techniques to improve both the storage capacity of devices and the transfer data rate. Among the materials proposed as storage data media, azobenzene containing polymers have received much attention. Some of their properties seem...... to be 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...

  2. 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...

  3. 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 characteris...... 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.......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...

  4. 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...

  5. 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.

  6. 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.

  7. 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...

  8. 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.

  9. 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....

  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. A remarkably efficient azobenzene peptide for holographic information storage

    DEFF Research Database (Denmark)

    Rasmussen, P.H.; Ramanujam, P.S.; Hvilsted, S.;

    1999-01-01

    A new family of proline-based azobenzene peptides (DNO) for holographic information storage is reported.:By use of polarization holography, it was found that gratings with extraordinarily high diffraction efficiency (up to 80%) can be recorded in hundreds of milliseconds in a similar to 13-mu m......-thick film of dimer 10. This represents a decrease of the response time by more than 2 orders of magnitude when compared to that of the ornithine-based DNO dimer previously reported. Furthermore, it supports the expectation that increasing the rigidity of the peptide backbone is: crucial in the design...... of effective azobenzene peptides for optical recording. Gratings recorded in 10 can be erased-by circularly polarized light in a few-seconds. It is also noted that, unlike DNOs previously reported, 10 is soluble in common organic solvents and can be assembled by solution phase synthesis, which is mandatory...

  12. Photophysical characteristics of polyaniline with photochromic azobenzene side groups

    Institute of Scientific and Technical Information of China (English)

    Feng Wei; Huang Kun; Wan Mei-Xiang

    2005-01-01

    Photochromic characteristics and optical molecular reorientation in conducting polymer such as polyaniline derivatives containing photochromic azobenzene moieties (PAPNPAPOA) in side chain are studied. Changes in the UV-vis absorption, refractive index, thickness, contact angle and morphology of these films after irradiation of a linearly polarized light with a wavelength of 365nm are measured. The trans-cis isomerization of PAPNPAPOA is proved irreversible even after withdrawing the UV light for a long time. That the structure of main-chain attends by the trans-cis isomerization of side-chain is confirmed by the absorption and the solution colour during the UV irradiation. These effects are discussed by taking the trans-cis isomerization of azobenzene into consideration.

  13. 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...

  14. 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

    . A transition route based on experimental results for the theoretically calculated energy level scheme is proposed. Physical observations of surface relief in thin films of azobenzene polymers when irradiated with polarized light are reported. These include two beam polarization holographic observations...... and 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....

  15. 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...... materials, both copolymethacrylates and dendritic or hyperbranched polyesters provide some materials that exhibit liquid crystallinity. However, none of these other scaffolds offer materials that allow long-lasting anisotropy to be laser Light induced....

  16. 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...... materials, both copolymethacrylates and dendritic or hyperbranched polyesters provide some materials that exhibit liquid crystallinity. However, none of these other scaffolds offer materials that allow long-lasting anisotropy to be laser Light induced....

  17. 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....

  18. Rewritable azobenzene polyester for polarization holographic data storage

    DEFF Research Database (Denmark)

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

    2000-01-01

    gratings was studied in case of films with and without a hard protective layer. We showed that the dominant contribution to the diffraction efficiency comes from the anisotropy in case of expositions below 1 sec even for high incident intensity. The usage of the same wavelength for writing, reading...... and erasing was tested. The ability of azobenzene polyester for rewriting was found satisfactory after many writing-erasing cycles....

  19. Light intensity dependent optical rotation in azobenzene polymers

    Science.gov (United States)

    Ivanov, M.; Ilieva, D.; Petrova, T.; Dragostinova, V.; Todorov, T.; Nikolova, L.

    2006-05-01

    We investigate the self-induced rotation of the azimuth of light polarization ellipse in azobenzene polymers. It is initiated by the photoreorientation and ordering of the azobenzenes on illumination with elliptically polarized light resulting in the appearance of an optical axis whose direction is gradually rotated along the depth of the film. A macroscopic chiral structure is created with a pitch depending on light ellipticity and the photobirefringence ▵n in the successive layers of the film. In this work we make use of the fact that at elevated temperatures ▵n is very sensitive to light intensity. In our acrylic amorphous azobenzene polymer at temperatures 50-65°C the saturated values of ▵n are much higher for low intensity of the exciting light than for higher intensity. In this temperature range the polarization azimuth of monochromatic blue light with different intensity is rotated to a different angle after passing through the polymer film. This effect can be used for passive elements rotating the polarization azimuth depending on light intensity and for the formation of light beams with a space-variant polarization state.

  20. 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

  1. 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

  2. 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 tran...

  3. 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.

  4. 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.

  5. Correlation between the molecular structure and trans←→ cis isomerization characteristics of azobenzenes

    Institute of Scientific and Technical Information of China (English)

    HAN Mina; HONDA Takumu

    2012-01-01

    Photochemical and thermal isomerization of various azobenzenes was systematically investigated to understand the correlation between the molecular structure and trans←→cis isomerization characteristics of azobenzenes.A blue shift in π-π* absorption band of ortho-alkylated azobenzenes (1o and 2o) was observed together with a reduction in molar extinction coefficient (ε) in comparison with both meta-alkylated azobenzenes (4m and 5m) and 7p lacking the meta and ortho substituents.For ortho-alkylated azobenzene,photochemical trans-to-cis isomerization and thermal back cis-to-trans isomerization in solution occurred slowly when compared with 4m,5m and 7p.The half-life time of the cis form of 2o was found to be 380 h,which is about 8-50 times longer than those of comparable 4m,5m (43-13 h) and 7p (7h).Furthermore,comparison of the molecular structure and isomerization characteristics of azobenzene thiol (2oand 5m) self-assembled monolayers on flat gold surfaces indicates that the trans-to-cis photoconversion in monolayer systems is influenced by steric hindrance and strong intermolecular interaction between azobenzene units.

  6. Azobenzene dye-coupled quadruply hydrogen-bonding modules as colorimetric indicators for supramolecular interactions

    Directory of Open Access Journals (Sweden)

    Yagang Zhang

    2012-04-01

    Full Text Available The facile coupling of azobenzene dyes to the quadruply hydrogen-bonding modules 2,7-diamido-1,8-naphthyridine (DAN and 7-deazaguanine urea (DeUG is described. The coupling of azobenzene dye 2 to mono-amido DAN units 4, 7, and 9 was effected by classic 4-(dimethylaminopyridine (DMAP-catalyzed peptide synthesis with N-(3-dimethylaminopropyl-N’-ethyl carbodiimide hydrochloride (EDC as activating agent, affording the respective amide products 5, 8, and 10 in 60–71% yield. The amide linkage was formed through either the aliphatic or aromatic ester group of 2, allowing both the flexibility and absorption maximum to be tuned. Azobenzene dye 1 was coupled to the DeUG unit 11 by Steglich esterification to afford the product amide 12 in 35% yield. Alternatively, azobenzene dye 16 underwent a room-temperature copper-catalyzed azide–alkyne Huisgen cycloaddition with DeUG alkyne 17 to give triazole 18 in 71% yield. Azobenzene coupled DAN modules 5, 8, and 10 are bright orange–red in color, and azobenzene coupled DeUG modules 12 and 18 are orange–yellow in color. Azobenzene coupled DAN and DeUG modules were successfully used as colorimetric indicators for specific DAN–DeUG and DAN–UPy (2-ureido-4(1H-pyrimidone quadruply hydrogen-bonding interactions.

  7. 76 FR 69659 - Methacrylic Acid-Methyl Methacrylate-Polyethylene Glycol Monomethyl Ether Methacrylate Graft...

    Science.gov (United States)

    2011-11-09

    ... copolymer when used as an inert ingredient in a pesticide chemical formulation. Akzo Noel Surface Chemistry... methacrylate graft copolymer on food or feed commodities. DATES: This regulation is effective November 9, 2011... (NAICS code 111). Animal production (NAICS code 112). Food manufacturing (NAICS code 311)....

  8. 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

  9. 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.

  10. An Optimized Glutamate Receptor Photoswitch with Sensitized Azobenzene Isomerization.

    Science.gov (United States)

    Gascón-Moya, Marta; Pejoan, Arnau; Izquierdo-Serra, Mercè; Pittolo, Silvia; Cabré, Gisela; Hernando, Jordi; Alibés, Ramon; Gorostiza, Pau; Busqué, Félix

    2015-10-16

    A new azobenzene-based photoswitch, 2, has been designed to enable optical control of ionotropic glutamate receptors in neurons via sensitized two-photon excitation with NIR light. In order to develop an efficient and versatile synthetic route for this molecule, a modular strategy is described which relies on the use of a new linear fully protected glutamate derivative stable in basic media. The resulting compound undergoes one-photon trans-cis photoisomerization via two different mechanisms: direct excitation of its azoaromatic unit and irradiation of the pyrene sensitizer, a well-known two-photon sensitive chromophore. Moreover, 2 presents large thermal stability of its cis isomer, in contrast to other two-photon responsive switches relying on the intrinsic nonlinear optical properties of push-pull substituted azobenzenes. As a result, the molecular system developed herein is a very promising candidate for evoking large photoinduced biological responses during the multiphoton operation of neuronal glutamate receptors with NIR light, which require accumulation of the protein-bound cis state of the switch upon repeated illumination.

  11. Conformational Dynamics of o-Fluoro-Substituted Z-Azobenzene.

    Science.gov (United States)

    Rastogi, S K; Rogers, R A; Shi, J; Gao, C; Rinaldi, P L; Brittain, W J

    2015-11-20

    A conformational analysis of o-fluoro Z-azobenzene reveals a slight preference for aromatic C-F/π interaction. Density functional theory (DFT) indicates that the conformation with a C-F/π interaction is preferred by approximately 0.3-0.5 kcal/mol. Ground-state conformations were corroborated with X-ray crystallography. (Z)-Azobenzene (Z-AB) with at least one o-fluoro per ring displays (19)F-(19)F through-space (TS) coupling. 2D J-resolved NMR was used to distinguish through-bond from TS coupling ((TS)JFF). (TS)JFF decreases as the temperature is lowered and the multiplets coalesce into broad singlets. We hypothesize that the coalescence temperature (Tc) corresponds to the barrier for phenyl rotation. The experimentally determined barrier of 8-10 kcal/mol has been qualitatively verified by DFT where transition states with a bisected geometry were identified with zero-point energies of 6-9 kcal/mol relative to ground state. These values are significantly higher that values estimated from previous theoretical studies but lie within a reasonable range for phenyl rotation in hydrocarbon systems.

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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

  17. Cis-trans isomerisation of azobenzenes studied by NMR spectroscopy with in situ laser irradiation and DFT calculations

    OpenAIRE

    Wazzan, Nuha

    2009-01-01

    NMR spectroscopy with in situ laser irradiation has been used to investigate the photo- and thermal isomerisation of eight azobenzene derivatives; diphenyldiazene (azobenzene), p-phenylazoaniline (p-aminoazobenzene), 4-(dimethylamino)azobenzene (Methyl Yellow), 4-dimethylamino-2-methylazobenzene (o-Methyl-Methyl Yellow), p-nitroazobenzene, 4-nitro-4’-dimethylaminoazobeneze (Dimethyl-nitroazobenzene), 4-(4-nitrophenylazo)aniline (Disperse Orange 3) and N-ethyl-N-(2-hydroxyethyl)-4-(4-nitrophen...

  18. 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.

  19. 40 CFR 721.10153 - Modified methyl methacrylate, 2-hydroxyethyl methacrylate polymer (generic).

    Science.gov (United States)

    2010-07-01

    ...-hydroxyethyl methacrylate polymer (generic). 721.10153 Section 721.10153 Protection of Environment...-hydroxyethyl methacrylate polymer (generic). (a) Chemical substance and significant new uses subject to... methacrylate polymer (PMN P-08-6) is subject to reporting under this section for the significant new...

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. Synthesis and Site-Specific Incorporation of Red-Shifted Azobenzene Amino Acids into Proteins.

    Science.gov (United States)

    John, Alford A; Ramil, Carlo P; Tian, Yulin; Cheng, Gang; Lin, Qing

    2015-12-18

    A series of red-shifted azobenzene amino acids were synthesized in moderate-to-excellent yields via a two-step procedure in which tyrosine derivatives were first oxidized to the corresponding quinonoidal spirolactones followed by ceric ammonium nitrate-catalyzed azo formation with the substituted phenylhydrazines. The resulting azobenzene-alanine derivatives exhibited efficient trans/cis photoswitching upon irradiation with a blue (448 nm) or green (530 nm) LED light. Moreover, nine superfolder green fluorescent protein (sfGFP) mutants carrying the azobenzene-alanine analogues were expressed in E. coli in good yields via amber codon suppression with an orthogonal tRNA/PylRS pair, and one of the mutants showed durable photoswitching with the LED light.

  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. Photo-Induced Magnetic Anisotropy of Polymer Film Containing Azobenzene Organic Free Radical Group

    Institute of Scientific and Technical Information of China (English)

    徐则达; 张勇; 陈小芳; 范星河; 宛新华; 周其凤

    2003-01-01

    The forward degenerate four-wave mixing geometry was employed to induce microstructure in an organic free radical azobenzene polymer film. Before irradiated with Ar+ laser beams (λ = 514.5 nm), the azobenzene organic free radical polymer exhibits magnetic isotropic measured by superconducting quantum interference device. After photo-induced microstructure, the polymer film becomes magnetic anisotropy. When the applied magnetic field H = 50 Gauss, the magnetization along the normal direction of the polymer film is Mz = 5.5 × 10-5 emu/g,which is larger than Mx = 4.1 × 10-5 emu/g in the direction parallel to the polymer film.

  7. 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.

  8. 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.

  9. Methacrylated glycol chitosan as a photopolymerizable biomaterial.

    Science.gov (United States)

    Amsden, Brian G; Sukarto, Abby; Knight, Darryl K; Shapka, Stephen N

    2007-12-01

    Glycol chitosan is a derivative of chitosan that is soluble at neutral pH and possesses potentially useful biological properties. With the goal of obtaining biocompatible hydrogels for use as tissue engineering scaffolds or drug delivery depots, glycol chitosan was converted to a photopolymerizable prepolymer through graft methacrylation using glycidyl methacrylate in aqueous media at pH 9. N-Methacrylation was verified by both (1)H NMR and (13)C NMR. The degree of N-methacrylation, measured via (1)H NMR, was easily varied from 1.5% to approximately 25% by varying the molar ratio of glycidyl methacrylate to glycol chitosan and the reaction time. Using a chondrocyte cell line, the N-methacrylated glycol chitosan was found to be noncytotoxic up to a concentration of 1 mg/mL. The prepolymer was cross-linked in solution using UV light and Irgacure 2959 photoinitiator under various conditions to yield gels of low sol content ( approximately 5%), high equilibrium water content (85-95%), and thicknesses of up to 6 mm. Cross-polarization magic-angle spinning (13)C solid state NMR verified the complete conversion of the double bonds in the gel. Chondrocytes seeded directly onto the gel surface, populated the entirety of the gel and remained viable for up to one week. The hydrogels degraded slowly in vitro in the presence of lysozyme at a rate that increased as the cross-link density of the gels decreased. PMID:18031015

  10. 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.

  11. 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...

  12. Novel Polymer Architectures for Optical Storage

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Forcén, Patrica; Oriol, Luis;

    2007-01-01

    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......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...

  13. 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

    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...

  14. 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.

  15. 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...

  16. Light propagation through photoinduced chiral structures in azobenzene-containing polymers

    DEFF Research Database (Denmark)

    Nedelchev, L; Nikolova, L; Todorov, T;

    2001-01-01

    We investigate light propagation through azobenzene-containing polymers with photoinduced chiral structures. The structures have large pitch but the Mauguin condition is not fulfilled. The eigenmodes are shown to be elliptical and their ellipticity is determined by the ellipticity e(o) of the exc...

  17. Synthesis and characterization of conjugated polymer containing azobenzene and oxadiazole units

    Institute of Scientific and Technical Information of China (English)

    Yue Zhang; Shi Jun Yu; Lu Wang; Cong Li

    2009-01-01

    A novel conjugated polymer containing azobenzene and oxadiazole units was synthesized through multi-step synthesis.The structures and properties of monomer and polymer were characterized and evaluated with IR,1H NMR,UV,TGA and GPC,respectively.Polymer with long side chain of alkoxy shows good solubility,thermal stability and photoisomerization property.

  18. 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......-cis-trans isomerizations of azobenzene molecules and it has been found that the 488 nm light power needed to induce the transition to the isotropic state increases when the film thickness decreases. The irradiation with the laser beam heats the film up and this seems to be responsible for the observed thickness dependence....... Optical absorption measurements show that azobenzene aggregates present in one of the polymers are broken down in the photoinduced phase transition. The birefringence induced with low power 488 nm light in films before and after undergoing that photoinduced phase transition has also been studied...

  19. 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

  20. 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...

  1. 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...

  2. 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....

  3. 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 ...

  4. 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

  5. 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.

  6. pH-sensitive methacrylic copolymers and the production thereof

    Science.gov (United States)

    Mallapragada, Surya K.; Anderson, Brian C.; Bloom, Paul D.; Sheares Ashby, Valerie V.

    2007-01-09

    The present invention provides novel multi-functional methacrylic copolymers that exhibit cationic pH-sensitive behavior as well as good water solubility under acidic conditions. The copolymers are constructed from tertiary amine methacrylates and poly(ethylene glycol) containing methacrylates. The copolymers are useful as gene vectors, pharmaceutical carriers, and in protein separation applications.

  7. The synthesis and characterization of 2-mercaptoethyl methacrylate

    Directory of Open Access Journals (Sweden)

    Knežević Marija

    2005-01-01

    Full Text Available The synthesis of 2-mercaptoethyl methacrylate from methacrylic acid and 2-mercaptoethanol by etherification using acetyl chloride as catalyst was optimized. The purity of the obtained product was controlled by gas chromatography and its identity confirmed by H-NMR and FTIR spectroscopy. 2-Mercapto-ethyl methacrylate could find application as a chain transfer agent in radical polymerizations.

  8. 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...

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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

  14. Cis-trans isomerisation of azobenzenes studied by laser-coupled NMR spectroscopy and DFT calculations.

    Science.gov (United States)

    Wazzan, Nuha A; Richardson, Patricia R; Jones, Anita C

    2010-07-30

    In a combined experimental and computational study of a group of para-substituted azobenzenes, the effects of substituents and solvent on the kinetics of thermal cis-to-trans isomerisation have been examined and the success of DFT calculations in predicting kinetic parameters assessed. Mono-substituted species are predicted to isomerise by inversion in both non-polar and polar solvent, whereas for push-pull azobenzenes the mechanism is predicted to change from inversion to rotation on going from non-polar to polar solvent. Computed free energies of activation qualitatively reproduce experimental trends but do not quantitatively predict the kinetics of cis-trans isomerisation. The polarisable continuum model of solvation fails to predict the experimentally observed influence of solvent on the entropy of activation.

  15. Preparation of a cationic azobenzene dye-montmorillonite intercalation compound and its photochemical behavior

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Montmorillonite/cationic azobenzene dye (GTL) intercalation compounds were prepared by the conventional ion exchange method. As compared with that of pure GTL, the thermal stability of the intercalated GTL was greatly enhanced, and the absorption band corresponding to azobenzene group in intercalated GTL shifted towards a longer wavelength by 55 nm, which could be ascribed to the strong conjugation of GTL supramolecular order structure (J cluster) confined in a nanoscale space of montmorillonite interlayer gallery. The microstructures of the resulting intercalation compounds could be successfully controlled by varying the amount of dye loaded as evidenced by the basal spacing of the intercalation compounds. The intercalated azo dye in the montmorillonite interlayer space exhibited reversible trans-to-cis photoisomerization and thermal cis-to-trans reaction. FTIR proved the successful intercalation of GTL into the silicate layer.

  16. 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.

  17. 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

  18. Theoretical study of solvent effects on the ground and low-lying excited free energy surfaces of a push-pull substituted azobenzene.

    Science.gov (United States)

    Corchado, Jose C; Sánchez, M Luz; Fdez Galván, Ignacio; Martín, M Elena; Muñoz-Losa, Aurora; Barata-Morgado, Rute; Aguilar, Manuel A

    2014-10-30

    The ground and low-lying excited free energy surfaces of 4-amino-4'-cyano azobenzene, a molecule that has been proposed as building block for chiroptical switches, are studied in gas phase and a variety of solvents (benzene, chloroform, acetone, and water). Solvent effects on the absorption and emission spectra and on the cis-trans thermal and photo isomerizations are analyzed using two levels of calculation: TD-DFT and CASPT2/CASSCF. The solvent effects are introduced using a polarizable continuum model and a QM/MM method, which permits one to highlight the role played by specific interactions. We found that, in gas phase and in agreement with the results found for other azobenzenes, the thermal cis-trans isomerization follows a rotation-assisted inversion mechanism where the inversion angle must reach values close to 180° but where the rotation angle can take almost any value. On the contrary, in polar solvents the mechanism is controlled by the rotation of the CN═NC angle. The change in the mechanism is mainly related to a better solvation of the nitrogen atoms of the azo group in the rotational transition state. The photoisomerization follows a rotational pathway both in gas phase and in polar and nonpolar solvents. The solvent introduces only small modifications in the nπ* free energy surface (S1), but it has a larger effect on the ππ* surface (S2) that, in polar solvents, gets closer to S1. In fact, the S2 band of the absorption spectrum is red-shifted 0.27 eV for the trans isomer and 0.17 eV for the cis. In the emission spectrum the trend is similar: only S2 is appreciably affected by the solvent, but in this case a blue shift is found.

  19. Inverse Relaxation of Photoinduced Birefringence in a Liquid-Crystalline Azobenzene Side-Chain Polymer

    Institute of Scientific and Technical Information of China (English)

    PAN Xu; WANG Chang-Shun; ZHANG Xiao-Qiang

    2008-01-01

    Photoinduced birefringence in a liquid-crystalline azobenzene side-chain polymer is investigated. It is observed that the birefringence does not show any decay but increases after switching off the pump light at room temperature. The magnitude of the birefringence relaxation is found to depend on the exposure dose of the pump light.A discussion about the mechanism of the inverse relaxation of birefringence is presented.

  20. 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

  1. 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...

  2. 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.

  3. 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...

  4. 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.

  5. Microscopic theory of light-induced deformation in amorphous side-chain azobenzene polymers.

    Science.gov (United States)

    Toshchevikov, V; Saphiannikova, M; Heinrich, G

    2009-04-16

    We propose a microscopic theory of light-induced deformation of side-chain azobenzene polymers taking into account the internal structure of polymer chains. Our theory is based on the fact that interaction of chromophores with the polarized light leads to the orientation anisotropy of azobenzene macromolecules which is accompanied by the appearance of mechanical stress. It is the first microscopic theory which provides the value of the light-induced stress larger than the yield stress. This result explains a possibility for the inscription of surface relief gratings in glassy side-chain azobenzene polymers. For some chemical architectures, elongation of a sample demonstrates a nonmonotonic behavior with the light intensity and can change its sign (a stretched sample starts to be uniaxially compressed), in agreement with experiments. Using a viscoplastic approach, we show that the irreversible strain of a sample, which remains after the light is switched off, decreases with increasing temperature and can disappear at certain temperature below the glass transition temperature. This theoretical prediction is also confirmed by recent experiments.

  6. Photo Induced Membrane Separation for Water Purification and Desalination Using Azobenzene Modified Anodized Alumina Membranes.

    Science.gov (United States)

    Fujiwara, Masahiro; Imura, Tatsuki

    2015-06-23

    Water purification and desalination to produce end-use water are important agendas in 21st century, because the global water shortage is becoming increasingly serious. Those processes using light energy, especially solar energy, without the consumption of fossil fuels are desired for creating sustainable society. For these earth-friendly water treatments, nanoporous materials and membranes are expected to provide new technologies. We have reported before that the repetitive photo isomerization of azobenzene groups between the trans and cis isomers induced by the simultaneous irradiation of UV and visible lights accelerates the molecular movement of nearby molecules in nanoporous materials. After further studies, we recently found that the permeation of water through azobenzene modified anodized alumina membranes as a photo responsive nanoporous membrane was achieved by the simultaneous irradiation of UV and visible lights, while no water penetration occurred under no light, only single UV or visible light. The photo induced permeation of water was promoted by the vaporization of water with the repetitive photo isomerization of azobenzene. This membrane permeation achieved the purification of water solutions, because dye molecules and a protein dissolved in aqueous solutions were not involved in the photo induced penetrated water. When 3.5% of sodium chloride solution as model seawater was employed for this membrane separation, the salt content of the permeated water was less than 0.01% to accomplish the complete desalination of seawater. PMID:26005901

  7. Femtosecond pump-probe photoionization-photofragmentation spectroscopy of azobenzene cation

    Institute of Scientific and Technical Information of China (English)

    HO; JrWei

    2010-01-01

    We report the studies of ultrafast dynamics of azobenzene cations using femtosecond photoionization-photofragmentation spectroscopy. In our experiment,a femtosecond pump pulse first prepares an ensemble of azobenzene cations via photoionization of neutrals. A delayed probe pulse then brings the evolving ionic system to higher states that ultimately undergo ion fragmentation. The dynamics is followed by monitoring either the parent-ion depletion or fragment-ion formation as a function of the pump-probe delay time. The observed transients for azobenzene cations are characterized by a constant ion depletion modulated by a rapidly damped oscillatory signal with a period of about 1 ps. Theoretical calculations suggest that the oscillation arises from a vibration motion along the twisting inversion coordinate involving displacements in CNNC and phenyl-ring torsions. The oscillation is damped rapidly with a time constant of about 1.2 ps,suggesting that energy dissipation from the active mode to bath modes takes place on this time scale.

  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. 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

  10. 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

  11. 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

  12. 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.

  13. 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;

    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...... candidates for azo components used in materials for data storage....

  14. 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

    2016-06-16

    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.

  15. 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

  16. 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.

  17. 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 ...

  18. 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.

  19. Vibrational spectra study of phosphorus dendrimer containing azobenzene units on the surface

    Science.gov (United States)

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

    2013-08-01

    The FTIR and FT Raman spectra of the first generation dendrimers, possessing oxybenzaldehyde (G1) or oxyphenylazobenzaldehyde (G2) terminal groups and sodium 4-[4-oxyphenyl)azo]-benzaldehyde (SOAB) were studied. The structural optimization and normal mode analysis were performed for dendrimer G2 on the basis of the density functional theory (DFT). These calculations gave the frequencies of vibrations, infrared intensities and Raman scattering activities for the E- and Z-forms of azobenzene unit. The energy differences between the E- and Z-forms are 12.62 and 25.16 kcal/mol for SOAB and G2. The calculated in gas phase dipole moments for the E- and Z-forms are equal to 20.86, 18.28 D (SOAB) and 7.56, 8.88 D (G2). The calculated geometrical parameters and harmonic vibrational frequencies are predicted in a good agreement with the experimental data. It was found that dendrimer G2 molecule has a concave lens structure with planar sbnd Osbnd C6H4sbnd CHdbnd Nsbnd N(CH3)Pdbnd S and sbnd Osbnd C6H4sbnd Ndbnd Nsbnd C6H4sbnd CHdbnd O fragments and slightly non-planar cyclotriphosphazene core. The experimental IR and Raman spectra of dendrimer G2 were interpreted by means of potential energy distributions. Relying on DFT calculations a complete vibrational assignment is proposed. The strong band 1598 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 SOAB and 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.

  20. 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.

  1. 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

  2. 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.

  3. Second-order nonlinear optical properties of mexylaminotriazine-functionalized glass-forming azobenzene derivatives

    Science.gov (United States)

    Umezawa, Hirohito; Jackson, Matthew; Lebel, Olivier; Nunzi, Jean-Michel; Sabat, Ribal Georges

    2016-10-01

    The second-order nonlinear optical coefficients of thin films of mexylaminotriazine-functionalized azobenzene molecular glass derivatives were measured using second harmonic generation. The thin films were poled using a custom corona poling set-up and the second harmonic light from a pulsed 1064-nm laser was detected. Four out of the six tested compounds showed optical nonlinearity and a maximum coefficient of 75 pm/V was obtained. The time dependence of the nonlinear coefficients was studied under ambient light and under dark; the second harmonic generation intensity stayed constant for thiazole-containing derivatives while a significant decay was measured for the other compounds.

  4. Azobenzene side-chain liquid crystalline polyesters with outstanding optical storage properties

    DEFF Research Database (Denmark)

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

    1998-01-01

    ,000 are routinely obtained by melt transesterification of the novel diols and selected diacid precursors (parameter iii). Prominent storage features include no prealignment of thin SCLC polyester films prior to the writing process, and sensitivity in a broad laser wavelength window (415-532 nm). Additionally......, the observed surface roughness is strongly dependent on the laser polarization. Polarization Fourier-Transform infrared studies of laser induced segmental motion in selectively deuterated SCLC cyanoazobenzene polyesters have revealed that not only the azobenzene chromophores but also main-chain and side......-chain spacers align preferentially perpendicular to laser polarization....

  5. Azobenzene Polyesters Used as Gate‐Like Scaffolds in Nanoscopic Hybrid Systems

    DEFF Research Database (Denmark)

    Bernardos, Andrea; Mondragón, Laura; Javakhishvili, Irakli;

    2012-01-01

    The synthesis and characterisation of new capped silica mesoporous nanoparticles for on‐command delivery applications is reported. Functional capped hybrid systems consist of MCM‐41 nanoparticles functionalised on the external surface with polyesters bearing azobenzene derivatives and rhodamine B...... inside the mesopores. Two solid materials, Rh‐PAzo8‐S and Rh‐PAzo6‐S, containing two closely related polymers, PAzo8 and PAzo6, in the pore outlets have been prepared. Materials Rh‐PAzo8‐S and Rh‐PAzo6‐S showed an almost zero release in water due to steric hindrance imposed by the presence of anchored...

  6. 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 ...... to interfere on a film illuminated with blue light. Polarized holographic gratings are also created with two orthogonally circularly polarized He-Ne beams. All these gratings are stable in darkness but can be erased with blue light. (C) 2000 American Institute of Physics....

  7. Synthesis and Characterization of Nonsymmetric Liquid Crystal Dimer Containing Biphenyl and Azobenzene Moiety

    Directory of Open Access Journals (Sweden)

    S. Sandy Subala

    2013-01-01

    Full Text Available Calamitic liquid crystalline dimer containing azobenzene moiety and a decyloxy biphenyl linked by flexible spacers {4-[7-(4′-decyloxy-biphenyl-4-yloxy-alkyloxy]-phenyl}-(4-decyl-phenyl-diazene has been synthesized and characterized by spectroscopic methods. The transition temperatures and phase behaviours were studied by Differential Scanning Calorimeter (DSC and Polarizing Optical Microscope (POM. The synthesized compounds exhibited enantiotropic liquid crystal phase with higher spacer display nematic and smectic C phases while lower spacer shows nematic and smectic A phases.

  8. 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.

  9. 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 ...

  10. 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…

  11. 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

  12. 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...

  13. Investigation of Methacrylic Acid at High Pressure Using Neutron Diffraction

    DEFF Research Database (Denmark)

    Marshall, William G.; Urquhart, Andrew; Oswald, Iain D. H.

    2015-01-01

    This article shows that pressure can be a low-intensity route to the synthesis of polymethacrylic acid. The exploration of perdeuterated methacrylic acid at high pressure using neutron diffraction reveals that methacrylic acid exhibits two polymorphic phase transformations at relatively low press...

  14. 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.

  15. OPTICAL PHASE CONJUGATION RESPONSE OF PHOTOINDUCED POLYMER FILMS CONTAINING AZOBENZENE MOIETIES WITH CHIRAL GROUP

    Institute of Scientific and Technical Information of China (English)

    Ze-da Xu; Yong Zhang; Xing-he Fan; Xin-hua Wan; Qi-feng Zhou

    2002-01-01

    An optically active monomer containing azobenzene moieties with chiral group (s-2-methyl-butyl), 4-[2-(methacryloyloxy)ethyloxy]-4'-(s-2-methyl-1-butyloxycarbonyl) azobenzene (M1) was synthesized. Polymer (PM1) possessing optical phase conjugated response was obtained by homopolymerization of the optically active monomer (M1) using free radical polymerization. The polymer was very soluble in common solvents and good optical quality films could be easily fabricated by spin coating. The optical phase conjugated responses of the polymer PM1 were measured by degenerate four-wave mixing (DFWM). In comparison with polymer containing no chiral group, it was found from the preliminary measurement of photoisomeric change that optical phase conjugated response of the PM1 in the long-range order hexagonal symmetry microstructure could be easily controlled by choosing the appropriate polarization direction of the irradiating beams (514.5 nm) and the irradiating number, presumably due to the chiral group in the PM1 molecular structure. For the case of the polymer investigated here, a chiral group side chain was introduced to increase optical phase conjugated response intensity with different polarization directions of the irradiating beams, which aims originally at searching for a new photoactive material.

  16. 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...

  17. Remarkable enhancement of the photoreactivity of a polyfluoroalkyl azobenzene derivative in an organic-inorganic nano-layered microenvironment.

    Science.gov (United States)

    Ramakrishnan, Vivek; Yamamoto, Daisuke; Sasamoto, Shin; Shimada, Tetsuya; Nabetani, Yu; Tachibana, Hiroshi; Inoue, Haruo

    2014-11-21

    Organic-inorganic hybrids composed of polyfluoroalkyl azobenzene surfactant (abbreviated as C3F-Azo-C6H) and inorganic layered compounds are able to undergo reversible three-dimensional morphology changes such as interlayer space changes and nanosheet sliding in a giant scale due to reversible trans-cis isomerization of the azobenzene moiety upon photo-irradiation. In this paper, we have systematically studied the relationship between the layered hybrid microstructures of C3F-Azo-C6H-clay and their photoreactivity for understanding the mechanism of the photo-induced morphology change. The photoreactivity was found to be very much affected by the surrounding microenvironments. As compared with it in solution, the cis-trans photo-isomerization in C3F-Azo-C6H-clay nano-layered film was substantially enhanced with the quantum yield exceeding unity (Φ = 1.9), while the trans-cis isomerization was rather retarded. The corresponding hydrocarbon analogue of the azobenzene surfactant (C3H-Azo-C6H) did not show such an enhancement. The enhancement was discussed in terms of a cooperative effect among adjacent azobenzene moieties along with polyfluoroalkyl chains and the inorganic clay nanosheet to prevent a dissipation of the excess energy being liberated during the photo-isomerization within the nano-layered microenvironment.

  18. 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

  19. 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

    We show far what is believed to he the first time that it is possible tu generate 10,000 rapid write, read, and erase cycles optically in an azobenzene sidechain liquid-crystalline polyester. We do this by exposing the film alternately to visible light from an argon laser at 488 nm and ultraviolet...

  20. 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...

  1. 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...

  2. 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.

  3. 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

  4. 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.

  5. Preparation of mesoporous SiO2@azobenzene-COOH chemoselective nanoprobes for comprehensive mapping of amino metabolites in human serum.

    Science.gov (United States)

    Li, Hua; Qin, Qian; Qiao, Lizhen; Shi, Xianzhe; Xu, Guowang

    2015-06-30

    A novel type of mesoporous SiO2@H4/D4 tagged azobenzene-COOH chemoselective nanoprobe was developed for comprehensive mapping of amino metabolites in complex biological samples with high specificity and sensitivity.

  6. 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

  7. 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

  8. 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

  9. 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.

  10. SYNTHESIS AND PROPERTIES OF A NEW AZOBENZENE SIDE-CHAIN POLYMER CONTAINING A TEMPO RADICAL

    Institute of Scientific and Technical Information of China (English)

    Yong Zhang; Ze-da Xu; Xing-he Fan; Xiao-fang Chen; Xin-hua Wan; Qi-feng Zhou

    2002-01-01

    To allow anisotropies of optical properties in a magnetic field, nitroxide radical is introduced into the ortho-position of the phenylene ring in the side chain. A new azobenzene side-chain polymer (TEMPO-PAZ) containing TEMPOradical was synthesized. The polymer has a good solubility in organic solvents. The ESR spectrum of the polymer indicatedthree absorption lines characteristic of TEMPO radical. The optical phase conjugated responses (I4) of the polymer filmswere investigated by degenerate four-wave mixing (DFWM). The experimental results showed that optical phase conjugatedresponse of the TEMPO-PAZ could be easily controlled by choosing the appropriate direction of magnetic field presumablydue to the nitroxide radical in the TEMPO-PAZ molecular structure. For the polymer investigated here, the nitroxide radicalwas introduced to increase optical phase conjugated response intensity in a magnetic field, aiming originally at searching fora new photo-active organic magnetic multifunctional materials.

  11. SYNTHESIS AND CHARACTERIZATION OF POLYMERS BEARING AZOBENZENE AND CARBAZOLE GROUPS VIA POST-AZO-COUPLING REACTION

    Institute of Scientific and Technical Information of China (English)

    Jun Shi; Zhi-wei Jiang; Li Zhang; Shao-kui Cao

    2005-01-01

    A series of polymers bearing azobenzene and carbazole groups for photorefractive purpose were prepared via post-azo-coupling reaction. The successful reaction was identified by spectroscopic analysis and gel permeation chromatography. This approach is more facile compared with the direct polymerization of corresponding functional monomer. The polymers prepared have weight average molecular weight of higher than 1.5 × 104 and are easily soluble in common organic solvents like chloroform and tetrahydrofuran, polymer films with high optical quality could be easily fabricated through solution casting. Glass transition temperature (Tg) of the polymers ranges from 60℃ to 182℃, depending on the alkylene spacer length between the functional side group and the polymer backbone, and the polymers are relatively stable under 300℃.

  12. 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.

  13. 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

  14. 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 w...... is kept in darkness. Red light illumination of the erased film increases the recovered efficiency value and the recovery rate....... 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...

  15. Influence of UV irradiation on the blue and red light photoinduced processes in azobenzene polyesters

    DEFF Research Database (Denmark)

    Rodríguez, F.J.; Sánchez, C.; Villacampa, B.;

    2004-01-01

    Birefringence induced in a series of liquid crystalline side-chain azobenzene polyesters with different substituent groups was investigated under irradiation with 488 and 633 nm linearly polarized lights. Two different initial conditions have been used: the effect of a previous irradiation with UV...... light that yields the films into the isotropic state at room temperature (RT) was compared with the quenching from temperatures above the isotropic transition temperature Ti. UV–visible spectra of the thermally quenched films show the presence of aggregates when measured at RT. We have found that UV...... light irradiation creates a high concentration of cis isomers and breaks the aggregates, but they are formed again after a few days in dark at RT. Orientation of the chromophores perpendicular to the polarization of the 488 nm light and parallel to the polarization of the 633 nm light was confirmed...

  16. Zitongxi Block

    Institute of Scientific and Technical Information of China (English)

    1996-01-01

    @@ Zitongxi Block (Western Zitong Block), is located in Zitong County, northwest of Sichuan Province (as shown on Fig. 8 ). Geologically. it is situated in the Zitong Depression, southwest of the middle Longmenshan faulted and folded belt, covering an area of 1 830 km2. Transportation is very convenient. A crisscross network of highways run through the block and the Baocheng railway is nearby. The climate is moderate. Most area belongs to hilly land with the elevation of 500-600 m.The Tongjiang River runs across the area.

  17. 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(...

  18. 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

  19. 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)

  20. 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.

  1. 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...

  2. Large work function shift of gold induced by a novel perfluorinated azobenzene-based self-assembled monolayer.

    Science.gov (United States)

    Crivillers, Núria; Osella, Silvio; Van Dyck, Colin; Lazzerini, Giovanni M; Cornil, David; Liscio, Andrea; Di Stasio, Francesco; Mian, Shabbir; Fenwick, Oliver; Reinders, Federica; Neuburger, Markus; Treossi, Emanuele; Mayor, Marcel; Palermo, Vincenzo; Cacialli, Franco; Cornil, Jérôme; Samorì, Paolo

    2013-01-18

    Tune it with light! Self-assembled monolayers on gold based on a chemisorbed novel azobenzene derivative with a perfluorinated terminal phenyl ring are prepared. The modified substrate shows a significant work function increase compared to the bare metal. The photo-conversion between trans and cis isomers chemisorbed on the surface shows great perspectives for being an accessible route to tune the gold properties by means of light.

  3. 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

  4. 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

  5. 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

  6. 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 ...

  7. 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 ...

  8. Thick methacrylate sections devoid of lost caps simplify stereological quantifications based on the optical fractionator design

    DEFF Research Database (Denmark)

    Andersen, Stine Hasselholt; Lykkesfeldt, Jens; Larsen, Jytte Overgaard

    2015-01-01

    and/or optical limitations. Restricting the disector within the section thickness potentially introduces bias in two ways. Firstly, the need to measure section thickness in order to obtain the disector height/section thickness fraction is challenging since both microcator measurements, microtome block...... advance, and measurements on re-embedded sections are potentially biased. Secondly, disector placement is not uniform random within the section thickness resulting in a bias in most sections with inhomogeneous cell distribution along the z-axis. Re-embedded 2-hydroxyethylmethacrylate (hereafter...... 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. Huhe Block

    Institute of Scientific and Technical Information of China (English)

    1996-01-01

    @@ Huhe Block is located in the mid-west part of Inner Mogolia Autonomous Region, covering an area of 15 079km2, in the range of 109°40'-112°00'E and 39°23()-40°40'N. Topographically. the Fengzhen hill is to the east, the Yinshan Mounts is to the north, the Hetao Plain and Ordos Plateau are respectively in its west and south.The Yellow River flows across this block. The elevation is 1 000 m in the flat area and in the range of 1 000-1 300m. in the plateau area, good for the development of agriculture and industry as well as husbandry. It belongs to inland plateau climate with annually averaged temperature of 8℃, the minimum being -12℃ in winter and the maximum 22℃ in summer.

  10. Degree of conversion and leached monomers of urethane dimethacrylate-hydroxypropyl methacrylate-based dental resin systems.

    Science.gov (United States)

    Zhang, Meng; Puska, Mervi A; Botelho, Michael G; Säilynoja, Eija S; Matinlinna, Jukka P

    2016-01-01

    The degree of conversion (DC) and monomer leaching of three experimental urethane dimethacrylate (UEDMA)-hydroxypropyl methacrylate (HPMA)-based resin systems were studied. Three experimental resins (E1: 70.6 wt% UEDMA + 27.4 wt% HPMA, E2: 80.6 wt% UEDMA + 17.4 wt% HPMA, E3: 90.6 wt% UEDMA + 7.4 wt% HPMA) and one control resin [C: 70.6 wt% bis-phenol A glycidyl methacrylate (bis-GMA) + 27.4 wt% methyl methacrylate (MMA)] were prepared. For the DC test, cylindrical specimens [1.5 mm (h) × 6 mm (d)] were scanned with an ATR-FTIR instrument before and after light-curing (n = 5). For the monomer leaching test, block-shaped specimens [5.67 mm (l) × 2.00 mm (w) × 2.00 mm (h)] were light-cured (n = 6), stored in a 75% ethanol:water solution for 3 days, and then analyzed with HPLC. The UEDMA-HPMA-based experimental groups showed higher DC (62-78%) than the bis-GMA-MMA-based control group (58-66%), and the DC decreased as the UEDMA content increased (P < 0.05). Amongst the four groups, E3 exhibited the lowest leaching of both mono methacrylate (0.1% HPMA) and dimethacrylate (<0.043% UEDMA) monomers after 30 or 40 s of curing. The UEDMA-HPMA-based resins, therefore, exhibited higher DC and less monomer leaching compared to the bis-GMA-MMA-based resin. (J Oral Sci 58, 15-22, 2016).

  11. 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.

  12. 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.

  13. 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.

  14. 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).

  15. 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.

  16. Collision induced dissociation study of azobenzene and its derivatives: computational and experimental results

    Science.gov (United States)

    Rezaee, Mohammadreza; Compton, Robert

    2015-03-01

    Experimental and computational investigation have been performed in order to study the bond dissociation energy of azobenzene and its derivatives using collision induced dissociation method as well as other energy and structural characteristics. The results have been verified by comparing with results obtained from computational quantum chemistry. We used different density functional methods as well as the Möller-Plesset perturbation theory and the coupled cluster methods to explore geometric, electronic and the spectral properties of the sample molecules. Geometries were calculated and optimized using the 6-311 + + G(2d,2p) basis set and the B3LYP level of theory and these optimized structures have been subjected to the frequency calculations to obtain thermochemical properties by means of different density functional, Möller-Plesset, and coupled cluster theories to obtain a high accuracy estimation of the bond dissociation energy value. The results from experiments and the results obtained from computational thermochemistry are in close agreement. Physics and Astronomy Department

  17. Photochromic molecular gyroscope with solid state rotational states determined by an azobenzene bridge.

    Science.gov (United States)

    Commins, Patrick; Garcia-Garibay, Miguel A

    2014-02-21

    We describe the synthesis, characterization, photochemical isomerization, and rotational dynamics of a crystalline molecular gyroscope containing an azobenzene bridge (trans-2) that spans from one end of the stator to other, with the intention of exploring its function as a molecular brake. While single crystal X-ray diffraction analysis of a photochemically inactive dichloromethane solvate was used to confirm the molecular and packing structures of trans-2, a nanocrystalline pseudopolymorph was shown to be photoactive, and it was analyzed by powder X-ray diffraction (PXRD), scanning electron microscopy, and variable temperature solid state (2)H NMR before and after photoisomerization. It was shown that the nanocrystalline suspension irradiated with λ = 340 nm reaches a photostationary state with 34% of cis-isomer, as compared to that observed in solution where the corresponding value is 74%. Line shape analysis of solid state (2)H NMR spectra of a phenylene-d4 isotopologue, obtained as a function of temperature, indicated that rotation in crystals of the trans-2 isomer, with a mean activation energy of 4.6 ± 0.6 kcal/mol and a pre-exponential factor exp(29.4 ± 1.7), is ten times faster than that of samples containing the cis-2 isomer, which has a higher mean activation energy of 5.1 ± 0.6 kcal/mol and a lower pre-exponential factor of exp(27.9 ± 1.3).

  18. 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

  19. Application of peptide nucleic acids containing azobenzene self-assembled electrochemical biosensors in detecting DNA sequences

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Hybridization of peptide nucleic acids probe containing azobenzene (NH2-TNT4, N-PNAs) with DNA was performed by covalently immobilizing of NH2-TNT4 in sequence on the 3-mercaptopropionic acid self-assembled monolayer modified gold electrode with the helps of N-(3-dimethylaminopropy1)-N’-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS), and the hybrid was coded as N-PNAs/DNA. Using [Fe(CN)6]4-/3- (1:1) as the electrochemical indicator, the electrochemical properties of the N-PNAs self-assembled monolayer (N-PNAs-SAMs) and N-PNAs/DNA hybridization system under the conditions of before and after UV light irradiation were characterized with cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectra (EIS). Results showed that the redox currents decreased with the increase of irradiation time, suggesting that the ability of the charge transfer on the electrode surface was weakened and the conformation of hybrid system had been changed, and the control of PNAs/DNA hybridization could be realized by UV light irradiation.

  20. Photoinduced formation of an azobenzene-based CD-active supramolecular cyclic dimer.

    Science.gov (United States)

    Sogawa, Hiromitsu; Terada, Kayo; Miyagi, Yu; Shiotsuki, Masashi; Inai, Yoshihito; Masuda, Toshio; Sanda, Fumio

    2015-04-27

    A series of new photo-responsive amino acid-derived azobenzenedicarboxylic acid derivatives (S)-1 a-e were synthesized. Compound (S)-1 a in the trans form exhibited no circular dichroism (CD) signal in DMF under ambient conditions, whereas intense Cotton effects were observed upon UV irradiation, indicating the formation of a chiral supramolecular structure in the cis form. The CD signals disappeared when trifluoroacetic acid (TFA) was added to the solution. The ester counterpart [(S)-1 a'] showed no CD signal. Hydrogen bonding between the carboxy groups seemed necessary for constructing the supramolecular structure. The kinetic studies of cis to trans isomerization of (S)-1 a demonstrated that the formation of a chiral supramolecule enhances the stability of the cis-azobenzene structure. The ESI mass spectrum of stilbenedicarboxylic acid (S)-4, an analogue of (S)-1 b, confirmed the formation of a dimer. A theoretical CD study revealed that (S)-1 a in the cis form should be present as a cyclic chiral dimer.

  1. 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.

  2. Two-photon brightness of azobenzene photoswitches designed for glutamate receptor optogenetics.

    Science.gov (United States)

    Carroll, Elizabeth C; Berlin, Shai; Levitz, Joshua; Kienzler, Michael A; Yuan, Zhe; Madsen, Dorte; Larsen, Delmar S; Isacoff, Ehud Y

    2015-02-17

    Mammalian neurotransmitter-gated receptors can be conjugated to photoswitchable tethered ligands (PTLs) to enable photoactivation, or photoantagonism, while preserving normal function at neuronal synapses. "MAG" PTLs for ionotropic and metabotropic glutamate receptors (GluRs) are based on an azobenzene photoswitch that is optimally switched into the liganding state by blue or near-UV light, wavelengths that penetrate poorly into the brain. To facilitate deep-tissue photoactivation with near-infrared light, we measured the efficacy of two-photon (2P) excitation for two MAG molecules using nonlinear spectroscopy. Based on quantitative characterization, we find a recently designed second generation PTL, L-MAG0460, to have a favorable 2P absorbance peak at 850 nm, enabling efficient 2P activation of the GluK2 kainate receptor, LiGluR. We also achieve 2P photoactivation of a metabotropic receptor, LimGluR3, with a new mGluR-specific PTL, D-MAG0460. 2P photoswitching is efficiently achieved using digital holography to shape illumination over single somata of cultured neurons. Simultaneous Ca(2+)-imaging reports on 2P photoswitching in multiple cells with high temporal resolution. The combination of electrophysiology or Ca(2+) imaging with 2P activation by optical wavefront shaping should make second generation PTL-controlled receptors suitable for studies of intact neural circuits.

  3. 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)

  4. Genotoxicity of a variety of azobenzene and aminoazobenzene compounds in the hepatocyte/DNA repair test and the Salmonella/mutagenicity test.

    Science.gov (United States)

    Mori, H; Mori, Y; Sugie, S; Yoshimi, N; Takahashi, M; Ni-i, H; Yamazaki, H; Toyoshi, K; Williams, G M

    1986-04-01

    Genotoxicity of 39 azo dye compounds of azobenzenes, aminoazobenzenes, and diaminoazobenzenes was examined in the hepatocyte primary culture/DNA repair test. Azobenzene (AzB) and 3,3'- or 4,4'-substituted azobenzenes such as (CH3)2AzB, (CH2OH)2AzB, (CH2OCOCH3)2AzB, and (CH2Cl)2AzB did not generate DNA repair, indicating lack of genotoxicity of these compounds. In contrast, all of 24 aminoazobenzenes, including those of unknown carcinogenicity, i.e., 3'-methyl-4-aminoazobenzene, 3'-CH2OH-aminoazobenzene, 3'-hydroxymethyl-N-methyl-4-aminoazobenzene, 3'-COOH-methylaminoazobenzene, 4'-formyl-N,N-dimethyl-4-aminoazobenzene, 3'-CH2Cl-dimethylaminoazobenzene, 4'-CH2Cl-dimethylaminoazobenzene, and 2'-, 3'-, or 4'-CH2OCOCH3-dimethylaminoazobenzene, elicited DNA repair synthesis. A positive DNA repair response was obtained for the 3 of 6 tested diaminoazobenzenes, i.e., N'-acetyl-N'-methyl-4-amino-dimethylaminoazobenzene, N'-acetyl-N'-methyl-4-amino-methylaminoazobenzene, and N'-acetyl-N'-methyl-4-amino-N-acetyl-methylaminoazobenzene, which are known to be carcinogenic. These results indicate that the amino group is functional for the expression of genotoxicity of azobenzene compounds. Twenty-one azobenzenes of these 3 classes were also examined for their mutagenicity in the Salmonella/mutagenicity assay. These results were almost identical with those of the DNA repair test except for several azo dyes such as AzB and 4,4'-(CH2Oacetyl)2AzB of the azobenzenes and N'-acetyl-4-amino-dimethylaminoazobenzene and N'-acetyl-N-methyl-4-amino-N-acetyl methylaminoazobenzene of the diaminoazobenzenes.

  5. 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.

  6. Allergic contact dermatitis to methacrylates in ECG electrode dots.

    Science.gov (United States)

    Lyons, Georgina; Nixon, Rosemary

    2013-02-01

    Acrylates are used widely in acrylic nails, dental restorative materials, paint, varnish, printing ink, adhesives, glue, orthopaedic prostheses, bone cement and diathermy pads. This is the first case of allergic contact dermatitis to methacrylates in electrocardiogram electrode dots reported in the literature.

  7. 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)

  8. Stereocomplex Formation of Atactic Poly(methyl methacrylate)

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Stereocomplexes formed in atactic poly(methyl methacrylate) (a-PMMA) films cast form different solvents were studied by means of Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC). The growth of stereocomplex was a function of annealing temperature and annealing time, respectively.

  9. Fictitious crack modelling of polymethyl methacrylate porous material

    NARCIS (Netherlands)

    Jimenez Pique, E.; Dortmans, L.J.M.G.; With, G. de

    2002-01-01

    Fracture tests were performed on a granular polymethyl methacrylate porous material used as a mould for white were castings. Two types of sample geometry (single-edge notch beam and wedge opening load) and two types of environment (dry at room temperature and in water at 45°C) were used and the forc

  10. Cytotoxicity evaluation of methacrylate- and silorane-based composite resins

    Directory of Open Access Journals (Sweden)

    Gulsah Goktolga Akin

    2012-10-01

    Full Text Available

    Objectives: The objective of this study was to investigate and compare the cytotoxic effects of four composite resin materials with different content.

    Material and Methods: Two traditional methacrylate-based (Clearfil AP-X, RefleXions, as well as a self-adhering methacrylate-based (Vertise Flow and a silorane-based (Filtek Silorane composite resin were tested in the experiment. Ten cylindrical specimens were made of each material, using a mould (2mm. thick and 8 mm. in diameter. An agar diffusion method was employed, and cytotoxicity rankings were determined using lysis index scores. For statistical analysis, Kruskal-Wallis and Mann-Whitney U-tests were used.

    Results: Amongst the composite resins, the silorane-based composite was found to be less cytotoxic than the methacrylate-based composite resins, which all had the same cytotoxicity ranking.

    Conclusions: The silorane-based composite resin was considered more biocompatible than the methacrylate-based composite resins.

  11. 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.

  12. 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...

  13. 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

  14. 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...

  15. Polymerization contraction and conversion of light-curing BisGMA-based methacrylate resins.

    Science.gov (United States)

    Venhoven, B A; de Gee, A J; Davidson, C L

    1993-09-01

    The aim of this study was to investigate the polymerization contraction and the conversion of light-curing methacrylate resins based on bisphenol-A bis(2-hydroxypropyl)methacrylate (BisGMA) diluted with triethylene glycol dimethyacrylate (TEGDMA), methyl methacrylate (MMA), hydroxypropyl methacrylate (HPMA) or (+/-)-2-ethylhexyl methacrylate (EHMA). The contraction measurements were carried out with a linometer, a simple device to determine true linear polymerization contraction of liquid monomers at ambient temperature. The contraction increased with the amount of diluting monomer. The estimated conversion of the BisGMA-TEGDMA, calculated using the contraction, is consistent with literature values. The BisGMA-HPMA mixtures showed high conversions at moderate contraction.

  16. 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

  17. 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...

  18. 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

  19. 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.

  20. Through-space (19)F-(19)F spin-spin coupling in ortho-fluoro Z-azobenzene.

    Science.gov (United States)

    Rastogi, Shiva K; Rogers, Robert A; Shi, Justin; Brown, Christopher T; Salinas, Cindy; Martin, Katherine M; Armitage, Jacob; Dorsey, Christopher; Chun, Gao; Rinaldi, Peter; Brittain, William J

    2016-02-01

    We report through-space (TS) (19)F-(19)F coupling for ortho-fluoro-substituted Z-azobenzenes. The magnitude of the TS-coupling constant ((TS) JFF ) ranged from 2.2-5.9 Hz. Using empirical formulas reported in the literature, these coupling constants correspond to non-bonded F-F distances (dFF) of 3.0-3.5 Å. These non-bonded distances are significantly smaller than those determined by X-ray crystallography or density functional theory, which argues that simple models of (19)F-(19)F TS spin-spin coupling solely based dFF are not applicable. (1)H, (13)C and (19)F data are reported for both the E and Z isomers of ten fluorinated azobenzenes. Density functional theory [B3YLP/6-311++G(d,p)] was used to calculate (19) F chemical shifts, and the calculated values deviated 0.3-10.0 ppm compared with experimental values.

  1. Dethreading of a Photoactive Azobenzene-Containing Molecular Axle from a Crown Ether Ring: A Computational Investigation.

    Science.gov (United States)

    Tabacchi, Gloria; Silvi, Serena; Venturi, Margherita; Credi, Alberto; Fois, Ettore

    2016-06-17

    Pseudorotaxanes formed by a dibenzo[24]crown-8 ring (R) and a dialkylammonium axle bearing either two E- or two Z-azobenzene units (EE-A or ZZ-A) revealed useful for the construction of light-powered molecular machines and motors, as they provide the opportunity of photocontrolling self-assembly/disassembly processes. The potential energies profiles for the dethreading of these complexes have been investigated by adopting a combination of first-principles molecular dynamics, metadynamics and quantum-chemical geometry optimization approaches. While the dethreading of the EE-A axle is associated with a monotonic energy increase, for that of the ZZ-A axle a transition state and an intermediate structure, in which the components are still threaded together, are found. The rate determining step for the dethreading of the ZZ axle has a higher energy barrier than that of the EE axle, in agreement with the experimental kinetic data. Moreover, the results suggest that the elliptic shape of the ring cavity is important for discriminating between the E and Z terminal azobenzene during dethreading.

  2. Properties of mixed-crystalline organic material prepared by zone levelling IV. Melting properties and excess enthalpies of (trans-azobenzene + trans-stilbene)

    NARCIS (Netherlands)

    Bouwstra, J.A.; Leeuw, V.V. de; Miltenburg, J.C.

    1985-01-01

    Homogeneous mixed crystals of (trans-azobenzene + trans-stilbene) were prepared. Molar heat capacities of the pure substances and the mixed crystals were determined at temperatures from 300 to 400 K. The melting temperatures and molar enthalpies of fusion were measured for trans-stilbene and trans-a

  3. Micro- and nanophase separations in hierarchical self-assembly of strongly amphiphilic block copolymer-based ionic supramolecules

    DEFF Research Database (Denmark)

    Ayoubi, Mehran Asad; Zhu, Kaizheng; Nyström, Bo;

    2013-01-01

    block), a class of ionic supramolecules are successfully synthesized whose molecular architecture consists of a poly(styrene) PS block (Linear block) covalently connected to a strongly amphiphilic comb-like block (AmphComb block), i.e. Linear-b-AmphComb. In the melt state, these ionic supramolecules can......By a selective complexation between different alkyltrimethylammonium amphiphiles (C8, C12 and C16) and three different diblock copolymer systems of poly(styrene)-b-poly(methacrylic acid) at various grafting densities X (X = number of alkyl chains per acidic group of the poly(methacrylic acid) PMAA...... supramolecules, based on complexation between a homopolymer of PMAA and the various alkyltrimethylammonium amphiphiles, were prepared, which nanophase separated into S (C8) or C (C12 and C16) domains....

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. Swelling behavior of poly (2-hydroxyethyl methacrylate copolymer gels

    Directory of Open Access Journals (Sweden)

    Sari S.M. Chabane

    2013-09-01

    Full Text Available Hydrogels based on 2-hydroxyethyl methacrylate/dimethyl-aminoethyl methacrylate copolymers were prepared by gamma radiation-inducedco-polymerization at low temperature (−78°C. The swelling behavior of hydrogels was studied by immersion of the polymer discs in buffered solutions at pH from 2 to 10. The hydration process was followed gravimetrically by measuring the water uptake of the discs as a function of time. The results obtained have shown that the swelling behavior is reversible and depends on the polymer nature. Moreover, polymeric discs exhibited a good stability after repeating cycles of hydration in different buffer solutions. Scanning electron microscopy analysis reveals that hydrogel porosity can be controlled.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. Langmuir-Blodgett mono- and multilayers of preformed poly(octadecyl methacrylate)s, 2. Structural studies by IR spectroscopy and small-angle X-ray scattering

    NARCIS (Netherlands)

    Arndt, Thomas; Schouten, Arend Jan; Schmidt, Günther F.; Wegner, Gerhard

    1991-01-01

    Langmuir-Blodgett (LB) mono- and multilayers of preformed atactic and isotactic poly(octadecyl methacrylate)s were studied on gold surfaces and silicon wafers. The average orientation of the carbonyl bond of the ester group was found to be about 50° with respect to the normal to the substrate, and t

  14. 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

  15. 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...

  16. 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.

  17. 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.

  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. 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.

  20. 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.

  1. Reflection Band Control of Inverse Opal Film with Photoresponse Properties of Push-Pull Type Azobenzene LC Polymers

    Directory of Open Access Journals (Sweden)

    Takahiro Shiozawa

    2008-07-01

    Full Text Available DcAz2Mc and DR1Mc molecules having push-pull type of azobenzene groups are synthesized, and their photo-orientational behaviors are investigated in the polymer system. In order to understand the relationship between a molecular structure and its physical properties, electronic structure calculation is computationally carried out. Regarding to their photo response properties, the copolymers of poly(DcAz2Mc-co-M6PBMe and poly(DR1Mc-co-M6PBMe are infiltrated into inverse opal films, and Bragg reflection shifts are observed under photostimuli. When the linearly polarized light is irradiated, Bragg reflection bands are shifted to the longer wavelength region as reflective index increases.

  2. 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.

  3. 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.

  4. 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).

  5. Deterioration of polymethyl methacrylate dentures in the oral cavity.

    Science.gov (United States)

    Matsuo, Hiroshi; Suenaga, Hanako; Takahashi, Masatoshi; Suzuki, Osamu; Sasaki, Keiichi; Takahashi, Nobuhiro

    2015-01-01

    Polymethyl methacrylate (PMMA)-made prostheses used in the oral cavity were evaluated by multimodal assessment in order to elucidate the biodeterioration of PMMA. In used dentures (UD), the micro-Vickers hardness of the polished denture surface and denture basal surface was lower than that of the torn surface (pPMMA deteriorated during long-term use in the oral cavity in terms of hardness and volatile content with component alteration, and suggests the involvement of biodeterioration, possibly due to saliva and oral microbiota.

  6. 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)

  7. 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.

  8. Jumpwise deformation of polymethyl methacrylate in the microplasticity region

    Science.gov (United States)

    Shpeizman, V. V.; Yakushev, P. N.; Mukhina, Zh. V.; Kuznetsov, E. V.; Smolyanskii, A. S.

    2013-05-01

    The deformation rate with a step of 325 nm has been measured under uniaxial compression at the initial stage of creep and shape recovery of a polymethyl methacrylate (PMMA) sample after unloading. The effect of low γ-ray doses and magnetic fields on the deformation has been studied. It has been shown that a weak pre-exposure of the PMMA sample structure to radiation and magnetic fields can cause a slight hardening in the microplasticity region. The deformation jump sizes have been determined on micro- and nanoscales. The effect of irradiation and magnetic fields manifests itself as redistributed contributions of various jumps to the deformation.

  9. 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

  10. 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.

  11. 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

  12. 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.

  13. A New Biindenylidenedione Compound with Two Azobenzene Units:Synthesis and Photochromic Behavior Both in Solution and in the Solid State

    Institute of Scientific and Technical Information of China (English)

    LIU Juyan; HAN Jie; WANG Juanyu; PANG Meili; MENG Jiben

    2009-01-01

    A new photochromic biindenylidenedione compound bearing two azobenzene units was synthesized and characterized by means of 1H NMR,13C NMR,ESI-MS and elemental analysis.The photochromic and photo-induced radical properties were investigated by means of UV-Vis and electron spin resonance spectroscopy,respectively.The results showed that the title compound exhibited photochromic behavior with good fatigue resistances both in solution and in the solid state.

  14. 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.

  15. 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.

  16. 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

  17. 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...

  18. Shrinkage kinetics of a methacrylate- and a silorane-based resin composite: effect on marginal integrity

    NARCIS (Netherlands)

    L. Gregor; T. Bortolotto; A.J. Feilzer; I. Krejci

    2013-01-01

    Purpose: To evaluate the relation between the linear displacement (LD), shrinkage force (SF) and marginal adaptation of a methacrylate- and a silorane-based composite. Materials and Methods: The LD and SF of 8 samples made of Filtek Supreme XT (methacrylate-based composite) and Filtek Silorane (silo

  19. 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

  20. Creative Construction: Unit Blocks.

    Science.gov (United States)

    Texas Child Care, 1999

    1999-01-01

    Describes the use of unit blocks with young children in early childhood education (ECE) settings to expand all areas of the curriculum. Discusses the origin of blocks in ECE programs, presents developmental stages of block play, describes children's building styles, and makes recommendations for getting started in block play for children of…

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Structural characterization of a poly(methacrylic acid)-poly(methyl methacrylate) copolymer by nuclear magnetic resonance and mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Giordanengo, Remi [Universites Aix-Marseille I, II et III - CNRS, UMR 6264: Laboratoire Chimie Provence, Spectrometries Appliquees a la Chimie Structurale, F-13397 Marseille (France); Viel, Stephane [Aix-Marseille Universite - CNRS, UMR 6263: Institut des Sciences Moleculaires de Marseille, Chimiometrie et Spectrometries, F-13397 Marseille (France); Hidalgo, Manuel; Allard-Breton, Beatrice [ARKEMA, Centre de Recherche Rhone Alpes, Rue Henri Moissan, F-69493 Pierre-Benite (France); Thevand, Andre [Universites Aix-Marseille I, II et III - CNRS, UMR 6264: Laboratoire Chimie Provence, Spectrometries Appliquees a la Chimie Structurale, F-13397 Marseille (France); Charles, Laurence, E-mail: laurence.charles@univ-provence.fr [Universites Aix-Marseille I, II et III - CNRS, UMR 6264: Laboratoire Chimie Provence, Spectrometries Appliquees a la Chimie Structurale, F-13397 Marseille (France)

    2009-11-03

    Mass spectrometry (MS) and nuclear magnetic resonance (NMR) have been combined to achieve the complete microstructural characterization of a poly(methacrylic acid)-poly(methyl methacrylate) (PMAA-PMMA) copolymer synthesized by nitroxide-mediated polymerization. Various PMAA-PMMA species could be identified which mainly differ in terms of terminaisons. {sup 1}H and {sup 13}C NMR experiments revealed the structure of the end-groups as well as the proportion of each co-monomer in the copolymers. These end-group masses were further confirmed from m/z values of doubly charged copolymer anions detected in the single stage mass spectrum. In contrast, copolymer composition derived from MS data was not consistent with NMR results, obviously due to strong mass bias well known to occur during electrospray ionization of these polymeric species. Tandem mass spectrometry could reveal the random nature of the copolymer based on typical dissociation reactions, i.e., water elimination occurred from any two contiguous MAA units while MAA-MMA pairs gave rise to the loss of a methanol molecule. Polymer backbone cleavages were also observed to occur and gave low abundance fragment ions which allowed the structure of the initiating end-group to be confirmed.

  8. Adhesion of Escherichia coli on to a series of poly(methacrylates) differing in charge and hydrophobicity

    NARCIS (Netherlands)

    Harkes, G.; Feijen, J.; Dankert, J.

    1991-01-01

    The adhesion of three Escherichia coli strains on to six poly(methacrylates) differing in hydrophobicity and surface charge was measured as a function of time under laminar flow conditions. Polymers used were poly(methy) methacrylate) (PMMA), poly(hydroxyethy) methacrylate) (PHEMA) and copolymers of

  9. Light-induced reversible modification of the work function of a new perfluorinated biphenyl azobenzene chemisorbed on Au (111)

    Science.gov (United States)

    Masillamani, Appan Merari; Osella, Silvio; Liscio, Andrea; Fenwick, Oliver; Reinders, Federica; Mayor, Marcel; Palermo, Vincenzo; Cornil, Jérôme; Samorì, Paolo

    2014-07-01

    We describe the synthesis of a novel biphenyl azobenzene derivative exhibiting: (i) a protected thiol anchoring group in the α-position to readily form self-assembled monolayers (SAMs) on Au surfaces; and (ii) a terminal perfluorinated benzene ring in the ω-position to modify the surface properties. The design of this molecule ensured both an efficient in situ photoswitching between the trans and cis isomers when chemisorbed on Au(111), due to the presence of a biphenyl bridge between the thiol protected anchoring group and the azo dye, and a significant variation of the work function of the SAM in the two isomeric states, induced by the perfluorinated phenyl head group. By exploiting the light responsive nature of the chemisorbed molecules, it is possible to dynamically modify in situ the work function of the SAM-covered electrode, as demonstrated both experimentally and by quantum-chemical calculations, revealing changes in work function up to 220 meV. These findings are relevant for tuning the work function of metallic electrodes, and hence to dynamically modulate charge injection at metal-semiconductor interfaces for organic opto-electronic applications.We describe the synthesis of a novel biphenyl azobenzene derivative exhibiting: (i) a protected thiol anchoring group in the α-position to readily form self-assembled monolayers (SAMs) on Au surfaces; and (ii) a terminal perfluorinated benzene ring in the ω-position to modify the surface properties. The design of this molecule ensured both an efficient in situ photoswitching between the trans and cis isomers when chemisorbed on Au(111), due to the presence of a biphenyl bridge between the thiol protected anchoring group and the azo dye, and a significant variation of the work function of the SAM in the two isomeric states, induced by the perfluorinated phenyl head group. By exploiting the light responsive nature of the chemisorbed molecules, it is possible to dynamically modify in situ the work function of

  10. 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.

  11. Synthesis of Methacrylate Monomers with Antibacterial Effects Against S. Mutans

    Directory of Open Access Journals (Sweden)

    Jingwei He

    2011-11-01

    Full Text Available A series of polymerizable quaternary ammonium compounds were synthesized with the aim of using them as immobilized antibacterial agents in methacrylate dental composites, and their structures were characterized by FT-IR, 1H-NMR, and 13C-NMR analysis. Their antibacterial activities against the oral bacterium Streptococcus mutans were evaluated in vitro by a Minimum Inhibitory Concentration test, and the results showed that 2-dimethyl-2-hexadecyl-1-methacryloxyethyl ammonium iodide (C16 had the highest antibacterial activity against S. mutans, and 2-dimethyl-2-pentyl-1-methacryloxyethyl ammonium iodide (C5 and 2-dimethyl-2-octyl-1-methacryloxyethyl ammonium iodide (C8 did not show any inhibition.

  12. 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.

  13. Preparation and modification of itaconic anhydride–methyl methacrylate copolymers

    Directory of Open Access Journals (Sweden)

    MILOS B. MILOVANOVIC

    2007-12-01

    Full Text Available The free radical copolymerisation of itaconic anhydride and methyl methacrylate in solution was studied at 60 °C. The copolymer composition was determined by 1H-NMR spectroscopy and the obtained monomer reactivity ratios were calculated, rITA = 1.35±0.11; rMMA = 0.22±0.22 (by the Fineman–Ross method and rITA = 1.27±0.38; rMMA = 0.10±0.05 (by the Mayo–Lewis method. The synthesised copolymers were modified by reaction with di-n-butyl amine. The copolymer composition after amidation was determined by elemental analysis via the nitrogen content. Amidation of the anhydride units in the copolymers with di-n-butyl amine resulted in complete conversion to itaconamic acid.

  14. 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

  15. 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

  16. Anti-Biofouling Effect of PEG-Grafted Block Copolymer Synthesized by RAFT Polymerization.

    Science.gov (United States)

    Kim, Seon-Mi; Han, Sang Suk; Kim, A Young; Choi, Beom-Jin; Paik, Hyun-Jong; Lee, Inwon; Park, Hyun; Chun, Ho Hwan; Cho, Youngjin; Hwang, Do-Hoon

    2015-10-01

    Poly(glycidyl methadrylate-block-styrene) (PGMA-b-PS), a block copolymer consisting of glycidyl methacrylate and styrene, was synthesized via reversible addition-fragmentation chain transfer living polymerization. The synthesized PGMA-b-PS was then grafted with low-molecular-weight polyethylene glycol (PEG) via epoxy ring opening to give PGMA-g-PEG-b-PS, which was evaluated as an anti-biofouling coating material. As a preliminary test for the anti-biofouling effect, a protein adsorption experiment was performed on the synthesized block copolymer surface. The block copolymers were spin-coated onto silicon wafers, and protein adsorption experiments were carried out using fluorescein isothiocyanate conjugate-labeled bovine serum albumin. The fluorescence intensity of the protein adsorbed on the block copolymer surface was compared with that of a polystyrene film as a reference. The synthesized PGMA-g-PEG-b-PS film showed much lower fluorescence intensity than that of the PS film.

  17. 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

  18. Blocking and associability change.

    Science.gov (United States)

    Jones, Peter M; Haselgrove, Mark

    2013-07-01

    Blocking of learning about a conditioned stimulus (the "blocked" cue) occurs when it is trained alongside an additional stimulus (the "blocking" cue) that has been previously presented with the outcome. A number of theories (e.g., N. J. Mackintosh. 1975a. A Theory of Attention: Variations in the Associability of Stimuli With Reinforcement. Psychological Review, 82, 276-298; J. M. Pearce & G. Hall. 1980. A Model for Pavlovian Learning: Variation in the Effectiveness of Conditioned But Not Unconditioned Stimuli. Psychological Review, 87, 532-552) account for this attenuation in learning by proposing that attention paid to the blocked cue is restricted. In three experiments, we examined the associability of both blocked and blocking cues. In Experiment 1, rats were trained with a blocking protocol before being given a test discrimination composed of two components; one of these components required the use of the previously blocked cue as a discriminative stimulus, and the other component was soluble by using the blocking cue. To our surprise, the component that depended on the blocked cue was more readily solved than the component dependent on the blocking cue. The results of Experiments 2 and 3 suggest that this is due to the quantity of exposure that each stimulus received during initial training. Implications for theories of blocking, and more widely associative learning, are discussed. PMID:23668185

  19. Blocking and associability change.

    Science.gov (United States)

    Jones, Peter M; Haselgrove, Mark

    2013-07-01

    Blocking of learning about a conditioned stimulus (the "blocked" cue) occurs when it is trained alongside an additional stimulus (the "blocking" cue) that has been previously presented with the outcome. A number of theories (e.g., N. J. Mackintosh. 1975a. A Theory of Attention: Variations in the Associability of Stimuli With Reinforcement. Psychological Review, 82, 276-298; J. M. Pearce & G. Hall. 1980. A Model for Pavlovian Learning: Variation in the Effectiveness of Conditioned But Not Unconditioned Stimuli. Psychological Review, 87, 532-552) account for this attenuation in learning by proposing that attention paid to the blocked cue is restricted. In three experiments, we examined the associability of both blocked and blocking cues. In Experiment 1, rats were trained with a blocking protocol before being given a test discrimination composed of two components; one of these components required the use of the previously blocked cue as a discriminative stimulus, and the other component was soluble by using the blocking cue. To our surprise, the component that depended on the blocked cue was more readily solved than the component dependent on the blocking cue. The results of Experiments 2 and 3 suggest that this is due to the quantity of exposure that each stimulus received during initial training. Implications for theories of blocking, and more widely associative learning, are discussed.

  20. Photo-induced Alignment Behavior of Azobenzene-containing Polymer Films with Different Cross-linking Degree

    Institute of Scientific and Technical Information of China (English)

    Jing Shen; Jin-tang Huang; Yan-hua Luo; Qi-jin Zhang; Ke-yi Wang

    2008-01-01

    Three series of amorphous copolymers containing azobenzene groups with various substituents and certain amounts of crosslinkable acrylic groups were prepared. The cross-linked polymer films were obtained by thermal polymerization of the acrylic groups in the copolymers, during which, by controlling the time of cross-linking reaction, the films can be made with different cross-linking degree (from 0 to 32%, which was monitored by FT-IR spectra measurement). Photo-induced alignment process of the films was performed under irradiation with linearly polarized light at 442 nm, and the effect of cross-linking degree on the photo-induced alignment rate was investigated. The dynamics of the photo-induced alignment was analyzed with biexponential curve fitting. The photo-induced alignment rate and the maximum transmittance of the films decreased because of the cross-linking. Furthermore, for the cross-linked samples, it was found that their saturated value of transmittances keep constant after repeated "writing" and "erasing" cycles. The findings reveal that the cross-linking of the film can effectively restrain the phototactic mass transport of azopolymer during irradiation by polarized light. The relationship between the cross-linking degree and the photo-induced alignment behavior of azopolymer is discussed in detail.

  1. 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.

  2. 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.

  3. Assessing computationally efficient isomerization dynamics: Delta-SCF density-functional theory study of azobenzene molecular switching

    CERN Document Server

    Maurer, Reinhard J; 10.1063/1.3664305

    2012-01-01

    We present a detailed comparison of the S0, S1 (n -> \\pi*) and S2 (\\pi -> \\pi*) potential energy surfaces (PESs) of the prototypical molecular switch azobenzene as obtained by Delta-self-consistent-field (Delta-SCF) Density-Functional Theory (DFT), time-dependent DFT (TD-DFT) and approximate Coupled Cluster Singles and Doubles (RI-CC2). All three methods unanimously agree in terms of the PES topologies, which are furthermore fully consistent with existing experimental data concerning the photo-isomerization mechanism. In particular, sum-method corrected Delta-SCF and TD-DFT yield very similar results for S1 and S2, when based on the same ground-state exchange-correlation (xc) functional. While these techniques yield the correct PES topology already on the level of semi-local xc functionals, reliable absolute excitation energies as compared to RI-CC2 or experiment require an xc treatment on the level of long-range corrected hybrids. Nevertheless, particularly the robustness of Delta-SCF with respect to state c...

  4. 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.

  5. Generalized Block Failure

    DEFF Research Database (Denmark)

    Jönsson, Jeppe

    2015-01-01

    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.......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...

  6. 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

  7. Polymerization of sodium methacrylate induced by irradiation; Polimerizacion del metacrilato de sodio inducida por la irradiacion

    Energy Technology Data Exchange (ETDEWEB)

    Galvan S, A. [Instituto Nacional de Investigaciones Nucleares, Gerencia de Ciencias Basicas, A.P. 18-1027, 11801 Mexico D.F. (Mexico)

    1998-07-01

    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)

  8. 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

  9. Wireless Connection between Guide Wires and Bone Cement: Extravasated Methyl Methacrylate Mimicking a Retained Guide Wire

    Directory of Open Access Journals (Sweden)

    Kevin C. Ching

    2013-01-01

    Full Text Available We present the case of a 56-year-old double lung transplant recipient with chest pain who underwent an attempted endovascular retrieval of what was described as a retained guide wire in the azygos vein. After successfully grasping the tip, the object further migrated to the right pulmonary artery complicating the retrieval. It was realized that the “wire” was extravasated methyl methacrylate from a recent percutaneous kyphoplasty. This is believed to be the first report of attempted endovascular retrieval of extravasated methyl methacrylate in the azygos system. We include the details of this case and briefly review the current literature on the management of extravasated methyl methacrylate from vertebral augmentation procedures. Extravasated methyl methacrylate in the venous system is a common finding after vertebral augmentation procedures and any radiopaque stripe arising from a cemented vertebral body should be first described as probable cement leakage.

  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

    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.

  11. 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.

  12. 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

  13. 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...

  14. 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-...

  15. 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...

  16. Barrier layers against oxygen transmission on the basis of electron beam cured methacrylated gelatin

    Science.gov (United States)

    Scherzer, Tom

    1997-08-01

    The development of barrier layers against oxygen transmission on the basis of radiation-curable methacrylated gelatin will be reported. The electron beam cured gelatin coatings show an extremely low oxygen permeability and a high resistance against boiling water. Moreover, the methacrylated gelatins possess good adhesion characteristics. Therefore, they are suited as barrier adhesives in laminates for food packaging applications. If substrate foils from biodegradable polymers are used, the development of completely biodegradable packaging materials seems to be possible.

  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. 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.

  19. Right- and Left-Handed Helices, What is in between? Interconversion of Helical Structures of Alternating Pyridinedicarboxamide/m-(phenylazo)azobenzene Oligomers.

    Science.gov (United States)

    Tao, Peng; Parquette, Jon R; Hadad, Christopher M

    2012-12-11

    Some unnatural polymers/oligomers have been designed to adopt a well-defined, compact, three-dimensional folding capability. Azobenzene units are common linkages in these oligomer designs. Two alternating pyridinedicarboxamide/m-(phenylazo)azobenzene oligomers that can fold into both right- and left-handed helices were studied computationally in order to understand their dynamical properties. Helical structures were shown to be the global minima among the many different conformations generated from the Monte Carlo simulations, and extended conformations have higher potential energies than compact ones. To understand the interconversion process between right- and left-handed helices, replica-exchange molecular dynamic (REMD) simulations were performed on both oligomers, and with this method, both right- and left-handed helices were successfully sampled during the simulations. REMD trajectories revealed twisted conformations as intermediate structures in the interconversion pathway between the two helical forms of these azobenzene oligomers. This mechanism was observed in both oligomers in current study and occurred locally in the larger oligomer. This discovery indicates that the interconversion between helical structures with different handedness goes through a compact and partially folded structure instead of globally unfold and extended structure. This is also verified by the nudged elastic band (NEB) calculations. The temperature weighted histogram analysis method (T-WHAM) was applied on the REMD results to generate contour maps of the potential of mean force (PMF). Analysis showed that right- and left-handed helices are equally sampled in these REMD simulations. In large oligomers, both right- and left-handed helices can be adopted by different parts of the molecule simultaneously. The interconversion between two helical forms can occur in the middle of the helical structure and not necessarily at the termini of the oligomer.

  20. 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.

  1. 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

  2. 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.

  3. 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

  4. 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)

  5. 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'.

  6. 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)

  7. 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)

  8. Structures of Silk Fibers Grafted with Hexafluorobutyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The relationship between the graft yield and the effect of hexafluorobutyl methacrylate graft treatment on the structural changes of the silk fibers was studied on the basis of the results of scanning electron micrograph photographs (SEM), infrared spectroscopy (IR), Raman spectrum,wide-angle X-ray diffraction patterns (WAXD), nuclear magnetic resonance(NMR) and amion acid analysis. The results showed that the crystalline regions of grafted fibers were hardly affected and the fiber fission occurred on the cross sections of grafted fibers. The surface of fibers was covered with a high polymer film. The Raman spectrum showed there was little change in the conformation of grafted fibers which mainly remained β-sheet conformation. The IR of the grafted silk fibers showed new absorption of bands occurred which belonged to the stretching-vibrationabsorption-peak bands of VC=O and VC-F of aliphatic ester species. The CF3-,-CF2- and -CFH- structures of grafted silk macromdlecule were verified in the NMR spectrum.The amion acid analysis indicated fluoride monomers were inclined to graft with TYR,ARG and GLU of silk fibers.

  9. 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.

  10. In vivo genotoxicity assessment of acrylamide and glycidyl methacrylate.

    Science.gov (United States)

    Dobrovolsky, Vasily N; Pacheco-Martinez, M Monserrat; McDaniel, L Patrice; Pearce, Mason G; Ding, Wei

    2016-01-01

    Acrylamide (ACR) and glycidyl methacrylate (GMA) are structurally related compounds used for making polymers with various properties. Both chemicals can be present in food either as a byproduct of processing or a constituent of packaging. We performed a comprehensive evaluation of ACR and GMA genotoxicity in Fisher 344 rats using repeated gavage administrations. Clastogenicity was measured by scoring micronucleated (MN) erythrocytes from peripheral blood, DNA damage in liver, bone marrow and kidneys was measured using the Comet assay, and gene mutation was measured using the red blood cell (RBC) and reticulocyte Pig-a assay. A limited histopathology evaluation was performed in order to determine levels of cytotoxicity. Doses of up to 20 mg/kg/day of ACR and up to 250 mg/kg/day of GMA were used. ACR treatment resulted in DNA damage in the liver, but not in the bone marrow. While ACR was not a clastogen, it was a weak (equivocal) mutagen in the cells of bone marrow. GMA caused DNA damage in the cells of bone marrow, liver and kidney, and induced MN reticulocytes and Pig-a mutant RBCs in a dose-dependent manner. Collectively, our data suggest that both compounds are in vivo genotoxins, but the genotoxicity of ACR is tissue specific.

  11. Characterization of methacrylate chromatographic monoliths bearing affinity ligands.

    Science.gov (United States)

    Černigoj, Urh; Vidic, Urška; Nemec, Blaž; Gašperšič, Jernej; Vidič, Jana; Lendero Krajnc, Nika; Štrancar, Aleš; Podgornik, Aleš

    2016-09-16

    We investigated effect of immobilization procedure and monolith structure on chromatographic performance of methacrylate monoliths bearing affinity ligands. Monoliths of different pore size and various affinity ligands were prepared and characterized using physical and chromatographic methods. When testing protein A monoliths with different protein A ligand densities, a significant nonlinear effect of ligand density on dynamic binding capacity (DBC) for IgG was obtained and accurately described by Langmuir isotherm curve enabling estimation of protein A utilization as a function of ligand density. Maximal IgG binding capacity was found to be at least 12mg/mL exceeding theoretical monolayer adsorption value of 7.8mg/mL assuming hexagonal packing and IgG hydrodynamic diameter of 11nm. Observed discrepancy was explained by shrinkage of IgG during adsorption on protein A experimentally determined through calculated adsorbed IgG layer thickness of 5.4nm from pressure drop data. For monoliths with different pore size maximal immobilized densities of protein A as well as IgG dynamic capacity linearly correlates with monolith surface area indicating constant ligand utilization. Finally, IgGs toward different plasma proteins were immobilized via the hydrazide coupling chemistry to provide oriented immobilization. DBC was found to be flow independent and was increasing with the size of bound protein. Despite DBC was lower than IgG capacity to immobilized protein A, ligand utilization was higher. PMID:27554023

  12. 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.

  13. 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 ...

  14. 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...... 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....

  15. 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.

  16. 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

  17. 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…

  18. Surviving Block Scheduling.

    Science.gov (United States)

    Haley, Marjorie

    A discussion of block scheduling for second language instruction looks at the advantages and disadvantages and offers some suggestions for classroom management and course organization. It is argued that block scheduling may offer a potential solution to large classes, insufficient time for labs, too little individualized instruction; few…

  19. Azobenzene mesogens mediated preparation of SnS nanocrystals encapsulated with in-situ N-doped carbon and their enhanced electrochemical performance for lithium ion batteries application

    Science.gov (United States)

    Wang, Meng; Zhou, Yang; Duan, Junfei; Chen, Dongzhong

    2016-09-01

    In this work, azobenzene mesogen-containing tin thiolates have been synthesized, which possess ordered lamellar structures persistent to higher temperature and serve as liquid crystalline precursors. Based on the preorganized tin thiolate precursors, SnS nanocrystals encapsulated with in-situ N-doped carbon layer have been achieved through a simple solventless pyrolysis process with the azobenzene mesogenic thiolate precursor served as Sn, S, N, and C sources simultaneously. Thus prepared nanocomposite materials as anode of lithium ion batteries present a large specific capacity of 604.6 mAh·g-1 at a current density of 100 mA·g-1, keeping a high capacity retention up to 96% after 80 cycles, and display high rate capability due to the synergistic effect of well-dispersed SnS nanocrystals and N-doped carbon layer. Such encouraging results shed a light on the controlled preparation of advanced nanocomposites based on liquid crystalline metallomesogen precursors and may boost their novel intriguing applications. Project supported by the National Natural Science Foundation of China (Grant No. 21574062) and the Huaian High-Technology Research Institute of Nanjing University, China (Grant No. 2011Q1).

  20. Azobenzene mesogens mediated preparation of SnS nanocrystals encapsulated with in-situ N-doped carbon and their enhanced electrochemical performance for lithium ion batteries application

    Science.gov (United States)

    Wang, Meng; Zhou, Yang; Duan, Junfei; Chen, Dongzhong

    2016-09-01

    In this work, azobenzene mesogen-containing tin thiolates have been synthesized, which possess ordered lamellar structures persistent to higher temperature and serve as liquid crystalline precursors. Based on the preorganized tin thiolate precursors, SnS nanocrystals encapsulated with in-situ N-doped carbon layer have been achieved through a simple solventless pyrolysis process with the azobenzene mesogenic thiolate precursor served as Sn, S, N, and C sources simultaneously. Thus prepared nanocomposite materials as anode of lithium ion batteries present a large specific capacity of 604.6 mAh·g‑1 at a current density of 100 mA·g‑1, keeping a high capacity retention up to 96% after 80 cycles, and display high rate capability due to the synergistic effect of well-dispersed SnS nanocrystals and N-doped carbon layer. Such encouraging results shed a light on the controlled preparation of advanced nanocomposites based on liquid crystalline metallomesogen precursors and may boost their novel intriguing applications. Project supported by the National Natural Science Foundation of China (Grant No. 21574062) and the Huaian High-Technology Research Institute of Nanjing University, China (Grant No. 2011Q1).

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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

  9. 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

  10. 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.

  11. 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

  12. 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

  13. 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.

  14. 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...

  15. Effects of surfactants on the properties of mortar containing styrene/methacrylate superplasticizer.

    Science.gov (United States)

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

    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 order to study their effects on the properties of mortar. The properties of mortar examined included flow table, W/C ratio, setting time, water absorption, compressive strength, and combined water. The results indicate that the latex causes improvement in mortar properties compared with cosurfactants. Also polymer latex containing DBSS/POE is more effective than that containing DBSS/PVA.

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

    Directory of Open Access Journals (Sweden)

    El-Sayed Negim

    2014-01-01

    Full Text Available 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 order to study their effects on the properties of mortar. The properties of mortar examined included flow table, W/C ratio, setting time, water absorption, compressive strength, and combined water. The results indicate that the latex causes improvement in mortar properties compared with cosurfactants. Also polymer latex containing DBSS/POE is more effective than that containing DBSS/PVA.

  17. Chondrocyte Generation of Cartilage-Like Tissue Following Photoencapsulation in Methacrylated Polysaccharide Solution Blends.

    Science.gov (United States)

    Hayami, James W S; Waldman, Stephen D; Amsden, Brian G

    2016-07-01

    Chondrocyte-seeded, photo-cross-linked hydrogels prepared from solutions containing 50% mass fractions of methacrylated glycol chitosan or methacrylated hyaluronic acid (MHA) with methacrylated chondroitin sulfate (MCS) are cultured in vitro under static conditions over 35 d to assess their suitability for load-bearing soft tissue repair. The photo-cross-linked hydrogels have initial equilibrium moduli between 100 and 300 kPa, but only the MHAMCS hydrogels retain an approximately constant modulus (264 ± 5 kPa) throughout the culture period. Visually, the seeded chondrocytes in the MHAMCS hydrogels are well distributed with an apparent constant viability in culture. Multicellular aggregates are surrounded by cartilaginous matrix, which contain aggrecan and collagen II. Thus, co-cross-linked MCS and MHA hydrogels may be suited for use in an articular cartilage or nucleus pulposus repair applications. PMID:27061241

  18. 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.

  19. Free radical (co)polymerization of methyl methacrylate and styrene in room temperature ionic liquids

    Science.gov (United States)

    Zhang, Hongwei

    Conventional free radical polymerizations were carried out in a variety of room temperature ionic liquids (RTILs). Generally, methyl methacrylate (MMA) and styrene (St) were used as typical monomers to compare the polymerization behavior both in RTILs and in common volatile organic compound solvents (VOCs). In most cases, it was observed that both yields and molecular weights are enhanced in the RTIL. While we believe the "diffusion-controlled termination" mechanism makes the termination of the radical propagating chains difficult due to the highly viscous nature of RTIL, other researchers have suggested that the rapid polymerization rates are due to the high polarity of these reaction media. By employing more than a dozen RTILs with a wide range of anions and cations, we attempted to correlate the viscosity and polarity of the RTILs with the molecular weights and polymerization rates. This correlation was not successful, suggesting that other parameters may also play a role in affecting the polymerization behavior. Other kinds of polymerizations have also been attempted including nitroxide-mediated living radical polymerizations of St and MMA in 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6), and redox initiation system initiated polymerization of MMA through redox pair formed by cation of trihexyl-tetradecyl-phosphonium bis(2,4,4-trimethylpentyl) phosphinate ([H3TDP] [(PM3) 2P]) and BPO. The formation of PSt-b-PMMA by sequential monomer addition through the standard free radical polymerization mechanism, using BPO as initiator, can be realized in [BMIM]PF6 due to the insolubility of polymerized first block---PSt in [BMIM]PF6. The macroradicals wrapped inside the chain coils have prolonged lifetimes because of the diminished termination, which allow some of these radicals to initiate polymerization of MMA at room temperature to form diblock copolymer. Solvents effects on reactivity ratios for free radical statistical copolymerization have been

  20. Investigation of dairy cattle ease of movement on new methyl methacrylate resin aggregate floorings.

    Science.gov (United States)

    Franco-Gendron, N; Bergeron, R; Curilla, W; Conte, S; DeVries, T; Vasseur, E

    2016-10-01

    Freestall dairy farms commonly present issues with cattle slips and falls caused by smooth flooring and manure slurry. This study examined the effect of 4 new methyl methacrylate (MMA) resin aggregate flooring types (1-4) compared with rubber (positive) and concrete (negative control) on dairy cow (n=18) ease of movement when walking on straight and right-angled corridors. Our hypothesis was that cow ease of movement when walking on the MMA surfaces would be better than when walking on traction milled concrete, and at least as good as when walking on rubber. Cattle ease of movement was measured using kinematics, accelerometers, and visual observation of gait and associated behaviors. Stride length, swing time, stance time, and hoof height were obtained from kinematic evaluation. Acceleration and asymmetry of variance were measured with accelerometers. Locomotion score and behaviors associated with lameness, such as arch back, head bob, tracking up, step asymmetry, and reluctance to bear weight were visually observed. Stride length, swing time, stance time, and the number of steps taken were the only variables affected by flooring type. Differences between flooring types for these variables were tested using a generalized linear mixed model with cow as a random effect, week as a random block factor, and flooring type as a fixed effect. Multiple comparisons with a Scheffé adjustment were done to analyze differences among flooring types. Stride length was 0.14 m longer (better) on rubber when compared with concrete, and 0.11 and 0.17 m shorter on MMA 1 and 2 compared with rubber. On MMA 3 and 4, stride length did not differ from either rubber or concrete. Swing time was 0.04 s shorter (worse) on MMA 1 than on rubber, but did not differ from any other flooring. Stance time was 0.18 s longer (worse) on MMA 2 when compared with rubber, but it did not differ from any other treatment. The number of steps was higher on MMA 4 compared with rubber (4.57 vs. 3.95 steps), but

  1. 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

  2. Synthesis and characterization of carbon fibers functionalized with poly (glycidyl methacrylate) via atom transfer radical polymerization

    Science.gov (United States)

    Wu, Yongwei; Xiong, Lei; Qin, Xiaokang; Wang, Zhengyue; Ding, Bei; Ren, Huan; Pi, Xiaolong

    2015-07-01

    In this work, polyacrylonitrile (PAN)-based carbon fibers (CF) were chemically modified with poly (glycidyl methacrylate) (PGMA) via atom transfer radical polymerization (ATRP) to improve the interaction between the CF and polymer matrix. The FT-IR, TGA, and XPS were used to determine the chemical structure of the resulting products and the quantities of PGMA chains grafted from the CF surface. The experimental results confirm that the CF surface was functionalized and glycidyl methacrylate was graft-polymerized onto the CF, and the grafting content of polymer could reach 10.2%.

  3. Modification of polyethylene films by radiation grafting of glycidyl methacrylate and immobilization of {beta}-cyclodextrin

    Energy Technology Data Exchange (ETDEWEB)

    Nava-Ortiz, C.A.B. [Departamento de Quimica de Radiaciones y Radioquimica, Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria, Mexico DF 04510 (Mexico); Burillo, G. [Departamento de Quimica de Radiaciones y Radioquimica, Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria, Mexico DF 04510 (Mexico)], E-mail: burillo@nucleares.unam.mx; Bucio, E. [Departamento de Quimica de Radiaciones y Radioquimica, Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria, Mexico DF 04510 (Mexico); Alvarez-Lorenzo, C. [Departamento de Farmacia y Tecnologia Farmaceutica, Facultad de Farmacia, Universidad de Santiago de Compostela, 15782 Santiago de Compostela (Spain)

    2009-01-15

    Glycidyl methacrylate was grafted onto polyethylene films using a preirradiation method with {gamma} 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. {beta}-Cyclodextrin was immobilized onto polypropylene modified with glycidyl methacrylate, and the ability of the cavities of {beta}-cyclodextrin to form inclusion complexes was demonstrated using the typically organic compound approach with m-toluic acid (3-MBA) as a probe.

  4. Growing Up with Their Blocks.

    Science.gov (United States)

    Winarski, Diana L.

    1995-01-01

    Describes one teacher's use of traditional wooden blocks in fifth-grade curriculum. Notes that use of blocks can teach communication, teamwork, precision, and arithmetic concepts. Also describes four easy classroom block projects. (TM)

  5. Synthesis of Comblike Poly(methyl methacrylate) by Atom Transfer Radical Polymerization with Poly(ethyl 2-bromoacrylate) as Macroinitiator

    Institute of Scientific and Technical Information of China (English)

    Yan SHI; Zhi Feng FU; Yu Dong ZHANG; Shu Ke JIAO

    2003-01-01

    Comblike poly(methyl methacrylate) was synthesized by atom transfer radical polymerization of methyl methacrylate with poly(ethyl 2-bromoacrylate) as a macroinitiator, which was prepared by conventional free radical polymerization of ethyl 2-bromoacrylate. The obtained comblike polymers were characterized by GPC and 1H NMR.

  6. 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)

  7. 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)

  8. 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.

  9. 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...

  10. Effect of block length on the self-assembly of end-capping perfluoroalkyl moieties on the polymer surface

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Most research on copolymers with fluorinated monomers has focused on the relationship between fluorinated monomer content and the corresponding surface structure. However,the influence of the non-fluorinated block on the surface structure of the copolymer film is unknown. Various molecular weight poly(butyl methacrylates) (PBMA) end-capped with 2-perfluorooctylethyl methacrylate (FMA) units (PBMA-ec-FMA) have been synthesized by atom transfer radical polymerization (ATRP). The effect of the PBMA block length on the surface structure and properties of the polymers both in the solid state and in solution was investigated using various techniques. X-ray photoelectron spectroscopy (XPS),sum frequency generation (SFG) vibrational spectroscopy and X-ray diffraction (XRD) analyses indicated that longer PBMA blocks enhanced both the enrichment of the fluorinated moieties and the order of the packing orientation of the perfluoroalkyl side chains on the surface. This enhancement was attributed mainly to the molecular aggregate structure of the end-capped polymers with long PBMA blocks in the solution and to the interfacial structure at the air/liquid interface,which favors the -(CF2)7CF3 moieties self-assembling on the polymer surface during film formation. This observation suggests that the polyacrylate block structure in fluorinated diblock copolymers,in addition to the fluorinated monomer content,plays an important role in structure formation on the solid surface.

  11. Electrochemical impedance spectroscopy study of a surface confined redox reaction: The reduction of azobenzene on mercury in the absence of diffusion

    Energy Technology Data Exchange (ETDEWEB)

    Prieto, Francisco, E-mail: dapena@us.es [Department of Physical Chemistry, University of Seville, c/Profesor Garcia Gonzalez no 2, 41012 Seville (Spain); Rueda, Manuela; Hidalgo, Jose; Martinez, Elisa; Navarro, Inmaculada [Department of Physical Chemistry, University of Seville, c/Profesor Garcia Gonzalez no 2, 41012 Seville (Spain)

    2011-09-30

    The kinetics of azobenzene reduction on mercury electrodes in the absence of diffussional mass transport is studied by electrochemical impedance spectroscopy (EIS) in acetic acid/acetate buffered solutions at different pH values. Cyclic voltammetry experiments confirm the absence of diffusion effects and provide the values of the surface equilibrium potential. The analysis of the impedance frequency spectrums at every potential within the faradaic region conforms well the model and provides the global rate constant of the process, k{sub f}. The potential dependence of k{sub f} suggests the existence of an EE mechanism, with two electron transfers controlling the overall rate. The kinetic parameters of every step are obtained and their pH dependences clarify the role played by the protonation steps.

  12. 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.......5%/2.3% in women, P 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 block was associated...

  13. 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

  14. 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

  15. 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

  16. 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.

  17. 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...

  18. 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...

  19. Photopolymerization-Induced Two-Beam Coupling and Light-Induced Scattering in Polymethyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    LI Wei; GAO Feng; TANG Bai-Quan; Christian Pruner; ZHANG Xin-Zheng; SHI Yan-Li; XU Jing-Jun; QIAO Hai-Jun; WU Qiang; Romano A. Rupp; LOU Ci-Bo; WANG Zhen-Hua

    2008-01-01

    @@ Light amplification due to two-beam coupling is realized in doped polymethyl methacrylate (PMMA) glasses. A coupling gain as large as 14 cm-1 is obtained. The dynamic behaviour of absorption and light-induced scattering due to the process of photopolymerization are also studied. The results show that the amplification and its dynamic process enable possible applications of PMMA in optical devices.

  20. 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.

  1. Refractive microlenses produced by excimer laser machining of poly(methyl methacrylate)

    DEFF Research Database (Denmark)

    Jensen, Martin Frøhling; Krühne, Ulrich; H., L.;

    2005-01-01

    A method has been developed whereby refractive microlenses can be produced in poly (methyl methacrylate) by excimer laser irradiation at λ = 248 nm. The lenses are formed by a combined photochemical and thermal process. The lenses are formed as depressions in the substrate material (negative foca...

  2. 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

  3. Wettability and ζ potentials of a series of methacrylate polymers and copolymers

    NARCIS (Netherlands)

    Hogt, A.H.; Gregonis, D.E.; Andrade, J.D.; Kim, S.W.; Dankert, J.; Feijen, J.

    1985-01-01

    Polymers and copolymers of different methacrylates were synthesized and coated on glass slides. The surfaces of the polymer films were characterized by their water contact angles and potentials using the Wilhelmy plate technique and streaming potential measurements, respectively. From contact-angle

  4. 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...

  5. 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

  6. Polymer PCF Bragg grating sensors based on poly(methyl methacrylate) and TOPAS cyclic olefin copolymer

    DEFF Research Database (Denmark)

    Johnson, Ian P; Webb, David J; Kalli, Kyriacos;

    2011-01-01

    Fibre Bragg grating (FBG) sensors have been fabricated in polymer photonic crystal fibre (PCF). Results are presented using two different types of polymer optical fibre (POF); first multimode PCF with a core diameter of 50μm based on poly(methyl methacrylate) (PMMA) and second, endlessly single m...

  7. 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...

  8. Textural properties of poly(glycidyl methacrylate) : acid-modified bentonite nanocomposites

    NARCIS (Netherlands)

    Zunic, M.; Milutinovic-Nikolic, A.; Nastasovic, A.; Vukovic, Z.; Loncarevic, D.; Vukovic, I.; Loos, K.; ten Brinke, G.; Jovanovic, D.; Sharma, Bhaskar; Ubaghs, Luc; Keul, Helmut; Höcker, Hartwig; Loontjens, Ton; Benthem, Rolf van; Žunić, M.; Milutinović-Nikolić, A.; Nastasović, A.; Vuković, Z.; Lončarević, D.; Vuković, I.; Jovanović, D.

    2013-01-01

    The aim of this study was to obtain enhanced textural properties of macroporous crosslinked copolymer poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) by synthesizing nanocomposites with acid-modified bentonite. Nanocomposites were obtained by introducing various amounts of acid-modifie

  9. 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)

  10. 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

  11. ON COPOLYMERIZATION KINETICS OF N-VINYL PYRROLIDONE METHYL METHACRYLATE AT HIGH CONVERSION

    Institute of Scientific and Technical Information of China (English)

    WEN Jianyie; Sun Yishi

    1988-01-01

    In this work, Fourier transform infrared spectroscopy was used to study the copolymerization kinetics of N-vinyl pyrrolidone-methyl methacrylate (VPMMA) at high conversion. Through computer simulation,copolymerization rate equation based on the free volume theory, diffusion theory and modified MH model was established. The activation energy of copolymerization was also estimated.

  12. Recent Origin of the Methacrylate Redox System in Geobacter sulfurreducens AM-1 through Horizontal Gene Transfer.

    Directory of Open Access Journals (Sweden)

    Oksana V Arkhipova

    Full Text Available The origin and evolution of novel biochemical functions remains one of the key questions in molecular evolution. We study recently emerged methacrylate reductase function that is thought to have emerged in the last century and reported in Geobacter sulfurreducens strain AM-1. We report the sequence and study the evolution of the operon coding for the flavin-containing methacrylate reductase (Mrd and tetraheme cytochrome с (Mcc in the genome of G. sulfurreducens AM-1. Different types of signal peptides in functionally interlinked proteins Mrd and Mcc suggest a possible complex mechanism of biogenesis for chromoproteids of the methacrylate redox system. The homologs of the Mrd and Mcc sequence found in δ-Proteobacteria and Deferribacteres are also organized into an operon and their phylogenetic distribution suggested that these two genes tend to be horizontally transferred together. Specifically, the mrd and mcc genes from G. sulfurreducens AM-1 are not monophyletic with any of the homologs found in other Geobacter genomes. The acquisition of methacrylate reductase function by G. sulfurreducens AM-1 appears linked to a horizontal gene transfer event. However, the new function of the products of mrd and mcc may have evolved either prior or subsequent to their acquisition by G. sulfurreducens AM-1.

  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. Morphology and film formation of poly(butyl methacrylate)-polypyrrole core-shell latex particles

    NARCIS (Netherlands)

    Huijs, F; Lang, J

    2000-01-01

    Core-shell latex particles made of a poly(butyl methacrylate) (PBMA) core and a thin polypyrrole (PPy) shell were synthesized by two-stage polymerization. In the first stage, PBMA latex particles were synthesized in a semicontinuous process by free-radical polymerization. PBMA latex particles were l

  15. 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.

  16. 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.

  17. A Place for Block Play.

    Science.gov (United States)

    Moore, Gary T.

    1997-01-01

    Discusses the importance of block play--including its contributions to perceptual, fine motor, and cognitive development--and components of a good preschool block play area. Recommends unit blocks complemented by stacking blocks, toys, beads, cubes, and Brio wooden toys. Makes recommendations for space, size, locations and connections to other…

  18. 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

  19. 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.

  20. 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…

  1. 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

  2. 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

  3. 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...

  4. 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.

  5. Mechanisms of Action of (Methacrylates in Hemolytic Activity, in Vivo Toxicity and Dipalmitoylphosphatidylcholine (DPPC Liposomes Determined Using NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Seiichiro Fujisawa

    2012-01-01

    Full Text Available We investigated the quantitative structure-activity relationships between hemolytic activity (log 1/H50 or in vivo mouse intraperitoneal (ip LD50 using reported data for α,β-unsaturated carbonyl compounds such as (methacrylate monomers and their 13C-NMR β-carbon chemical shift (δ. The log 1/H50 value for methacrylates was linearly correlated with the δCβ value. That for (methacrylates was linearly correlated with log P, an index of lipophilicity. The ipLD50 for (methacrylates was linearly correlated with δCβ but not with log P. For (methacrylates, the δCβ value, which is dependent on the π-electron density on the β-carbon, was linearly correlated with PM3-based theoretical parameters (chemical hardness, η; electronegativity, χ; electrophilicity, ω, whereas log P was linearly correlated with heat of formation (HF. Also, the interaction between (methacrylates and DPPC liposomes in cell membrane molecular models was investigated using 1H-NMR spectroscopy and differential scanning calorimetry (DSC. The log 1/H50 value was related to the difference in chemical shift (ΔδHa (Ha: H (trans attached to the β-carbon between the free monomer and the DPPC liposome-bound monomer. Monomer-induced DSC phase transition properties were related to HF for monomers. NMR chemical shifts may represent a valuable parameter for investigating the biological mechanisms of action of (methacrylates.

  6. Phase behavior for the poly(alkyl methacrylate)+supercritical CO{sub 2}+DME mixture at high pressures

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Yong-Seok; Chio, Sang-Won; Byun, Hun-Soo [Chonnam National University, Yeosu (Korea, Republic of)

    2016-01-15

    The phase behavior curves of binary and ternary system were measured for poly(alkyl methacrylate) in supercritical CO{sub 2}, as well as for the poly(alkyl methacrylate)+dimethyl ether (DME) (or 1-butene) in CO{sub 2}. The solubility curves are reported for the poly(alkyl methacrylate)+DME in supercritical CO{sub 2} at temperature from (300 to 465) K and a pressure from (3.66 to 248) MPa. Also, The high-pressure static-type apparatus of cloud-point curve was tested by comparing the measured phase behavior data of the poly(methyl methacrylate) [PMMA]+CO{sub 2}+20.0 and 30.4 wt% methyl methacrylate (MMA) system with literature data of 10.4, 28.8 and 48.4 wt% MMA concentration. The phase behavior data for the poly(alkyl methacrylate)+CO{sub 2}+DME mixture were measured in changes of the pressure-temperature (p, T) slope and with DME concentrations. Also, the cloud-point pressure for the poly(alkyl methacrylate)+1- butene solution containing supercritical CO{sub 2} shows from upper critical solution temperature (UCST) region to lower critical solution temperature (LCST) region at concentration range from (0.0 to 95) wt% 1-butene at below 455 K and at below 245MPa.

  7. 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.

  8. 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

  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. 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.

  11. Managing access block.

    Science.gov (United States)

    Cameron, Peter; Scown, Paul; Campbell, Donald

    2002-01-01

    There is pessimism regarding the ability of the Acute Health Sector to manage access block for emergency and elective patients. Melbourne Health suffered an acute bed crisis in 2001 resulting in record ambulance diversions and emergency department (ED) delays. We conducted an observational study to reduce access block for emergency patients whilst maintaining elective throughput at Melbourne Health. This involved a clinician-led taskforce using previously proven principles for organisational change to implement 51 actions to improve patient access over a three-month period. The primary outcome measures were ambulance diversion, emergency patients waiting more than 12 hours for an inpatient bed, elective throughput and theatre cancellations. Despite a reduction in multi-day bed numbers all primary objectives were met, ambulance diversion decreased to minimal levels, 12-hour waits decreased by 40% and elective throughput was maintained. Theatre cancellations were also minimised. We conclude that access block can be improved by clinician-led implementation of proven process improvements over a short time frame. The ability to sustain change over the longer term requires further study.

  12. 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.

  13. 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

  14. Block Transfer Handbook: Constructing and Negotiating Block Transfer Agreements.

    Science.gov (United States)

    Finlay, Finola

    The purpose of this handbook is to provide resources for institutions or articulation committees who are engaged in the task of investigating the feasibility of block transfer agreements. Block transfer is the process whereby a block of credits is granted to students who have successfully completed a certificate, diploma, or cluster of courses…

  15. 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 .

  16. 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.

  17. 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...

  18. 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.

  19. Structure and properties of hybrid poly(2-hydroxyethyl methacrylate)/SiO2 monoliths

    DEFF Research Database (Denmark)

    Ji, Xiangling; Jiang, Shichun; Qiu, Xuepeng;

    2003-01-01

    Abstract: Hybrid poly(2-hydroxyethyl methacrylate) (PHEMA)/SiO2 monoliths were synthesized via a sol-gel process of the precursor tetraethyl orthosilicate (TEOS) and the in situ free-radical polymerization of 2-hydroxyethyl methacrylate (HEMA). The weight ratio of the starting chemicals, TEOS...... to HEMA, was varied between 100/0 and 0/100. Structural analysis was performed by IR and NMR. The NMR results indicated that the introduction of PHEMA in the silica networks gave rise to a lower degree of condensation of TEOS. The resulting monoliths showed more than 75% transmittance in the visible...... related to some degree of chemical crosslinking between the polymer and the silica moiety, which would greatly improve the thermal stability of such hybrid monoliths compared with a pure PHEMA....

  20. 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.

  1. STUDY ON CASTOR OIL POLYURETHANE/POLY (METHYL METHACRYLATE) AB CROSSLINKED POLYMERS

    Institute of Scientific and Technical Information of China (English)

    DU Ying; HAN Xiaozu; LIU Wenzhong

    1991-01-01

    Castor oil polyurethane/poly(methyl methacrylate) AB crosslinked polymers (ABCP) were synthesized by free radical copolymerization of MMA and vinyl-terminated castor oil polyurethane which was obtained from isocyanate-terminated castor oil polyurethane and hydroxyethyl methacrylate.The mechanical properties, transition and relaxation, as well as compatibility and morphology of the ABCP were investigated by changing the component. The results show that the ABCP is a semicompatible system and the compatibility of the two components decreases with increasing content of the hard segment. The mechanical and damping properties of the ABCP are obviously superior to that of their homopolymers. The damping value is mainly controlled by crosslink density of the ABCP but the Tg value by component.

  2. Removal of Dyes from Aqueous Solutions Using Radiation Synthesized (2-Hydroxyethyl Methacrylate/Acrylic acid) Hydrogels

    International Nuclear Information System (INIS)

    Acrylic acid/2-hydroxyethyl methacrylate super absorbent hydrogels (AAc/ HEMA) were prepared by γ-radiation copolymerization of 2-hydroxyethyl methacrylate (HEMA) and acrylic acid (AAc). Characterization of AAc/HEMA hydrogel was done by FTIR, TGA, SEM and XRD. The swelling properties were studied as a function of time, ph and irradiation dose. The diffusion behavior of water into these hydrogels followed the Fickian character at all investigated irradiation doses. The adsorption of Direct Congo Red and Direct Blue dyes onto the AAc/ HEMA hydrogel was studied. Physico-chemical parameters like dye concentration, solution ph and temperature were varied to characterize the adsorption phenomenon. Experimental data were modeled by Freundlich isotherm. Thermodynamic parameters ( ΔHo, ΔGo and ΔSo ) were evaluated for the dyes adsorbent systems, which suggest that the adsorption process is a typical physical process and endothermic in nature

  3. Separation of heavy metals from water by functionalized glycidyl methacrylate poly (high internal phase emulsions).

    Science.gov (United States)

    Huš, Sebastjan; Kolar, Mitja; Krajnc, Peter

    2016-03-11

    Removal of silver, lead and cadmium ions from both model solutions and real contaminated water was achieved, in a flow through manner, by using highly porous functionalized poly(glycidyl methacrylate) materials, prepared by the polymerisation of high internal phase emulsions (polyHIPE), with significant sorption differences between metals allowing for selective removal. PolyHIPEs, initially prepared from glycidyl methacrylate as a functional monomer, were functionalized with pentaerythritol tetrakis(3-mercaptopropionate), 1,9-nonanedithiol and 2-aminobenzenethiol via the epoxy ring opening on the polymer supports and applied in a flow-through manner via encasements into dedicated disk holders. Capacity of 21.7mg Ag per gram of polymer was found for 1,9-nonanedithiol functionalized polymers, while the capacity was decreasing with the decreasing ionic radius of the metal; the dynamics of sorption also depended on metal ion size and furthermore on the thiol used for the polymer functionalization.

  4. 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

  5. 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)

  6. Preparation and performances of porous polyacrylonitrile-methyl methacrylate membrane for lithium-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, D.Y.; Wang, G.Z.; Tan, C.L.; Rao, M.M.; Liao, Y.H. [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Li, W.S.; Li, G.L. [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Key Lab of Technology on Electrochemical Energy Storage and Power Generation in Guangdong Universities, Guangzhou 510006 (China)

    2008-10-01

    A copolymer, polyacrylonitrile-methyl methacrylate P(AN-MMA), was synthesized by suspension polymerization with acrylonitrile (AN) and methyl methacrylate (MMA) as monomers. With this copolymer, polymer membrane was prepared by phase inversion. The performances of the polymer were characterized by FTIR, SEM, DSC/TG, EIS and LSV. The copolymer contains CH{sub 2}, CN and CO bonds, and shows its thermal stability up to 300 C. The polymer membrane has a porous structure with an average pore diameter of 0.5 {mu}m. The conductivity of the polymer electrolyte is 1.25 mS cm{sup -1} at room temperature, and it is electrochemically stable up to 5 V (vs. Li). Using the polymer electrolyte as the gel polymer electrolyte (GPE), the cell Li/GPE/LiCoO{sub 2} shows its cyclic stability as good as the cell with liquid electrolyte. (author)

  7. 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.

  8. 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.

  9. 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.

  10. Effect of epoxidation on 30% poly(methyl methacrylate)-grafted natural rubber polymer electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Nazir, Khuzaimah; Aziz, Ahmad Fairoz [Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor (Malaysia); Adam, Nurul Ilham [Faculty of Applied Sciences, Universiti Teknologi MARA, KampusTapah, 35400 Tapah Road, Tapah, Perak (Malaysia); Yahya, Muhd Zu Azhan [Faculty of Defence Sciences and Technology, Universiti Pertahanan Nasional Malaysia, Kem Sungai Besi, 57000 Kuala Lumpur (Malaysia); Ali, Ab Malik Marwan [Institute of Science, Universiti Teknologi MARA, 40450 Shah Alam, Selangor (Malaysia)

    2015-08-28

    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 ({sup 1}HNMR) to investigate their chemical structure and differential scanning calorimeter to determine their crystallinity. A new peak in {sup 1}HNMR spectra (2.71 ppm) confirmed the appearance of epoxy group. SPE based on EMG30 doped with 40 wt% LiCF{sub 3}SO{sub 3} show the highest conductivity. The complexation between EMG30 and LiCF{sub 3}SO{sub 3} were confirmed by attenuated total reflection Fourier transform infrared (ATR-FTIR)

  11. 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).

  12. Photophysical, photochemical and laser behavior of some diolefinic laser dyes in sol-gel and methyl methacrylate/2-hydroxyethyl methacrylate copolymer matrices

    Science.gov (United States)

    Sakr, Mahmoud A. S.; Abdel Gawad, El-Sayed A.; Abou Kana, Maram T. H.; Ebeid, El-Zeiny M.

    2015-08-01

    The photophysical properties such as singlet absorption, molar absorptivity, fluorescence spectra, dipole moment, fluorescence quantum yields, fluorescence lifetimes and laser activity of 1,4-bis (β-Pyridyl-2-Vinyl) Benzene (P2VB), 2,5-distyryl-pyrazine (DSP) and 1,4-bis(2-methylstyryl)benzene(MSB) diolefineic laser dyes have been measured in different restricted hosts. (P2VB), (DSP) and (MSB) are embedded in transparent sol-gel glass and a copolymer of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) media. The absorption and fluorescence properties of these laser dyes in sol-gel glass matrices are compared with their respective properties in copolymer host. The photostability of these laser dyes in sol-gel glass and (MMA/HEMA) copolymer samples are measured in terms of half-life method (using nitrogen laser 337.1 nm in pumping), as the number of pulses necessary to reduce the dye laser intensity to 50% of its original value. The gel laser materials show improved photostability upon pumping by nitrogen laser compared with those in organic polymeric host matrix.

  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. 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

  15. Self-Assembly of Magnetic Nanoparticles at the Surface and Within Block Copolymer Films

    Science.gov (United States)

    Xu, Chen; Ohno, Kohji; Composto, Russell

    2007-03-01

    We investigate the self-assembly of magnetic Fe3O4 nanoparticles in thin films of a symmetric block copolymer of poly(styrene-b-methyl methacrylate), PS-b-PMMA (75 kg/mol). The Fe3O4 nanoparticles (4nm) are grafted by poly(methyl methacrylate) (PMMA) (2.7 kg/mol) brushes to improve their compatibility. The weight percent of Fe3O4 in PS-b-PMMA is 1, 4 and 10. The Fe3O4 reside at the intermaterial dividing surface and also form small disk-like aggregates within the PMMA phase. The addition of Fe3O4 slows down the transition from perpendicular to parallel lamellae morphology at the surface and slowing down increases as weight percent Fe3O4 increases. Using cross-sectional TEM, nanoparticles are found to be rejected from the parallel lamellae and gather preferentially within the perpendicular lamellae. These studies demonstrate that the Fe3O4 particles influence thin film morphology and visa versa. Because of widespread interest in nanodevices, this study shows that arrays of functional nanoparticles can be formed using block copolymer templates.

  16. 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.

  17. Durability of Poly(Methyl Methacrylate) Lenses Used in Concentrating Photovoltaic Technology (Revised) (Presentation)

    Energy Technology Data Exchange (ETDEWEB)

    Miller, D. C.; Carloni, J. D.; Pankow, J. W.; Gjersing, E. L.; To, B.; Packard, C. E.; Kennedy, C. E.; Kurtz, S. R.

    2012-01-01

    Concentrating photovoltaic (CPV) technology recently gained interest based on its expected low levelized cost of electricity, high efficiency, and scalability. Many CPV systems employ Fresnel lenses composed of poly(methyl methacrylate) (PMMA) to obtain a high optical flux density on the cell. The optical and mechanical durability of these lenses, however, is not well established relative to the desired surface life of 30 years. Our research aims to quantify the expected lifetime of PMMA in key market locations (FL, AZ, and CO).

  18. A Novel Method for Preparing Approximately Micron-sized Polymethyl Methacrylate Microspheres with Clear Surface

    Institute of Scientific and Technical Information of China (English)

    Di Qiang WANG; Bai Ling LIU; Jie HU; Xiao Qin LIN; Min ZHANG

    2004-01-01

    Polymethyl methacrylate (PMMA) microspheres with clear surface and diameter close to 1 μm were synthesized by newly soap-free emulsion polymerization. The results showed that the presence of ethanol and NaCl made the increase of diameter and distribution, while the presence of toluene could avoid the problem of the increase of distribution, resulting a harvest of PMMA microspheres with a diameter close to 1 μm.

  19. A novel antibacterial orthodontic cement containing a quaternary ammonium monomer dimethylaminododecyl methacrylate

    OpenAIRE

    Melo, Mary A. S.; Wu, Junling; Weir, Michael D; Xu, Hockin H. K.

    2014-01-01

    Demineralized lesions in tooth enamel around orthodontic brackets are caused by acids from cariogenic biofilm. This study aimed to develop a novel antibacterial orthodontic cement by incorporating a quaternary ammonium monomer dimethylaminododecyl methacrylate (DMADDM) into a commercial orthodontic cement, and to investigate the effects on microcosm biofilm response and enamel bond strength. DMADDM, a recently-synthetized antibacterial monomer, was incorporated into orthodontic cement at 0%, ...

  20. Optimum dose of 2-hydroxyethyl methacrylate based bonding material on pulp cells toxicity

    OpenAIRE

    Widya Saraswati

    2010-01-01

    Background: 2-hydroxyethyl methacrylate (HEMA), one type of resins commonly used as bonding base material, is commonly used due to its advantageous chemical characteristics. Several preliminary studies indicated that resin is a material capable to induce damage in dentin-pulp complex. It is necessary to perform further investigation related with its biological safety for hard and soft tissues in oral cavity. Purpose: The author performed an in vitro test to find optimum dose of HEMA resin mon...

  1. Polymethyl methacrylate based open-cell porous plastics for high-pressure ceramic casting

    OpenAIRE

    Ergün, Yelda; Dirier, C.; Tanoğlu, Metin

    2004-01-01

    The aim of the present study is to investigate the microstructure-property relation in polymethyl methacrylate (PMMA)-based porous mould materials used for high-pressure casting of ceramic articles. For this purpose, porous plastic materials were produced by the polymerization of water-in-oil emulsions with various compositions of emulsion constituents and particle sizes of the filler PMMA beads. Pore morphology, porosity and water permeability of the materials were measured. The compressive ...

  2. COMPATIBILITY IN POLYMER BLENDS OF POLY (VINYL ACETATE) AND POLY (METHYL METHACRYLATE)STUDIED BY NMR

    Institute of Scientific and Technical Information of China (English)

    SONG Mo; DAI Yingkun; HU Cheng; HUANG Yuhui; CONG Guangmin

    1992-01-01

    Compatibility of poly (vinyl acetate) (PVAc) with poly (methyl methacrylate) (PMMA) mixtures has been studied by using nuclear magnetic relaxation, differential scanning calorimeter and small-angle X-ray scattering techniques. The nuclear magnetic relaxation time T1's were measured as a function of composition in blends of PMMA and PVAc prepared from chloroform solution. The results show that the system is miscible for casting from chloroform solution.

  3. Synthesis and Characterization of Brush Copolymer Poly (propylene oxide)-graft-Poly(N,N-dimethylaminoethyl methacrylate)

    Institute of Scientific and Technical Information of China (English)

    ZHANG Wen-qian

    2016-01-01

    In this paper, a amphiphilic brush copolymer poly (propylene oxide)-graft -poly (N,N-dimethylaminoethyl methacrylate) (PPO-g-PDMAEMA) was successfully prepared via the combine of anionic ring opening polymerization and atom transfer radical polymerization(ATRP). The target products were confirmed by GPC and 1H NMR. This well-defined copolymer can supply a promising material as drug and gene carriers and protective materials.

  4. Electrical conduction mechanism of polyvinyl chloride (PVC)–polymethyl methacrylate (PMMA) blend film

    Indian Academy of Sciences (India)

    R S Gulalkari; Y G Bakale; D K Burghate; V S Deogaonkar

    2007-09-01

    The electrical conduction mechanism in polyvinyl chloride (PVC)–polymethyl methacrylate (PMMA) blend film has been studied at various temperatures in the range 313 K to 353 K. The results are presented in the form of – characteristics. Analysis has been made in the light of Poole–Frenkel, Fowler–Nordheim, Schottky, log() vs. plots and Arrhenius plots. It is observed that, Schottky–Richardson mechanism is primarily responsible for the observed conduction.

  5. Synthesis of indenyllanthanide amides: the effective initiators for polymerization of methyl methacrylate

    Institute of Scientific and Technical Information of China (English)

    赵群; 姚英明; 沈琪

    2000-01-01

    Diisopropylamido bisindenyl lanthanides ( C9H7)2LnN( i-Pr)2(Ln=Gd (1), Y(2), Er (3)) were successfully synthesized in satisfied yield by the reaction of Ln(N(i-Pr)2)3(THF) with indene in 1:2 molar ratio in toluene. All of the complexes exhibit very high catalytic activity in the polymerization of methyl methacrylate. The resulting polymers have narrow molecular weight distributions and syndiotacticity.

  6. Preparation and Characterization of Injectable Brushite Filled-Poly (Methyl Methacrylate) Bone Cement

    OpenAIRE

    Lucas C. Rodriguez; Jonathan Chari; Shant Aghyarian; Gindri, Izabelle M.; Victor Kosmopoulos; Rodrigues, Danieli C.

    2014-01-01

    Powder-liquid poly (methyl methacrylate) (PMMA) bone cements are widely utilized for augmentation of bone fractures and fixation of orthopedic implants. These cements typically have an abundance of beneficial qualities, however their lack of bioactivity allows for continued development. To enhance osseointegration and bioactivity, calcium phosphate cements prepared with hydroxyapatite, brushite or tricalcium phosphates have been introduced with rather unsuccessful results due to increased cem...

  7. Microleakage of silorane- and methacrylate-based class V composite restorations.

    Science.gov (United States)

    Krifka, Stephanie; Federlin, Marianne; Hiller, Karl-Anton; Schmalz, Gottfried

    2012-08-01

    The marginal integrity of class V restorations in a silorane- and a group of methacrylate-based composite resins with varying viscosities was tested in the present study. Different adhesives (OptiBond FL, KerrHawe; AdheSE One, Vivadent; or Silorane System Adhesive, 3M ESPE) were applied to 168 standardized class V cavities. The cavities (n = 12) were filled with a wide range of different viscous composite resins: Filtek Silorane, 3M ESPE; els and els flow, Saremco; Tetric EvoCeram and Tetric EvoFlow, Vivadent; Grandio, Voco; and Ultraseal XT Plus, Ultradent. Microleakage of the restoration was assessed by dye penetration (silver staining) on multiple sections with and without thermocycling and mechanical loading (TCML: 5,000 × 5-55°C; 30 s/cycle; 500,000 × 72.5 N, 1.6 Hz). Data were statistically analyzed with the Mann-Whitney U test and the Error Rates Method (ERM). The silorane-based composite resin yielded the lowest dye penetration after TCML. Microleakage of methacrylate-based composite restorations, in general (ERM), was statistically significantly influenced by the adhesive system, Moreover, dye penetration at enamel margins was significantly lower than dye penetration at dentin margins. The chemical basis of composite resins and adjacent tooth substance seems to strongly influence marginal sealing of class V restorations for methacrylate-based materials. Moreover, the steps of dental adhesives used affected marginal integrity. The silorane-based composite resin evaluated in the present study exhibits the best marginal seal. The three-step adhesive yielded better marginal sealing than the one-step adhesive for methacrylate-based class V composite restorations. PMID:21947906

  8. Mechanically Strong Double Network Photocrosslinked Hydrogels from N, N-Dimethylacrylamide and Glycidyl Methacrylated Hyaluronan

    OpenAIRE

    Weng, Lihui; Gouldstone, Andrew; Wu, Yuhong; Chen, Weiliam

    2008-01-01

    Hyaluronan (HA) is a natural polysaccharide abundant in biological tissues and it can be modified to prepare biomaterials. In this work, HA modified with glycidyl methacrylate was photocrosslinked to form the first network (PHA), and then a series of highly porous PHA/N, N-dimethylacrylamide (DAAm) hydrogels (PHA/DAAm) with high mechanical strength were obtained by incorporating a second network of photocrosslinked DAAm into PHA network. Due to synergistic effect produced by double network (D...

  9. Radiation-grafting of ethylene glycol dimethacrylate (EGDMA) and glycidyl methacrylate (GMA) onto silicone rubber

    Science.gov (United States)

    Flores-Rojas, G. G.; Bucio, E.

    2016-10-01

    Silicone rubber (SR) was modified with a graft of ethylene glycol dimethacrylate (EGDMA) and glycidyl methacrylate (GMA) using either gamma-radiation or azobisisobutyronitrile (AIBN). The graft efficiency was evaluated as a function of monomer concentration, absorbed dose, reaction temperature, and concentration of AIBN. The hydrophilicity of the grafted films was measured by contact angle and their equilibrium swelling time in ethanol. Additional characterization by infrared (FTIR-ATR) spectroscopy, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) is also reported.

  10. Raman spectra of bilayer graphene covered with Poly(methyl methacrylate) thin film

    OpenAIRE

    Minggang Xia; Zhidan Su; Shengli Zhang

    2012-01-01

    The Raman spectra of bilayer graphene covered with poly(methyl methacrylate) (PMMA) were investigated. Both the G and 2D peaks of PMMA-coated graphene were stiff and broad compared with those of uncovered graphene. This could be attributed to the residual strain induced by high-temperature baking during fabrication of the nanodevice. Furthermore, the two 2D peaks stiffened and broadened with increasing laser power, which is just the reverse to uncovered graphene. The stiffness is likely cause...

  11. CORE SATURATION BLOCKING OSCILLATOR

    Science.gov (United States)

    Spinrad, R.J.

    1961-10-17

    A blocking oscillator which relies on core saturation regulation to control the output pulse width is described. In this arrangement an external magnetic loop is provided in which a saturable portion forms the core of a feedback transformer used with the thermionic or semi-conductor active element. A first stationary magnetic loop establishes a level of flux through the saturation portion of the loop. A second adjustable magnet moves the flux level to select a saturation point giving the desired output pulse width. (AEC)

  12. Fabrication, modeling and characterization of multi-crosslinked methacrylate copolymeric nanoparticles for oral drug delivery.

    Science.gov (United States)

    Ngwuluka, Ndidi C; Pillay, Viness; Choonara, Yahya E; Modi, Girish; Naidoo, Dinesh; du Toit, Lisa C; Kumar, Pradeep; Ndesendo, Valence M K; Khan, Riaz A

    2011-01-01

    Nanotechnology remains the field to explore in the quest to enhance therapeutic efficacies of existing drugs. Fabrication of a methacrylate copolymer-lipid nanoparticulate (MCN) system was explored in this study for oral drug delivery of levodopa. The nanoparticles were fabricated employing multicrosslinking technology and characterized for particle size, zeta potential, morphology, structural modification, drug entrapment efficiency and in vitro drug release. Chemometric Computational (CC) modeling was conducted to deduce the mechanism of nanoparticle synthesis as well as to corroborate the experimental findings. The CC modeling deduced that the nanoparticles synthesis may have followed the mixed triangular formations or the mixed patterns. They were found to be hollow nanocapsules with a size ranging from 152 nm (methacrylate copolymer) to 321 nm (methacrylate copolymer blend) and a zeta potential range of 15.8-43.3 mV. The nanoparticles were directly compressible and it was found that the desired rate of drug release could be achieved by formulating the nanoparticles as a nanosuspension, and then directly compressing them into tablet matrices or incorporating the nanoparticles directly into polymer tablet matrices. However, sustained release of MCNs was achieved only when it was incorporated into a polymer matrix. The experimental results were well corroborated by the CC modeling. The developed technology may be potentially useful for the fabrication of multi-crosslinked polymer blend nanoparticles for oral drug delivery. PMID:22016653

  13. Fabrication and Characterization of Magnetoresponsive Electrospun Nanocomposite Membranes Based on Methacrylic Random Copolymers and Magnetite Nanoparticles

    Directory of Open Access Journals (Sweden)

    Ioanna Savva

    2012-01-01

    Full Text Available Magnetoresponsive polymer-based fibrous nanocomposites belonging to the broad category of stimuli-responsive materials, is a relatively new class of “soft” composite materials, consisting of magnetic nanoparticles embedded within a polymeric fibrous matrix. The presence of an externally applied magnetic field influences the properties of these materials rendering them useful in numerous technological and biomedical applications including sensing, magnetic separation, catalysis and magnetic drug delivery. This study deals with the fabrication and characterization of magnetoresponsive nanocomposite fibrous membranes consisting of methacrylic random copolymers based on methyl methacrylate (MMA and 2-(acetoacetoxyethyl methacrylate (AEMA (MMA-co-AEMA and oleic acid-coated magnetite (OA·Fe3O4 nanoparticles. The AEMA moieties containing β-ketoester side-chain functionalities were introduced for the first time in this type of materials, because of their inherent ability to bind effectively onto inorganic surfaces providing an improved stabilization. For membrane fabrication the electrospinning technique was employed and a series of nanocomposite membranes was prepared in which the polymer content was kept constant and only the inorganic (OA·Fe3O4 content varied. Further to the characterization of these materials in regards to their morphology, composition and thermal properties, assessment of their magnetic characteristics disclosed tunable superparamagnetic behaviour at ambient temperature.

  14. THE PHYSICAL PROPERTIES OF POLY(2-HYDROXYETHYL METHACRYLATE) COPOLYMER HYDROGELS USED AS INTRAVAGINAL RINGS

    Institute of Scientific and Technical Information of China (English)

    Young A Han; Eun MiLee; Byung Chul Ji

    2009-01-01

    Poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(2-hydroxyethyl methacrylate-co-sodium methacrylate) [P(HEMA-co-SMA)] hydrogels with different compositions were prepared to be used as intravaginal rings, and their gelation time, water content, mechanical properties and morphology were investigated. The water content of PHEMA and P(HEMA-co-SMA) hydrogels decreased as the concentration of the monomer and the degree of crosslinking increased, while the water content significantly increased as the content of SMA, the hydrophilic monomer, increased. The increasing of the concentration of the crosslinking agent affected the tensile and flexural properties highly. The presence of a proper small amount of SMA also led the tensile and flexural modulus to move to a higher level. The results showed that P(HEMA-co-SMA) hydrogel with high drug load and good mechanical properties at optimum preparation conditions can be prepared for intravaginal rings to deliver nonhormonal contraceptives. These results may be applied to prepare better intravaginal drug delivery devices.

  15. Preparation of Rhodamine B Fluorescent Poly(methacrylic acid Coated Gelatin Nanoparticles

    Directory of Open Access Journals (Sweden)

    Zhenhai Gan

    2011-01-01

    Full Text Available Poly(methacrylic acid (PMAA-coated gelatin nanoparticles encapsulated with fluorescent dye rhodamine B were prepared by the coacervation method with the aim to retard the release of rhodamine B from the gelatin matrix. With sodium sulfate as coacervation reagent for gelatin, a kind of biopolymer with excellent biocompatibility, the formed gelatin nanoparticles were cross-linked by formaldehyde followed by the polymerization of methacrylic acid coating. The fluorescent poly(methacrylic acid coated gelatin (FPMAAG nanoparticles had a uniform spherical shape and a size distribution of 60±5 nm. Infrared spectral analysis confirmed the formation of PMAA coating on the gelatin nanoparticles. Based on UV-Vis spectra, the loading efficiency of rhodamine B for the FPMAAG nanoparticles was 0.26 μg per mg nanoparticles. The encapsulated rhodamine B could sustain for two weeks. Favorable fluorescence property and fluorescence imaging of cells confirmed that the FPMAAG nanoparticles have promising biochemical, bioanalytical, and biomedical applications.

  16. Study of sodium dodecyl sulfate-poly(propylene oxide) methacrylate mixed micelles.

    Science.gov (United States)

    Bastiat, Guillaume; Grassl, Bruno; Khoukh, Abdel; François, Jeanne

    2004-07-01

    Sodium dodecyl sulfate (SDS)-poly(propylene oxide) methacrylate (PPOMA) (of molecular weight M(w) = 434 g x mol(-1)) mixtures have been studied using conductimetry, static light scattering, fluorescence spectroscopy, and 1H NMR. It has been shown that SDS and PPOMA form mixed micelles, and SDS and PPOMA aggregation numbers, N(ag SDS) and N(ag PPOMA), have been determined. Total aggregation numbers of the micelles (N(ag SDS) + N(ag PPOMA)) and those of SDS decrease upon increasing the weight ratio R = PPOMA/SDS. Localization of PPOMA inside the mixed micelles is considered (i) using 1H NMR to localize the methacrylate function at the hydrophobic core-water interface and (ii) by studying the SDS-PPO micellar system (whose M(w) = 400 g x mol(-1)). Both methods have indicated that the PPO chain of the macromonomer is localized at the SDS micelle surface. Models based on the theorical prediction of the critical micellar concentration of mixed micelles and structural model of swollen micelles are used to confirm the particular structure proposed for the SDS-PPOMA system, i.e., the micelle hydrophobic core is primarily composed of the C12 chains of the sodium dodecyl sulfate, the hydrophobic core-water interface is made up of the SDS polar heads as well as methacrylate functions of the PPOMA, the PPO chains of the macromonomer are adsorbed preferentially on the surface, i.e., on the polar heads of the SDS.

  17. Characterization of collagen fiber grafted with glycidyl methacrylate monomer and treated with dibutyl amine

    International Nuclear Information System (INIS)

    Leather grafted with poly (glycidyl methacrylate) (L-g-PGMA) having graft yield of 26% and epoxy content 69.4 m mol/ 100 gm was prepared according to the emulsion polymerization technique and impregnated in different dibutyl amine solutions using amine/ epoxy molar ratio range from 0.5 up to 2.5. The obtained samples were characterized with respect to the nitrogen content, infrared spectroscopy, thermogravimetric analysis (TGA) analysis and the scanning electron microscope. The nitrogen content of the treated leather samples was increased by increasing the dibutyl amine concentration up to amine/ epoxy molar ratio of 2 after which it began to decrease. The water absorption, tensile strength and elongation (%) as well as hardness of the modified leather samples were studied and compared with the unmodified one. The colour strength values of dyed leather samples with acid dye were increased by grafting or by increasing the amine/epoxy molar ratio up to a value of 1.0 after which it begin to decrease. Meanwhile, the colour strength value of dyed leather sample with reactive dye was sharply decreased after grafting with poly (glycidyl methacrylate). On the other hand, pronounced increment in the colour strength value was obtained for the samples grafted with glycidyl methacrylate and treated with dibutyl acrylate amine and the colour strength is directly proportional to the sample nitrogen content

  18. Mushroom-shaped Morphology Formed in Thin Films of Cylinder-forming Block Copolymer

    Institute of Scientific and Technical Information of China (English)

    GONG Yu-mei; SONG Jing-chuan; ZHANG Gui-xia

    2011-01-01

    The morphology of the film of polystyrene-block-poly(methyl methacrylate)(PS-b-PMMA) block copolymer having polystyrene(PS) cylinder forming composition spin-coated on a neutral brush modified silicon substrate has been investigated in this report. A mushroom-shaped morphology formed in the film with one period to two periods(L0-2L0) in thickness, which was spin-coated under a low humidity condition(RH ca.13%) and then thermally annealed at an extreme high temperature(230 ℃). The results suggest that the spin-coating condition together with the confinement conditions plays a crucial role in the interesting morphology formation.

  19. 含偶氮苯结构聚酯的合成及性能%Synthesis and propertiesof polyesters containing azobenzene unit

    Institute of Scientific and Technical Information of China (English)

    于世钧; 高博; 王璐; 王红; 高永久

    2011-01-01

    Three novel linear polyesters(P1~P3) containing azobenzene unit are synthesized by condensation polymerization of diethyl 5-(4-alkoxy phenylazo) isophthalate and different glycols(l,3-propyl-ene glycol, 1,6-hexylene glycol, polyethylene glycol-400). The structure and properties of the polyes-ters(Pl~P3) are confirmed by IR, UV-vis, 'H NMR, SEC and TG-DTA. Polyesters(Pl~P3) containing azobenzene unit dissolve in common organic solvents such as tetrahydrofuran and chloroform, et al The intrinsic viscosities of polyesters(Pl~P3) in chloroform are 0. 514 6, 0. 463 9,0. 565 7 dL/g, the Mw are 39 200,34 983,45 507 g/mol, 5% weight loss temperature of polyesters(P1~P3) are 287,276,335 V. Polyesters(P1~P3) take place trans-cis photoisomerization under 365 run UV irradiation. With the ultraviolet excitation at 350 nm, polyesters(Pl~P3) emit purple fluorescence at 398 nm.%以间苯二甲酸为原料合成了5-[4-(乙氧基)苯基偶氮]-1,3-苯二甲酸二乙酯,分别与1,3-丙二醇、1,6-己二醇和聚乙二醇-400熔融聚合得到了3种新型含有偶氮苯结构的线型聚酯(P1~P3),采用IR、UV-vis、1H NMR、SEC和TG-DTA等对聚酯结构和性能进行了表征.聚酯(P1~P3)易溶于THF、CHCl3等有机溶剂,特性黏度分别为0.514 6、0.463 9、0.565 7 dL/g,Mw分别为39 200、34 983、45 507 g/mol,5%失重温度分别为287、276、335℃.在365 nm紫外光照射下,聚酯(P1~P3)中偶氮苯结构发生反-顺异构化,在350 nm波长光激发下,聚酯(P1~P3)在398 nm附近发紫色光.

  20. 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

  1. 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...

  2. Tuning Cationic Block Copolymer Micelle Size by pH and Ionic Strength.

    Science.gov (United States)

    Sprouse, Dustin; Jiang, Yaming; Laaser, Jennifer E; Lodge, Timothy P; Reineke, Theresa M

    2016-09-12

    The formation, morphology, and pH and ionic strength responses of cationic block copolymer micelles in aqueous solutions have been examined in detail to provide insight into the future development of cationic micelles for complexation with polyanions such as DNA. Diblock polymers composed of a hydrophilic/cationic block of N,N-dimethylaminoethyl methacrylate (DMAEMA) and a hydrophobic/nonionic block of n-butyl methacrylate (BMA) were synthesized [denoted as DMAEMA-b-BMA (X-Y), where X = DMAEMA molecular weight and Y = molecular weight of BMA in kDa]. Four variants were created with block molecular weights of 14-13, 14-23, 27-14, 27-29 kDa and low dispersities less than 1.10. The amphiphilic polymers self-assembled in aqueous conditions into core-shell micelles that ranged in size from 25-80 nm. These cationic micelles were extensively characterized in terms of size and net charge in different buffers over a wide range of ionic strength (0.02-1 M) and pH (5-10) conditions. The micelle core is kinetically trapped, and the corona contracts with increasing pH and ionic strength, consistent with previous work on micelles with glassy polystyrene cores, indicating that the corona properties are independent of the dynamics of the micelle core. The contraction and extension of the corona scales with solution ionic strength and charge fraction of the amine groups. The aggregation numbers of the micelles were obtained by static light scattering, and the Rg/Rh ratios are close to that of a hard sphere. The zeta potentials of the micelles were positive up to two pH units above the corona pKa, suggesting that applications relying on micelle charge for stability should be viable over a wide range of solution conditions. PMID:27487088

  3. The wild tapered block bootstrap

    DEFF Research Database (Denmark)

    Hounyo, Ulrich

    In this paper, a new resampling procedure, called the wild tapered block bootstrap, is introduced as a means of calculating standard errors of estimators and constructing confidence regions for parameters based on dependent heterogeneous data. The method consists in tapering each overlapping block...... of the series first, the applying the standard wild bootstrap for independent and heteroscedastic distrbuted observations to overlapping tapered blocks in an appropriate way. Its perserves the favorable bias and mean squared error properties of the tapered block bootstrap, which is the state-of-the-art block......-order asymptotic validity of the tapered block bootstrap as well as the wild tapered block bootstrap approximation to the actual distribution of the sample mean is also established when data are assumed to satisfy a near epoch dependent condition. The consistency of the bootstrap variance estimator for the sample...

  4. Effects of copolymer composition, film thickness, and solvent vapor annealing time on dewetting of ultrathin block copolymer films.

    Science.gov (United States)

    Huang, Changchun; Wen, Gangyao; Li, Jingdan; Wu, Tao; Wang, Lina; Xue, Feifei; Li, Hongfei; Shi, Tongfei

    2016-09-15

    Effects of copolymer composition, film thickness, and solvent vapor annealing time on dewetting of spin-coated polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) films (annealed for different times were performed using X-ray photoelectron spectroscopy and contact angle measurement. With the annealing of acetone vapor, dewetting of the films with different thicknesses occur via the spinodal dewetting and the nucleation and growth mechanisms, respectively. The PS-b-PMMA films rupture into droplets which first coalesce into large ones to reduce the surface free energy. Then the large droplets rupture into small ones to increase the contact area between PMMA blocks and acetone molecules resulting from ultimate migration of PMMA blocks to droplet surface, which is a novel dewetting process observed in spin-coated films for the first time. PMID:27309943

  5. Block Voter Model

    CERN Document Server

    Sampaio, C I N

    2011-01-01

    We introduce and study the block voter model with noise on two-dimensional square lattices using Monte Carlo simulations and finite-size scaling techniques. The model is defined by an outflow dynamics where a central set of $N_{PCS}$ spins, here denoted by persuasive cluster spins (PCS), tries to influence the opinion of their neighbouring counterparts. We consider the collective behaviour of the entire system with varying PCS size. When $N_{PCS}>2$, the system exhibits an order-disorder phase transition at a critical noise parameter $q_{c}$ which is a monotonically increasing function of the size of the persuasive cluster. We conclude that how large the PCS is more power of persuasion it has. It also seems that the resulting critical behaviour is Ising-like independent of the range of the interactions.

  6. Spintronics: Conceptual Building Blocks

    Science.gov (United States)

    Ansermet, J.-Ph.

    The purpose of this introduction to spintronics is to provide some elementary description of its conceptual building blocks. Thus, it is intended for a newcomer to the field. After recalling rudimentary descriptions of spin precession and spin relaxation, spin-dependent transport is treated within the Boltzmann formalism. This suffices to introduce key notions such as the spin asymmetry of the conductivities in the two-current model, the spin diffusion length, and spin accumulation. Two basic mechanisms of spin relaxation are then presented, one arising from spin-orbit scattering and the other from electron-magnon collisions. Finally, the action of a spin-polarized current on magnetization is presented in a thermodynamics framework. This introduces the notion of spin torque and the characteristic length scale over which the transverse spin polarization of conduction electron decays as it is injected into a magnet.

  7. Photovoltaic building blocks

    DEFF Research Database (Denmark)

    Hanberg, Peter Jesper; Jørgensen, Anders Michael

    2014-01-01

    it directcompetitive with fossil energy sources a further reduction is needed. By increasing the efficiency of the solar cells one gain an advantage through the whole chain of cost. So that per produced Watt of power less material is spent, installation costs are lower, less area is used etc. With an average...... efficiency of about 15% for commercial Silicon solar cells there is still much to gain. DTU Danchip provides research facilities, equipment and expertise for the building blocks that comprises fabricating the efficient solar cell. In order to get more of the sun light into the device we provide thin film......Photovoltaics (PV), better known as solar cells, are now a common day sight on many rooftops in Denmark.The installed capacity of PV systems worldwide is growing exponentially1 and is the third most importantrenewable energy source today. The cost of PV is decreasing fast with ~10%/year but to make...

  8. Atomic Basic Blocks

    Science.gov (United States)

    Scheler, Fabian; Mitzlaff, Martin; Schröder-Preikschat, Wolfgang

    Die Entscheidung, einen zeit- bzw. ereignisgesteuerten Ansatz für ein Echtzeitsystem zu verwenden, ist schwierig und sehr weitreichend. Weitreichend vor allem deshalb, weil diese beiden Ansätze mit äußerst unterschiedlichen Kontrollflussabstraktionen verknüpft sind, die eine spätere Migration zum anderen Paradigma sehr schwer oder gar unmöglich machen. Wir schlagen daher die Verwendung einer Zwischendarstellung vor, die unabhängig von der jeweils verwendeten Kontrollflussabstraktion ist. Für diesen Zweck verwenden wir auf Basisblöcken basierende Atomic Basic Blocks (ABB) und bauen darauf ein Werkzeug, den Real-Time Systems Compiler (RTSC) auf, der die Migration zwischen zeit- und ereignisgesteuerten Systemen unterstützt.

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

    Science.gov (United States)

    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 addition-fragment transfer (RAFT) polymerization, was confirmed by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). While the hydrophilic PMOEP block within the amphiphilic block copolymer strongly binds to the enamel surface, the PMMA block forms a hydrophobic shell to prevent acid attack on tooth enamel, thus preventing/reducing acid erosion. The polymer treatment not only effectively decreased the mineral loss of hydroxyapatite (HAP) by 36-46% compared to the untreated control, but also protected the surface morphology of the enamel specimen following exposure to acid. Additionally, experimental results confirmed that low pH values and high polymer concentrations facilitate polymer binding. Thus, the preliminary data suggests that this new amphiphilic diblock copolymer has the potential to be used as a non-fluoride ingredient for mouth-rinse or toothpaste to prevent/reduce tooth erosion. PMID:25419457

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

    Directory of Open Access Journals (Sweden)

    Jürgen Bachl

    2015-05-01

    Full Text Available 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 case of miscible oil/water mixtures, the entire mixture was gelled, resulting in the formation of quasi-hydrogels. Importantly, PSG could be triggered at room temperature by ultrasound treatment of the mixture or by adding ultrasound-aided concentrated solution of the peptide in an oil-phase to a mixture of the same oil and water. Moreover, the PSG was not affected by the presence of salts or impurities existing in water from natural sources. The process could be scaled-up, and the oil phases (e.g., aromatic solvents, gasoline, diesel fuel recovered almost quantitatively after a simple distillation process, which also allowed the recovery and reuse of the gelator. Finally, these peptidic gelators could be used to quantitatively remove toxic dyes from aqueous solutions.

  11. Supramolecular phase-selective gelation by peptides bearing side-chain azobenzenes: effect of ultrasound and potential for dye removal and oil spill remediation.

    Science.gov (United States)

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

    2015-05-22

    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 case of miscible oil/water mixtures, the entire mixture was gelled, resulting in the formation of quasi-hydrogels. Importantly, PSG could be triggered at room temperature by ultrasound treatment of the mixture or by adding ultrasound-aided concentrated solution of the peptide in an oil-phase to a mixture of the same oil and water. Moreover, the PSG was not affected by the presence of salts or impurities existing in water from natural sources. The process could be scaled-up, and the oil phases (e.g., aromatic solvents, gasoline, diesel fuel) recovered almost quantitatively after a simple distillation process, which also allowed the recovery and reuse of the gelator. Finally, these peptidic gelators could be used to quantitatively remove toxic dyes from aqueous solutions.

  12. Research in Optical Properties of Azobenzene Doped Polymer%偶氮苯聚合物薄膜的光学性质研究

    Institute of Scientific and Technical Information of China (English)

    谢茹胜; 赵有源

    2012-01-01

    The UV-Vis absorption of the azobenzene doped polymersample is measured and analyzed. In the nonresonant absorption, its photo-induced birefringence is studied. The relation of photo-induced birefringence signal and polarization angle is measured and the experimental result fits the theoretical curve well. Furthermore, it possesses large photo-induced birefringence signal and the characteristic of long-term optical storage. On this basis, the optical holographic storage was achieved by using molecular orientation.%对偶氮苯聚合物薄膜各组分进行光谱特性分析,并在非吸收区用光泵浦测试法研究了薄膜光致双折射及其与偏振角度的关系,得出实验曲线与理论曲线相吻合的结果.该聚合物薄膜具有较大的光致双折射和长久存储特性.利用分子取向实现了全息存储实验,说明样品薄膜具有良好的光学性质.

  13. Photo-aligned blend films of azobenzene-containing polyimides with and without side-chains for inducing inclined alignment of liquid crystal molecules

    Science.gov (United States)

    Usami, Kiyoaki; Sakamoto, Kenji

    2011-08-01

    We have succeeded in controlling the pretilt angle of liquid crystal (LC) molecules over the whole range of 0 to 90° by using photo-aligned blend films of two azobenzene-containing polyimides (Azo-PIs) with and without side-chains. The Azo-PIs were synthesized from pyromellitic dianhydride and a mixture of 4,4'-diaminoazobenzene and 4-(4'-propylbi(cyclohexan)-4-yl)phenyl 3,5-diaminobenzoate (PBCP-DABA). PBCP-DABA is a diamine to introduce a side-chain structure into the polyimide. Defect-free uniform LC alignment was obtained in the pretilt angle (θp) ranges of θp ≤ 11° and θp ≥ 78°. Previously, we reported that the pretilt angle can be controlled using pure photo-aligned films of Azo-PIs with different molar fractions of PBCP-DABA. For the pure photo-aligned films, the defect-free pretilt angle ranges were θp < 5° and θp ≥ 85°. These results suggest that the azimuthal anchoring strength of the blend Azo-PI film is stronger than that of the pure films of Azo-PIs with side-chains, at least for the pretilt angle range from 5 to 11°. We found that the defect-free pretilt angle range can be extended by using the blend Azo-PI films instead of the pure Azo-PI films.

  14. Photoorientation of a liquid-crystalline polyester with azobenzene side groups: Effects of irradiation with linearly polarized red light after photochemical pretreatment

    DEFF Research Database (Denmark)

    Zebger, Ingo; Rutloh, Michael; Hoffmann, Uwe;

    2003-01-01

    In contrast to the conventional photoorientation process with blue light, an orientation of 4-cyano-4'-alkoxyazobenzene side groups parallel to the electric field vector of the incident light is generated upon irradiating films of a liquid-crystalline side-chain polymer with linearly polarized red...... of this two-step process is the angular-selective transformation of the bulky Z-isomers to the rodlike E-isomeric formed by the red light. The aligned E-azobenzene side groups become strongly J-aggregated. Very high values of dichroism of about 0.8 and birefringence of about 0.3 were generated as a result...... light. The polyester is characterized by smectic and nematic phases g24SX26SA34N46i and a strong tendency to form J-aggregates. The process requires a photochemical pretreatment by irradiation with UV light or an exposure to visible light of high power density to produce a certain concentration of the Z...

  15. Trajectory-based nonadiabatic molecular dynamics without calculating nonadiabatic coupling in the avoided crossing case: trans↔cis photoisomerization in azobenzene.

    Science.gov (United States)

    Yu, Le; Xu, Chao; Lei, Yibo; Zhu, Chaoyuan; Wen, Zhenyi

    2014-12-21

    We develop a novel method to simulate analytical nonadiabatic switching probability based on effective coupling and effective collision energy by using only electronic adiabatic potential energy surfaces and its gradients in the case of avoided crossing types of nonadiabatic transitions. In addition, the present method can keep the same time step for computing both on-the-fly trajectory and nonadiabatic transitions accurately. The present method is most useful for localized nonadiabatic transitions induced by conical intersection. We employ the on-the-fly surface hopping algorithm with an ab initio quantum chemistry calculation to demonstrate a dynamic simulation for photoisomerization in azobenzene. Simulated quantum yield and lifetime converge to 0.39 and 53 femtosecond, respectively (0.33 and 0.81 picosecond) for cis-to-trans (trans-to-cis) photoisomerization with up to 800 (600) sampling trajectories. The present results agree well with those of the experiment, as well as results simulated with use of nonadiabatic coupling within Tully's fewest switching method. The present trajectory-based nonadiabatic molecular dynamics free from nonadiabatic coupling greatly enhances the simulation power of molecular dynamics for large complex chemical systems.

  16. The Block-block Bootstrap: Improved Asymptotic Refinements

    OpenAIRE

    Donald W.K. Andrews

    2002-01-01

    The asymptotic refinements attributable to the block bootstrap for time series are not as large as those of the nonparametric iid bootstrap or the parametric bootstrap. One reason is that the independence between the blocks in the block bootstrap sample does not mimic the dependence structure of the original sample. This is the join-point problem. In this paper, we propose a method of solving this problem. The idea is not to alter the block bootstrap. Instead, we alter the original sample sta...

  17. Convergence rates of empirical block length selectors for block bootstrap

    OpenAIRE

    Nordman, Daniel J.; Lahiri, Soumendra N.

    2014-01-01

    We investigate the accuracy of two general non-parametric methods for estimating optimal block lengths for block bootstraps with time series – the first proposed in the seminal paper of Hall, Horowitz and Jing (Biometrika 82 (1995) 561–574) and the second from Lahiri et al. (Stat. Methodol. 4 (2007) 292–321). The relative performances of these general methods have been unknown and, to provide a comparison, we focus on rates of convergence for these block length selectors for the moving block ...

  18. Electron Transfer of Myoglobin Immobilized in Au Electrodes Modified with a RAFT PMMA-Block-PDMAEMA Polymer

    Directory of Open Access Journals (Sweden)

    Carla N. Toledo

    2014-01-01

    Full Text Available Myoglobin was immobilized with poly(methyl methacrylate-block-poly[(2-dimethylaminoethyl methacrylate]PMMA-block-PDMAEMA polymer synthesized by reversible addition-fragmentation chain transfer technique (RAFT. Cyclic voltammograms gave direct and slow quasireversible heterogeneous electron transfer kinetics between Mb-PMMA-block-PDMAEMA modified electrode and the redox center of the protein. The values for electron rate constant (Ks and transfer coefficient (α were 0.055±0.01·s−1 and 0.81±0.08, respectively. The reduction potential determined as a function of temperature (293–328 K revealed a value of reaction center entropy of ΔS0 of 351.3±0.0002 J·mol−1·K−1 and enthalpy change of -76.8±0.1 kJ·mol−1, suggesting solvent effects and charge ionization atmosphere involved in the reaction parallel to hydrophobic interactions with the copolymer. The immobilized protein also exhibits an electrocatalytical response to reduction of hydrogen peroxide, with an apparent Km of 114.7±58.7 μM. The overall results substantiate the design and use of RAFT polymers towards the development of third-generation biosensors.

  19. Large Block Test Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Lin, W

    2001-12-01

    This report documents the Large-Block Test (LBT) conducted at Fran Ridge near Yucca Mountain, Nevada. The LBT was a thermal test conducted on an exposed block of middle non-lithophysal Topopah Spring tuff (Tptpmn) and was designed to assist in understanding the thermal-hydrological-mechanical-chemical (THMC) processes associated with heating and then cooling a partially saturated fractured rock mass. The LBT was unique in that it was a large (3 x 3 x 4.5 m) block with top and sides exposed. Because the block was exposed at the surface, boundary conditions on five of the six sides of the block were relatively well known and controlled, making this test both easier to model and easier to monitor. This report presents a detailed description of the test as well as analyses of the data and conclusions drawn from the test. The rock block that was tested during the LBT was exposed by excavation and removal of the surrounding rock. The block was characterized and instrumented, and the sides were sealed and insulated to inhibit moisture and heat loss. Temperature on the top of the block was also controlled. The block was heated for 13 months, during which time temperature, moisture distribution, and deformation were monitored. After the test was completed and the block cooled down, a series of boreholes were drilled, and one of the heater holes was over-cored to collect samples for post-test characterization of mineralogy and mechanical properties. Section 2 provides background on the test. Section 3 lists the test objectives and describes the block site, the site configuration, and measurements made during the test. Section 3 also presents a chronology of events associated with the LBT, characterization of the block, and the pre-heat analyses of the test. Section 4 describes the fracture network contained in the block. Section 5 describes the heating/cooling system used to control the temperature in the block and presents the thermal history of the block during the test

  20. Plasticizer-free microspheres for ionophore-based sensing and extraction based on a methyl methacrylate-decyl methacrylate copolymer matrix

    Energy Technology Data Exchange (ETDEWEB)

    Peper, Shane; Ceresa, Alan; Qin Yu; Bakker, Eric

    2003-12-19

    Plasticizer-free methyl methacrylate-decyl methacrylate (MMA-DMA) microspheres were prepared under mild, non-reactive conditions using a high-throughput particle generator. The particles were perfectly smooth and monodisperse, with a particle diameter of approximately 10.0 {mu}m. In order to evaluate the suitability of the polymer as a matrix for bulk extraction processes, lipophilic sensing components were incorporated into the particles. Particles contained either a H{sup +}-selective chromoionophore (ETH 5294) only (type 1), or a K{sup +}-selective ionophore (BME-44), anionic sites (NaTFPB), and ETH 5294 (type 2). Type 1 particles responded according to an anion-proton coextraction mechanism and demonstrated Hofmeister selectivity by showing a preference for more lipophilic sample anions (ClO{sub 4}{sup -}>NO{sub 3}{sup -}>Cl{sup -}). Particles of type 2 functioned by way of an ion-exchange equilibrium and demonstrated a functional response for K{sup +}, with a dynamic range from 10{sup -1}-10{sup -4} M K{sup +}. These particles also exhibited selectivity comparable to that previously reported for analogous particles made from bis(2-ethylhexyl sebacate) (DOS)-plasticized poly(vinyl chloride) (PVC) and DMA-DOS. In addition, the behavior of both types1 and 2 particles was in agreement with analogous thin film optical sensors (optodes) prepared from MMA-DMA. With the advent of ionophore-based plasticizer-free microspheres a wide variety of ions may potentially be assessed using various popular bead-based sensing strategies, such as lab-on-a-chip technologies, bundled optical fiber arrays, and flow cytometry, without experiencing the deleterious effects resultant of plasticizer leaching.

  1. Covariant Approaches to Superconformal Blocks

    CERN Document Server

    Fitzpatrick, A Liam; Khandker, Zuhair U; Li, Daliang; Poland, David; Simmons-Duffin, David

    2014-01-01

    We develop techniques for computing superconformal blocks in 4d superconformal field theories. First we study the super-Casimir differential equation, deriving simple new expressions for superconformal blocks for 4-point functions containing chiral operators in theories with N-extended supersymmetry. We also reproduce these results by extending the "shadow formalism" of Ferrara, Gatto, Grillo, and Parisi to supersymmetric theories, where superconformal blocks can be represented as superspace integrals of three-point functions multiplied by shadow three-point functions.

  2. Dimensional Reduction for Conformal Blocks

    CERN Document Server

    Hogervorst, Matthijs

    2016-01-01

    We consider the dimensional reduction of a CFT, breaking multiplets of the d-dimensional conformal group SO(d+1,1) up into multiplets of SO(d,1). This leads to an expansion of d-dimensional conformal blocks in terms of blocks in d-1 dimensions. In particular, we obtain a formula for 3d conformal blocks as an infinite sum over 2F1 hypergeometric functions with closed-form coefficients.

  3. Adductor Canal Block versus Femoral Nerve Block and Quadriceps Strength

    DEFF Research Database (Denmark)

    Jæger, Pia Therese; Nielsen, Zbigniew Jerzy Koscielniak; Henningsen, Lene Marianne;

    2013-01-01

    : The authors hypothesized that the adductor canal block (ACB), a predominant sensory blockade, reduces quadriceps strength compared with placebo (primary endpoint, area under the curve, 0.5-6 h), but less than the femoral nerve block (FNB; secondary endpoint). Other secondary endpoints were...

  4. Synthesis and characterization of the silver methacrylate and its polymerization with gamma radiation

    International Nuclear Information System (INIS)

    One of the traditional objectives in research has been the development of new and useful materials that combine the properties of polymers with metals. Synthesis of monomers containing metal, followed by a polymerization process, is a method to introduce metal ions in the structure of a polymer, and the gamma radiation was easily applied to initiate polymerization. The coordination polymers have high insolubility, which is a general problem of these materials, besides the lack of structural information available. Also, due to the difficulty of obtaining single crystals, it has hindered the identification of the structures of some coordination polymers, requiring the use of indirect methods for structural characterization. In this work the synthesis of silver poly-methacrylate (PMAAg), was performed using the gamma radiation as polymerization initiator, having as precursor to silver methacrylate monomer (MAAg). The combination of spectroscopic methods revealed structural changes in the coordination polymers. With scanning electron microscopy, it was observed that the morphology of the monomer and its polymers is fiber, which grows with increasing radiation dose; furthermore, this increase in size is related to Bet analysis result, since the monomer has a bigger superficial area to the irradiated polymers. In monomer and irradiated polymers the crystalline structure CCC was observed by X-ray diffraction. By thermogravimetric analysis the decomposition temperature of the products was determined, finding around 150 degrees C. The infrared spectroscopy confirmed the silver methacrylate polymerization, as with increasing radiation dose, also increases the degree of polymerization; likewise the form of coordination of the monomer was determined and its irradiated polymers which corresponds to a bi-dentate chelate, confirmed by X-ray photoelectron spectroscopy. (Author)

  5. Addition of silver nanoparticles reduces the wettability of methacrylate and silorane-based composites

    Directory of Open Access Journals (Sweden)

    Shahin Kasraei

    2012-12-01

    Full Text Available Incorporation of silver nanoparticles into composite resins is recommended for their reported antibacterial properties, but this incorporation can affect the wettability of such materials. Therefore, this study evaluated the effect of nano-silver addition to silorane-based and methacrylate-based composites on their contact angle. Nano-silver particles were added to Z250 (methacrylate-based and P90 (silorane-based composites at 0.5% and 1% by weight. The control group had no additions. SEM-EDX analysis was performed to confirm the homogeneity of the nano-silver distribution. Seventy-two composite discs were prepared and standardized to the identical surface roughness values, and then distributed randomly into 6 groups containing 12 samples each (N = 12. Two random samples from each group were observed by atomic force microscopy. Distilled water contact angle measurements were performed for the wettability measurement. Two-way ANOVA, followed by the Tukey-HSD test, with a significance level of 5%, were used for data analysis. It was observed that wettability was significantly different between the composites (p = 0.0001, and that the addition of nano-silver caused a significant reduction in the contact angle (p = 0.0001. Wettability varied depending on the concentration of the nano silver (p = 0.008. Silorane-based composites have a higher contact angle than methacrylate-based composites. Within the limitations of this study, it can be concluded that the addition of 0.5% nano-silver particles to the composites caused a decrease in the contact angle of water.

  6. Effect of film thickness on the antifouling performance of poly(hydroxy-functional methacrylates) grafted surfaces.

    Science.gov (United States)

    Zhao, Chao; Li, Lingyan; Wang, Qiuming; Yu, Qiuming; Zheng, Jie

    2011-04-19

    The development of nonfouling biomaterials to prevent nonspecific protein adsorption and cell/bacterial adhesion is critical for many biomedical applications, such as antithrombogenic implants and biosensors. In this work, we polymerize two types of hydroxy-functional methacrylates monomers of 2-hydroxyethyl methacrylate (HEMA) and hydroxypropyl methacrylate (HPMA) into polymer brushes on the gold substrate via surface-initiated atom transfer radical polymerization (SI-ATRP). We systematically examine the effect of the film thickness of polyHEMA and polyHPMA brushes on their antifouling performance in a wide range of biological media including single-protein solution, both diluted and undiluted human blood serum and plasma, and bacteria culture. Surface plasmon resonance (SPR) results show a strong correlation between antifouling property and film thickness. Too thin or too thick polymer brushes lead to large protein adsorption. Surfaces with the appropriate film thickness of ∼25-45 nm for polyHPMA and ∼20-45 nm for polyHEMA can achieve almost zero protein adsorption (thickness of ∼20-30 nm adsorb only ∼3.0 and ∼3.5 ng/cm(2) proteins, respectively, while polyHPMA brushes at a film thickness of ∼30 nm adsorb more proteins of ∼13.5 and ∼50.0 ng/cm(2), respectively. Moreover, both polyHEMA and polyHPMA brushes with optimal film thickness exhibit very low bacteria adhesion. The excellent antifouling ability and long-term stability of polyHEMA and polyHPMA brushes make them, especially for polyHEMA, effective and stable antifouling materials for usage in blood-contacting devices. PMID:21405141

  7. Determination of thermodynamic properties of poly(cyclohexyl methacrylate)by inverse gas chromatography

    Institute of Scientific and Technical Information of China (English)

    Ismet KAYA; Cigdem Yigit PALA

    2014-01-01

    In this work,some thermodynamic properties of poly( cyclohexyl methacrylate)were studied by inverse gas chromatography( IGC). For this purpose,the polymeric substance was coated on Chromosorb W and which was filled into a glass column. The retention times(tr)of the probes were determined from the interactions of poly(cyclohexyl methacrylate)with n-pentane,n-hexane,n-heptane,n-octane,n-decane, methanol,ethanol,2-propanol,butanol,acetone,ethyl methyl ketone,benzene,toluene and o-xylene by IGC technique. Then,the specific volume(V0g)was determined for each probe molecule. By using(1/T;lnV0g) graphics,the glass transition temperature of poly( cyclohexyl methacrylate)was found to be 373 K. The adsorp-tion heat under the glass transition temperature(ΔH a ),and partial molar heat of sorption above the glass tran-sition(ΔHS1 ),partial molar free energy of sorption(ΔGS1 )and partial molar entropy of sorption(ΔSS1 )belong-ing to sorption for every probe were calculated. The partial molar heat of mixing at infinite dilution(ΔH∞1 ), partial molar free energy of mixing at infinite dilution(ΔG∞1 ),Flory-Huggins interaction parameter(χ∞12 )and weight fraction activity coefficient(a1/w1)∞ values of polymer-solute systems were calculated at different col-umn temperatures. The solubility parameters(δ2 )of the polymer were obtained by IGC technique.

  8. Utilization of Methacrylates and Polymer Matrices for the Synthesis of Ion Specific Resins

    Energy Technology Data Exchange (ETDEWEB)

    Czerwinski, Kenneth [Univ. of Nevada, Las Vegas, NV (United States)

    2013-10-29

    Disposal, storage, and/or transmutation of actinides such as americium (Am) will require the development of specific separation schemes. Existing efforts focus on solvent extraction systems for achieving suitable separation of actinide from lanthanides. However, previous work has shown the feasibility of ion-imprinting polymer-based resins for use in ion-exchange-type separations with metal ion recognition. Phenolic-based resins have been shown to function well for Am-Eu separations, but these resins exhibited slow kinetics and difficulties in the imprinting process. This project addresses the need for new and innovative methods for the selective separation of actinides through novel ion-imprinted resins. The project team will explore incorporation of metals into extended frameworks, including the possibility of 3D polymerized matrices that can serve as a solid-state template for specific resin preparation. For example, an anhydrous trivalent f-element chain can be formed directly from a metal carbonate, and methacrylic acid from water. From these simple coordination complexes, molecules of discrete size or shape can be formed via the utilization of coordinating ligands or by use of an anionic multi-ligand system incorporating methacrylate. Additionally, alkyl methyl methacrylates have been used successfully to create template nanospaces, which underscores their potential utility as 3D polymerized matrices. This evidence provides a unique route for the preparation of a specific metal ion template for the basis of ion-exchange separations. Such separations may prove to be excellent discriminators of metal ions, even between f-elements. Resins were prepared and evaluated for sorption behavior, column properties, and proton exchange capacity.

  9. Dielectric Relaxation of Methyl Methacrylate and Ethyl Methacrylate on Complexation with Phenols%甲基丙烯酸甲酯、甲基丙烯酸乙酯与酚络合的介电驰豫行为

    Institute of Scientific and Technical Information of China (English)

    LIAKATHALIKHAN Faize; SIVAGURUNATHAN Periyasamy

    2007-01-01

    Dielectric absorption studies of H-bonded complexes of methyl methacrylate (MMA) and ethyl methacrylate (EMA) with p-cresol, p-chlorophenol, 2,4-dichlorophenol, and p-bromophenol were studied at microwave frequency 9.37 GHz in dilute solution of carbon tetrachloride at 308 K. Different dielectric parameters like dielectric constant ε' and dielectric loss ε" at microwave frequency, static dielectric constant ε0 and dielectric constant ε∞ at optical frequency were determined. The validity of the single frequency equation of Higasi et al. for multiple relaxation time τ(1) was found to be a function of the hydrogen bonding strength of phenolic hydrogen, whereas the group rotation relaxation time τ(2) was a function of the steric interaction of proton donor. The relaxation time was the maximum at 50:50 (molar ratio) of methacrylates with phenols.

  10. Preparation and Characterization of Mesoporous Zirconia Made by Using a Poly (methyl methacrylate Template

    Directory of Open Access Journals (Sweden)

    Zhang Chunxiang

    2008-01-01

    Full Text Available AbstractSuperfine powders of poly (methyl methacrylate (PMMA have been prepared by means of an emulsion polymerization method. These have been used as templates in the synthesis of tetragonal phase mesoporous zirconia by the sol–gel method, using zirconium oxychloride and oxalic acid as raw materials. The products have been characterized by infrared spectroscopy, X-ray diffraction analysis, transmission electron microscopy, N2adsorption-desorption isotherms, and pore size distribution. The results indicate that the average pore size was found to be 3.7 nm.

  11. Thermal response of polystyrene/poly methyl methacrylate (PS/PMMA) polymeric blends

    Science.gov (United States)

    Mathur, Vishal; Sharma, Kananbala

    2016-02-01

    The present paper reports the investigationsto evaluate thermal behavior of polystyrene/poly methyl methacrylate (PS/PMMA) polymeric blends, prepared at different compositions through solution casting method. The glass transition temperatures have been obtained using dynamic mechanical analyzer. Simultaneous measurements of temperature dependentthermal transport properties (thermal conductivity and thermal diffusivity) have been made using Hot Disk Thermal Constants Analyzer based on transient plane source. The study reveals that blending of PS with PMMA leads to different phase morphologies corresponding to different composition range which further affects the thermal performance of respective blends.

  12. Kinetics of Vinyl Polymerization of Methyl Methacrylate Initiated by Ce(IV)-Vanillin Redox System

    OpenAIRE

    Palanivelu, M.; K. E. N. Nalla Mohamed; T. Hidayathulla Khan; M. Prem Nawaz

    2012-01-01

    The kinetics of polymerization of methyl methacrylate initiated by Ce(IV)-Vanillin redox system was studied in aqueous solution of sulfuric acid at 40°C. The rate of polymerization (Rp) and the reaction orders with respect to monomer, initiator and ligand have been determined and found to be 1.5, 0.5 and 0.5 respectively. The effect of concentration of sulfuric acid on the polymerization was also studied. The rate of polymerization was found to increase with increasing temperature 30–60°C and...

  13. Nano-engineered optical properties of iodine doped poly(methyl methacrylate)

    Science.gov (United States)

    Mehta, Sheetal; Keller, Jag Mohan; Das, Kallol

    2016-05-01

    Poly (methyl methacrylate) (PMMA) and Iodine hybrid matrixes have been prepared and characterized. The optical properties of the prepared I-PMMA hybrid composites were characterized by linear absorption studies and these composites have been found to contain embedded Iodine nanoparticles. The size of the nanoparticles was found to be a function of the Iodine content of PMMA. Refractive index measurements were undertaken for different wavelengths. The results showed that the refractive index of the composite is dependent on thermal annealing and also varies nonlinearly with the doping concentration at low Iodine concentration or in the region of nanoparticles formation.

  14. Poly (methyl methacrylate) Composites with Size-Selected Silver Nanoparticles Fabricated using Cluster Beam Technique

    DEFF Research Database (Denmark)

    Hanif, Muhammad; Juluri, Raghavendra Rao; Chirumamilla, Manohar;

    2016-01-01

    An embedment of metal nanoparticles of well-defined sizes in thin polymer films is of significant interest for a number of practical applications, in particular, for preparing materials with tunable plasmonic properties. In this article, we present a fabrication route for metal–polymer composites...... based on cluster beam technique allowing the formation of monocrystalline size-selected silver nanoparticles with a ±5–7% precision of diameter and controllable embedment into poly (methyl methacrylate). It is shown that the soft-landed silver clusters preserve almost spherical shape with a slight...

  15. Microstructure-property relationships in alumina trihydrate filled poly (methyl methacrylate) composite materials

    Science.gov (United States)

    Zhang, Ruoyu

    2015-07-01

    The mechanical properties (Young's modulus and fracture toughness) of composite made from a poly (methyl methacrylate) (PMMA) matrix filled with alumina trihydrate(ATH) are reported. The experiments were performed using flexural tests and single edge notched bend (SENB) tests. The composites samples were tested at a range of filler volume fractions (34.7%, 39.4% and 44.4%) and mean filler diameters (8 pm, 15 pm and 25 pm). The data of Young's modulus agreed well with the results of Lielens model and finite element analysis (FEA) model.

  16. VISCOMETRIC STUDY OF POLY(METHYL METHACRYLATE) AND POLYSTYRENE BLENDS IN DIFFERENT SOLVENTS

    Institute of Scientific and Technical Information of China (English)

    Chang-you Gao; An-zhen Zhang; Bai Yang; Jia-cong Shen

    2003-01-01

    The intermolecular interaction between poly(methyl methacrylate) (PMMA) and polystyrene (PS) in tetrahydrofuran (THF) and N,N'-dimethyl formamide (DMF) solvents was studied at 28℃ using a dilute solution viscometry method. Solvent is believed to play a key role in characterizing the viscosity behavior of the polymer solution. The intrinsic viscosity and viscosity interaction parameter were experimentally measured for the binary (solvent/polymer) and for the ternary systems in two solvents. The compatibility of the polymer mixture was discussed in terms of the sign of △bm. The results show that the compatibility of PMMA/PS blend in DMF is larger than that in THF.

  17. Fracture resistance of Kevlar-reinforced poly(methyl methacrylate) resin: a preliminary study.

    Science.gov (United States)

    Berrong, J M; Weed, R M; Young, J M

    1990-01-01

    The reinforcing effect of Kevlar fibers incorporated in processed poly(methyl methacrylate) resin samples was studied using 0% (controls), 0.5%, 1%, and 2% by weight of the added fibers. The samples were subjected to impact testing to determine fracture resistance, and sample groups were statistically compared using an ANOVA. Each reinforced sample had significantly greater fracture resistance (P less than 0.05) than the control, and no difference was found either within or between control groups. The use of reinforcing Kevlar fibers appears to enhance the fracture resistance of acrylic resin denture base materials.

  18. Electrochemical analysis on poly(ethyl methacrylate)-based electrolyte membranes

    Indian Academy of Sciences (India)

    Chithra M Mathew; B Karthika; M Ulaganathan; S Rajendran

    2015-02-01

    Polymer blend composed of poly(vinyl chloride) and poly(ethyl methacrylate) with lithium perchlorate (LiClO4) and the plasticizer ethylene carbonate (EC) mixture with propylene carbonate, -butyrolactone (GBL), dibutyl phthalate and diethyl carbonate have been synthesized using the solution casting technique. Structural changes and thermal stability of the films were resolved using X-ray diffraction analysis and thermogravimetric/differential thermal analysis, respectively. The membrane that contains EC+ GBL exhibits maximum ionic conductivity of the order of 1.208×10-3 S cm-1 at 303 K. The temperature-dependent ionic conductivity of the polymer membranes has been estimated using AC impedance analysis.

  19. Ionic liquids as porogens in the microwave-assisted synthesis of methacrylate monoliths for chromatographic application

    Energy Technology Data Exchange (ETDEWEB)

    Singco, Brenda; Lin, Chen-Lan; Cheng, Yi-Jie; Shih, Yung-Han [Department of Chemistry and Center for Nanotechnology, CYCU (Chung Yuan Christian University), 200 Chung Pei Road, Chung-Li 320, Taiwan (China); Huang, Hsi-Ya, E-mail: hyhuang@cycu.edu.tw [Department of Chemistry and Center for Nanotechnology, CYCU (Chung Yuan Christian University), 200 Chung Pei Road, Chung-Li 320, Taiwan (China)

    2012-10-09

    Highlights: Black-Right-Pointing-Pointer An efficient and cleaner monoliths preparation utilizing ionic liquids in conjunction with microwave Black-Right-Pointing-Pointer These ionic liquids with varied cation alkyl chain and anion type successfully tuned the morphology of different alkyl methacrylates Black-Right-Pointing-Pointer Small molecules and peptide digests separated well in these monoliths. - Abstract: Several imidazolium-based ionic liquids (ILs) with varying cation alkyl chain length (C{sub 4}-C{sub 10}) and anion type (tetrafluoroborate ([BF{sub 4}]{sup -}), hexafluorophosphate ([PF{sub 6}]{sup -}) and bis(trifluoromethylsulfonyl)imide ([Tf{sub 2}N]{sup -})) were used as reaction media in the microwave polymerization of methacrylate-based stationary phases. Scanning electron micrographs and backpressures of poly(butyl methacrylate-ethylene dimethacrylate) (poly(BMA-EDMA)) monoliths synthesized in the presence of these ionic liquids demonstrated that porosity and permeability decreased when cation alkyl chain length and anion hydrophobicity were increased. Performance of these monoliths was assessed for their ability to separate parabens by capillary electrochromatography (CEC). Intra-batch precision (n = 3 columns) for retention time and peak area ranged was 0.80-1.13% and 3.71-4.58%, respectively. In addition, a good repeatability of RSD{sub Retentiontime} = <0.30% and {approx}1.0%, RSD{sub Peakarea} = <1.30% and <4.3%, and RSD{sub Efficiency} = <0.6% and <11.5% for intra-day and inter-day, respectively exemplify monolith performance reliability for poly(BMA-EDMA) fabricated using 1-hexyl-3-methylimidazolium tetrafluoroborate ([C{sub 6}mim][BF{sub 4}]) porogen. This monolith was also tested for its potential in nanoLC to separate protein digests in gradient mode. ILs as porogens also fabricated different alkyl methacrylate (AMA) (C4-C18) monoliths. Furthermore, employing binary IL porogen mixture such as 1-butyl-3-methylimidazolium tetrafluoroborate

  20. Kinetics and mechanism of polymerization of methyl methacrylate initiated by stibonium ylide

    Indian Academy of Sciences (India)

    A K Srivastava; Ajey Kumar Chaurasia

    2004-01-01

    Homopolymerization of methyl methacrylate (MMA) was carried out in the presence of triphenylstibonium 1,2,3,4-tetraphenyl-cyclopentadienylide as an initiator in dioxane at 65°C ± 0·1°C. The system follows non-ideal radical kinetics ( ∝ [M]1.4 [I]0.44) due to primary radical termination as well as degradative chain-transfer reaction. The overall activation energy and average value of $k_{p}^{2}/k_{t}$ were 64 kJ mol-1 and 0.173 × 10-3 l mol-1 s-1 respectively.

  1. Influence of surface treatments to repair recent fillings of silorane-and methacrylate-based composites

    OpenAIRE

    Marina Kaneko; Ricardo Armini Caldas; Victor Pinheiro Feitosa; Rafael Leonardo Xediek Consani; Schneider, Luis Felipe J.; Ataís Bacchi

    2015-01-01

    Purpose: The aim of this study was to evaluate the tensile bond strength (TBS) of repairs in recent fillings of methacrylate- (MBC) or silorane-based composites (SBC) subsequent to different surface treatments. Materials and Methods: Fifty slabs of Filtek P60 (3M ESPE, St Paul, USA) and Filtek P90 (3M ESPE) were stored for 10 days in distilled water at 37°C. The surface of adhesion was abraded with a 600-grit silicone paper and repaired using each respective composite: G1, no treatment (...

  2. Far infrared-assisted encapsulation of filter paper strips in poly(methyl methacrylate) for proteolysis.

    Science.gov (United States)

    Chen, Qiwen; Bao, Huimin; Zhang, Luyan; Chen, Gang

    2016-02-01

    Filter paper strips were enclosed between two poly(methyl methacrylate) plates to fabricate paper-packed channel microchips under pressure in the presence of far infrared irradiation. After the enclosed paper strip was oxidized by periodate, trypsin was covalently immobilized in them to fabricate microfluidic proteolysis bioreactor. The feasibility and performance of the unique bioreactor were demonstrated by digesting BSA and lysozyme. The results were comparable to those of conventional in-solution proteolysis while the digestion time was significantly reduced to ∼18 s. The suitability of the microfluidic paper-based bioreactors to complex proteins was demonstrated by digesting human serum.

  3. Solid State Dye Lasers Based on Coumarin 440 and Pyrromethene 567 Codoped Polymethyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    FAN Rong-Wei; LI Xiao-Hui; XIA Yuan-Qin; JIANG Yu-Gang; HE Wei-Ming; CHEN De-Ying

    2008-01-01

    Laser dye coumarin 440(C440) is codoped with pyrromethene 567 (PM567) into polymethyl methacrylate (PMMA ).The effects of C440 concentration on the performance of the solid state dye medium,including spectra property,slope efficiency and photostability,are studied.When C440 is codoped with PM567 at the same concentration 1 × 10-4 mol/L,the highest efficiency and photostability can be obtained.Compared with the medium based on pure PM567 doped PMMA,about 50% increase in slope efficiency and at least five-fold enhancement in the photostabifity are observed.

  4. Mechanical and Thermal Properties of Polymethyl Methacrylate-BN Nanotube Composites

    Directory of Open Access Journals (Sweden)

    C. Y. Zhi

    2008-01-01

    Full Text Available Polymethyl methacrylate (PMMA-BN nanotube (BNNT composites were fabricated and their mechanical and thermal properties were analyzed. Using a 1 wt.% BNNTs fraction in a polymer, the elastic modulus of PMMA was increased up to 19%. In addition, thermal stability and glass transition temperature of PMMA were also positively affected. The thermal conductivity of PMMA with BNNT additions increased three times. The resultant BNNT-PMMA composites possess the high electrical breakover voltages. Thus our studies clearly indicate that BNNTs are promising nanofillers for improvement of mechanical and thermal conductivity of dielectric polymers under preservation of their electrical insulation.

  5. Kinetic Treatment for Copolymerization of Styrene or Methyl Methacrylate with N-phenylmaleimide

    Institute of Scientific and Technical Information of China (English)

    单国荣; 翁志学; 黄志明; 潘祖仁

    2000-01-01

    Shirota's kinetic model and our kinetic model were used to treat the kinetic data of styrene (St) and N-phenylmaleimide (PMI) copolymerization in which chaxge-transfer complex (CTC) was formed. The results obtained by Shirota's kinetic model were disagreed with the experiments and the experimental phenomena could not be explained. The kinetic data of all feed fractions can be treated with our kinetic model, and the experimental phenomena can be explained from the propagation constants and reactivity ratios. Our kinetic model is also suitable for the kinetic data of methyl methacrylate (MMA) and PMI copolymerization in which CTC can not be formed.

  6. Multi-block and path modelling procedures

    DEFF Research Database (Denmark)

    Høskuldsson, Agnar

    2008-01-01

    The author has developed a unified theory of path and multi-block modelling of data. The data blocks are arranged in a directional path. Each data block can lead to one or more data blocks. It is assumed that there is given a collection of input data blocks. Each of them is supposed to describe one...... or more intermediate data blocks. The output data blocks are those that are at the ends of the paths and have no succeeding data blocks. The optimisation procedure finds weights for the input data blocks so that the size of the total loadings for the output data blocks are maximised. When the optimal...... weight vectors have been determined, the score and loading vectors for the data blocks in the path are determined. Appropriate adjustment of the data blocks is carried out at each step. Regression coefficients are computed for each data block that show how the data block is estimated by data blocks...

  7. OPAL Various Lead Glass Blocks

    CERN Multimedia

    These lead glass blocks were part of a CERN detector called OPAL (one of the four experiments at the LEP particle detector). OPAL uses some 12 000 blocks of glass like this to measure particle energies in the electromagnetic calorimeter. This detector measured the energy deposited when electrons and photons were slowed down and stopped.

  8. Block storage subsystem performance analysis

    CERN Document Server

    CERN. Geneva

    2016-01-01

    You feel that your service is slow because of the storage subsystem? But there are too many abstraction layers between your software and the raw block device for you to debug all this pile... Let's dive on the platters and check out how the block storage sees your I/Os! We can even figure out what those patterns are meaning.

  9. Classical Virasoro irregular conformal block

    CERN Document Server

    Rim, Chaiho

    2015-01-01

    Virasoro irregular conformal block with arbitrary rank is obtained for the classical limit or equivalently Nekrasov-Shatashvili limit using the beta-deformed irregular matrix model (Penner-type matrix model for the irregular conformal block). The same result is derived using the generalized Mathieu equation which is equivalent to the loop equation of the irregular matrix model.

  10. The Shamrock lumbar plexus block

    DEFF Research Database (Denmark)

    Sauter, Axel R; Ullensvang, Kyrre; Niemi, Geir;

    2015-01-01

    BACKGROUND: The Shamrock technique is a new method for ultrasound-guided lumbar plexus blockade. Data on the optimal local anaesthetic dose are not available. OBJECTIVE: The objective of this study is to estimate the effective dose of ropivacaine 0.5% for a Shamrock lumbar plexus block. DESIGN: A...... prospective dose-finding study using Dixon's up-and-down sequential method. SETTING: University Hospital Orthopaedic Anaesthesia Unit. INTERVENTION: Shamrock lumbar plexus block performance and block assessment were scheduled preoperatively. Ropivacaine 0.5% was titrated with the Dixon and Massey up......-and-down method using a stepwise change of 5 ml in each consecutive patient. Combined blocks of the femoral, the lateral femoral cutaneous and the obturator nerve were prerequisite for a successful lumbar plexus block. PATIENTS: Thirty patients scheduled for lower limb orthopaedic surgery completed the study...

  11. Effect of Mixed Solvent on Fabrication, Morphology and Monodispersity of Microspheres with Hydrophobic Poly(butyl methacrylate) Shells

    Institute of Scientific and Technical Information of China (English)

    XIAO Xincai; LU Cheng

    2012-01-01

    Monodisperse microspheres (mean diameter 200-300 nm) with polystyrene cores and poly(acrylamide-co-buty1 methacrylate) shells were prepared by using a free radical polymerization method.Moreover,the effect of mixed solvent on the preparation,morphology and monodispersity was investigated.The experimental results showed that solubility parameter of butyl methacrylate and solvent affected mainly the molding of monodisperse core-shell microspheres.When the microspheres were fabricated in a sequential synthesis process,addition of hydrophilic and organic solvent including butyl methacrylate led to spherical degree of the particles becoming worse,and the mean diameter of the microspheres decreased and the monodispersity became better with increasing the crosslinker methylenebisacrylamide dosage.

  12. Thin Isoporous Block Copolymer Membranes: It Is All about the Process.

    Science.gov (United States)

    Hahn, Janina; Clodt, Juliana I; Abetz, Clarissa; Filiz, Volkan; Abetz, Volker

    2015-09-30

    The combination of the self-assembly of amphiphilic block copolymers and the nonsolvent induced phase inversion process offers an efficient way to isoporous integral-asymmetric membranes. In this context we report fast, easily upscalable and material reducing ways to thin self-assembled membranes. Therefore, we succeeded to implement a spray or dip coating step into the membrane formation process of different diblock copolymers like polystyrene-block-poly(4-vinylpyridine), poly(α-methylstyrene)-bock-poly(4-vinylpyridine), and polystyrene-block-poly(iso-propylglycidyl methacrylate). The formation of hexagonal pore structures was possible using a highly diluted one solvent system allowing the reduction of diblock copolymer consumption and therefore the production costs are minimized compared to conventional blade casting approaches. The broad applicability of the process was proven by using different flat and hollow fiber support materials. Furthermore, the membranes made by this new method showed a more than 6-fold increase in water flux compared to conventional polystyrene-block-poly(4-vinylpyridine) membranes with similar pore sizes prepared by blade casting. The membranes could be proven to be stable at transmembrane pressures of 2 bar and showed a pH responsive flux behavior over several cycles. PMID:26349610

  13. Micellar cathodes from self-assembled nitroxide-containing block copolymers in battery electrolytes.

    Science.gov (United States)

    Hauffman, Guillaume; Maguin, Quentin; Bourgeois, Jean-Pierre; Vlad, Alexandru; Gohy, Jean-François

    2014-01-01

    This contribution describes the synthesis of block copolymers containing electrochemically active blocks, their micellization, and finally their use as micellar cathodes in a lithium battery. The self-assembly of the synthesized poly(styrene)-block-poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PS-b-PTMA) diblock copolymers is realized in a typical battery electrolyte made of 1 m lithium trifluoromethanesulfonate dissolved in a mixture of ethylene carbonate/diethyl carbonate/dimethyl carbonate(1:1:1, in volume). Dynamic light scattering and atomic force micro-scopy indicate the formation of well-defined spherical micelles with a PS core and a PTMA corona. The electrochemical properties of those micelles are further investigated. Cyclic voltammograms show a reversible redox reaction at 3.6 V (vs Li(+) /Li). The charge/discharge profiles indicate a flat and reversible plateau around 3.6 V (vs Li(+) /Li). Finally, the cycling performances of the micellar cathodes are demonstrated. Such self-assembled block copolymers open new opportunities for nanostructured organic radical batteries. PMID:24127365

  14. Effect of Nanoclay on Thermal Conductivity and Flexural Strength of Polymethyl Methacrylate Acrylic Resin

    Directory of Open Access Journals (Sweden)

    Tahereh Ghaffari

    2016-06-01

    Full Text Available 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 powder. Scanning electron microscopy was used to verify homogeneous distribution of particles. Twenty-four 20×20×200-mm cubic samples were prepared for flexural strength test; 18 samples containing nanoclay and 6 samples for the control group. Another 24 cylindrical samples of 38×25 mm were prepared for thermal conductivity test. One-way ANOVA was used for statistical analysis, followed by multiple-comparison test (Scheffé’s test. Statistical significance was set at p< 0.05. Results: Increasing the concentration of nanoclay incorporated into the acrylic resin samples increased thermal conductivity but decreased flexural strength (p< 0.05. Conclusion: Based on the results of this study, adding nanoclay particles to PMMA improved its thermal conductivity, while it had a negative effect on the flexural strength.

  15. Study on polyethylene films grafted with vinyl acetate and ethyl methacrylate by radiation grafting

    International Nuclear Information System (INIS)

    Low density polyethylene (LDPE) films were grafted with a vinyl acetate (VAc) and ethyl methacrylate (EMA) commoner mixture by radiation using a 60Co gamma source. IR spectra and x-ray diffraction (XRD) for the original PE matrix and for the graft copolymers were studied. Electrical conductivity and thermal properties of the prepared grafted materials were also measured. XRD results showed that poly(vinyl acetate/ethyl methacrylate) P(VAc/EMA) graft chains cause a decrease in the crystallinity of the PE polymer substrate. The changes in thermal parameters such as melting (Tm) and crystallization (Tc) temperatures and heats of melting (ΔHm) and crystallization (ΔHc) of the graft copolymers were followed by differential scanning calorimetry (DSC) and for thermal stability by TGA. These thermal parameters of PE were influenced by grafting, with VAc and EMA and depended on the percent grafting, which reflected the change in crystallinity due to formation of branches via the grafted chains. (author)

  16. Low-cost fabrication of poly(methyl methacrylate) microchips using disposable gelatin gel templates.

    Science.gov (United States)

    Chen, Zhi; Yu, Zhengyin; Chen, Gang

    2010-06-15

    A simple method based on disposable gelatin gel templates has been developed for the low-cost fabrication of poly(methyl methacrylate) (PMMA) microfluidic chips. Gelatin was dissolved in glycerol aqueous solution under heat to prepare a thermally reversible impression material. The molten gel was then sandwiched between a glass plate and a SU-8 template bearing negative relief of microstructure. After cooling, the negative SU-8 template could be easily separated from the solidified gelatin gel and a layer of gelatin template bearing positive relief of the microstructure was left on the glass plate. Subsequently, prepolymerized methyl methacrylate molding solution containing a UV-initiator was sandwiched between the gel template and a PMMA plate and was allowed to polymerize under UV light to fabricate PMMA channel plate at room temperature. Complete microchips could be obtained by bonding the channel plates with covers using plasticizer-assisted thermal bonding at 90 degrees C. Gelatin gel template can be mass-produced and will find application in the mass production of PMMA microchips at low cost. The prepared microfluidic microchips have been successfully employed in the capillary electrophoresis analysis of several ions in connection with contactless conductivity detection.

  17. Molecular Interaction Studies of Benzyl Alcohols with Methacrylates in Carbon Tetrachloride using Frequency Domain Technique

    Directory of Open Access Journals (Sweden)

    S. Radhakrishnan

    2016-08-01

    Full Text Available The dielectric relaxation of benzyl alcohol substitutents (benzyl alcohol, m-methylbenzyl alcohol and m-nitrobenzyl alcohol with methyl methacrylate and butyl methacrylate in dilute solution of carbon tetrachloride is measured at 9.37 GHz using Frequency domain (X-band technique. Different dielectric parameters like dielectric constant (ε׳, dielectric loss factor (ε״ at Microwave frequency, static dielectric constant (ε0 and dielectric constant at infinite dilution (ε∞ at optical frequency have been determined. From the measured dielectric data, the relaxation time (t calculated using Higasi method and activation energies (∆Ft and ∆Fη have been determined. All the dielectric parameters that are vary with the substitutent change in benzyl alcohol andchain length of acrylic esters. Suggests that, the proton donating ability is varying with the substitution of benzyl alcohol and proton accepting ability is varying with the chain length of acrylic esters. The relaxation time and molar free energy activation of 1:1 molar ratio is greater than other higher molar ratios (i.e. 3:1, 2:1, 1:2, 1:3 confirm that the existence of most likely 1:1 complex formation between the studied systems and also complex formation formed between free hydroxyl group of substituted benzyl alcohols and carbonyl group of acrylic esters (MMA and EMA.

  18. Synthesis and characterization of poly(carbazole ethyl methacrylate) and its electrodeposition on ITO

    International Nuclear Information System (INIS)

    Poly(ethyl methacrylate) functionalized with pendant carbazole moieties was synthesized via reversible addition fragmentation chain-transfer (RAFT) polymerization. Structural characteristics of the homopolymers were studies using Fourier-transform Infrared (FT-IR) and proton nuclear magnetic resonance (“1H-NMR). Gel permeation chromatography (GPC) was utilized to determine the molecular weight and showed an average of 27,000 g/mol. To determine the carbazole pendants of poly(ethyl methacrylate), cylic voltammetry was employed. This was done by sweeping the potential across the three electrode system form 0-1.4V with indium tin oxide (ITO) coated glass slide serving as the working electrode. The structure and optical characteristics of the electrodeposited polycarbazole film were then observed using UV-Vis and FT-IR spectroscopy, respectively. Scanning electron microscopy (SEM) was used to investigate the surface morphology of the film while its thickness was measured using spectroscopic ellipsometry. Atomic force microscopy (AFM) was also employed to determine the surface roughness and topography of the film. Investigation of the characteristics of electropolymerized carbazole film may lead to interesting electrochromic properties, alternative materials in electro-optical devices and may have potential application in organic photovoltaic devices (OPVs). (author)

  19. Binding of leachable components of polymethyl methacrylate (PMMA) and peptide on modified SPR chip

    International Nuclear Information System (INIS)

    Many types of polymers are often used in dentistry, which may cause allergic reaction, mainly methyl methacrylate allergy due to the leachable, degradable components of polymerized dental products. The aim of this study was to investigate the interaction between the leachable components of PMMA and peptides by Fourier-transform Surface Plasmon Resonance (FT SPR). In our previous work binding of oligopeptides (Ph.D.-7 and Ph.D.-12 Peptide Library Kit) was investigated to PMMA surface by phage display technique. It was found that oligopeptides bounded specifically to PMMA surface. The most common amino acids were leucine and proline inside the amino acids sequences of DNA of phages. The binding of haptens, as formaldehyde and methacrylic acid, to frequent amino acids was to investigate on the modified gold SPR chip. Self assembled monolayer (SAM) modified the surface of gold chip and ensured the specific binding between the haptens and amino acids. It was found that amino acids bounded to modified SPR gold and the haptens bounded to amino acids by creating multilayer on the chip surface. By the application of phage display and SPR modern bioanalytical methods the interaction between allergens and peptides can be investigated

  20. A Hydrogen Ion-Selective Sensor Based on Non-Plasticised Methacrylic-acrylic Membranes

    Directory of Open Access Journals (Sweden)

    Musa Ahmad

    2002-08-01

    Full Text Available A methacrylic-acrylic polymer was synthesised for use as a non-plasticised membrane for hydrogen ion-selective sensor incorporating tridodecylamine as an ionophore. The copolymer consisted of methyl methacrylate and n-butyl acrylate monomers in a ratio of 2:8. Characterisation of the copolymer using FTNMR demonstrated that the amount of each monomer incorporated during solution polymerisation was found to be similar to the amount used in the feed before polymerisation. The glass transition temperature of the copolymer determined by differential scanning calorimetry was -30.9 ºC. Potentiometric measurements conducted showed a linear pH response range of 4.3 – 9.6 with the response slope of 56.7 mV/decade. The selectivity of the sensors towards hydrogen ions was similar to other plasticiser based membrane electrodes and the logarithmic selectivity coefficients for discrimination against interference cations is close to –9.7. However, the incorporation of a lipophilic anion as membrane additive is essential in ensuring optimum performance of the hydrogen ion sensor.