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Sample records for azobenzene methacrylate block

  1. Azobenzene

    Integrated Risk Information System (IRIS)

    Azobenzene ; CASRN 103 - 33 - 3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

  2. Azobenzene: A Photoactive Building Block for Supramolecular Architectures.

    PubMed

    Baroncini, Massimo; Bergamini, Giacomo

    2017-01-05

    The development of nanoscale systems capable to perform specific functions under external control is a challenging task and a fascinating objective in Chemistry. Photochromic compounds undergo radical changes in their physico-chemical properties upon light excitation, for this reason they are valuable building blocks for the construction of photo-controllable molecular devices, machines and materials. The E-Z photoisomerization of azobenzene has been known for almost 80 years and - owing to its high efficiency and excellent reversibility - has been widely employed to introduce an element of photo-control in a large variety of compounds, biomolecules, nanosystems and materials. Here we present some of our research results highlighting how this outstanding photochrome can be utilized to develop systems with light-induced functionalities.

  3. Synthesis and aqueous solution properties of novel sugar methacrylate-based homopolymers and block copolymers.

    PubMed

    Narain, Ravin; Armes, Steven P

    2003-01-01

    We report the facile preparation of a range of novel, well-defined cyclic sugar methacrylate-based polymers without recourse to protecting group chemistry. 2-Gluconamidoethyl methacrylate (GAMA) and 2-lactobionamidoethyl methacrylate (LAMA) were prepared directly by reacting 2-aminoethyl methacrylate with D-gluconolactone and lactobionolactone, respectively. Homopolymerization of GAMA and LAMA by atom transfer radical polymerization (ATRP) gave reasonably low polydispersities as judged by aqueous gel permeation chromatography. A wide range of sugar-based block copolymers were prepared using near-monodisperse macroinitiators based on poly(ethylene oxide) [PEO], poly(propylene oxide) [PPO], or poly(e-caprolactone) [PCL] and/or by sequential monomer addition of other methacrylic monomers such as 2-(diethylamino)ethyl methacrylate [DEA], 2-(diisopropylaminoethyl methacrylate [DPA], or glycerol monomethacrylate [GMA]. The reversible micellar self-assembly of selected sugar-based block copolymers [PEO23-GAMA50-DEA100, PEO23-LAMA30-DEA50, PPO33-GAMA50, and PPO33-LAMA50] was studied in aqueous solution as a function of pH and temperature using dynamic light scattering, transmission electron microscopy, surface tensiometry, and 1H NMR spectroscopy.

  4. Efficient Synthesis of Poly(hydroxyethyl Methacrylate)-b-Poly(dimethylaminoethyl Methacrylate) Block Copolymer by Atom Transfer Radical Polymerization.

    NASA Astrophysics Data System (ADS)

    Tang, Wei; Loo, Yueh-Lin

    2009-03-01

    Polymers containing hydroxyethyl methacrylate (HEMA) and dimethylaminoethyl methacrylate (DMAEMA) have found wide applications in areas such as bioseparation, tissue engineering and controlled drug delivery. The controlled synthesis of block copolymers of PDMAEMA-b-PHEMA from PDMAEMA macroinitiator by atom transfer radical polymerization (ATRP), however, has not been successful due to the loss of chain end functionality during polymerization. We report an ATRP system that affords efficient chain extension from PDMAEMA to HEMA using Cu(0)/1,1,4,7,10,10-hexamethyltriethylenetetramine as the catalyst, 2-chloropropionitrile as the initiator in methanol at room temperature. A clear peak shift in the gel permeation chromatography trace towards shorter elution times indicates chain growth on HEMA addition. The chain end functionalities of PDMAEMA are thus retained and can be used to efficiently initiate chain extension reaction of HEMA. This new synthetic route opens new possibilities for the synthesis of pH- and temperature-responsive systems containing DMAEMA.

  5. Enhanced surface segregation of poly(methyl methacrylate) end-capped with 2-perfluorooctylethyl methacrylate by introduction of a second block.

    PubMed

    Ni, Huagang; Gao, Jie; Li, Xuehua; Hu, Yanyan; Yan, Donghuan; Ye, XiuYun; Wang, Xinping

    2012-01-01

    New fluorinated copolymers of poly(methyl methacrylate)-b-poly(butyl methacrylate) or poly(n-octadecyl methacrylate) end-capped with 2-perfluorooctylethyl methacrylate (PMMA(x)-b-PBMA(y)-ec-PFMA(z) or PMMA(x)-b-PODMA(y)-ec-PFMA(z)) were synthesized by living atom transfer radical polymerization. Thin films made of PMMA(230)-b-PODMA(y)-ec-PFMA(1) were characterized by differential scanning calorimetry, angle-resolved X-ray photoelectron spectroscopy and X-ray diffraction. These films were found to exhibit robust surface segregation of the end groups. Furthermore, the fluorine enrichment factor at the film surface was found to increase linearly with increasing degree of polymerization of poly(n-octadecyl methacrylate) and its increasing fusion enthalpy in the second block, which enhances the segregation of the fluorinated moieties.

  6. Photoisomerization of azobenzene moiety in crosslinking polymer materials

    NASA Astrophysics Data System (ADS)

    Wang, Hui; Chen, Wei-Qiang; Jin, Feng; Dong, Xian-Zi; Zhao, Zhen-Sheng; Duan, Xuan-Ming

    2012-10-01

    In this study, a series of acryloyloxy-substituted azobenzene derivatives, 3-(tert-butyl)-4,4'-bisacryoloxy-azobenzene (tBu-Azo-AO), 3-(tert-butyl)-4,4'-bis[3-(acryoloxy)propoxy]-azobenzene (tBu-Azo-AO3) and 3-(tert-butyl)-4,4'-bis[6-(acryoloxy)hexyloxy]-azobenzene (tBu-Azo-AO6) were synthesized and employed as monomers to prepare polymer films by copolymerizing dipentaerythritol hexaacrylate (DPE-6A) and methyl methacrylate (MMA), respectively. When exposed to a nanosecond laser beam at the wavelength of 355 nm, ultraviolet-visible (UV-Vis) absorption spectra of the resultant polymer films with different irradiation time were monitored. On the basis of the absorbance of the π-π* electronic transition, the kinetics of trans-to-cis photoisomerization of three kinds of azobenzene moieties were demonstrated and found to be influenced by both the pump energy and azobenzene concentration.

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

    SciTech Connect

    Lokitz, Bradley S; Wei, Jifeng; Hinestrosa Salazar, Juan P; Ivanov, Ilia N; Browning, James B; Ankner, John Francis; Kilbey, II, S Michael; Messman, Jamie M

    2012-01-01

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

  8. Sub-5 nm Domains in Ordered Poly(cyclohexylethylene)-block-poly(methyl methacrylate) Block Polymers for Lithography.

    SciTech Connect

    Kennemur, Justin; Yao, Li; Bates, Frank Stephen; Hillmyer, Marc

    2014-01-01

    A series of poly(cyclohexylethylene)-block-poly- (methyl methacrylate) (PCHE PMMA) diblock copolymers with varying molar mass (4.9 kg/mol Mn 30.6 kg/mol) and narrow molar mass distribution were synthesized through a combination of anionic and atom transfer radical polymerization (ATRP) techniques. Heterogeneous catalytic hydrogenation of -(hydroxy)polystyrene (PS-OH) yielded -(hydroxy)poly(cyclohexylethylene) (PCHEOH) with little loss of hydroxyl functionality. PCHE-OH was reacted with -bromoisobutyryl bromide (BiBB) to produce an ATRP macroinitiator used for the polymerization of methyl methacrylate. PCHE PMMA is a glassy, thermally stable material with a large effective segment segment interaction parameter, eff = (144.4 6.2)/T (0.162 0.013), determined by meanfield analysis of order-to-disorder transition temperatures (TODT) measured by dynamic mechanical analysis and differential scanning calorimetry. Ordered lamellar domain pitches (9 D 33 nm) were identified by small-angle X-ray scattering from neat BCPs containing 43 52 vol % PCHE ( f PCHE). Atomic force microscopy was used to show 7.5 nm lamellar features (D = 14.8 nm) which are some of the smallest observed to date. The lowest molar mass sample (Mn = 4.9 kg/mol, f PCHE = 0.46) is characterized by TODT = 173 3 C and sub-5 nm nanodomains, which together with the sacrificial properties of PMMA and the high overall thermal stability place this material at the forefront of high- systems for advanced nanopatterning applications.

  9. Primer containing dimethylaminododecyl methacrylate kills bacteria impregnated in human dentin blocks

    PubMed Central

    Chen, Chen; Cheng, Lei; Weir, Michael D; Lin, Nancy J; Lin-Gibson, Sheng; Zhou, Xue-Dong; Xu, Hockin HK

    2016-01-01

    Antibacterial dimethylaminododecyl methacrylate (DMADDM) was recently synthesized. The objectives of this study were to: (1) investigate antibacterial activity of DMADDM-containing primer on Streptococcus mutans impregnated into dentin blocks for the first time, and (2) compare the antibacterial efficacy of DMADDM with a previous quaternary ammonium dimethacrylate (QADM). Scotchbond Multi-Purpose (SBMP) bonding agent was used. DMADDM and QADM were mixed into SBMP primer. Six primers were tested: SBMP control primer P, P+2.5% DMADDM, P+5% DMADDM, P+7.5% DMADDM, P+10% DMADDM, and P+10% QADM. S. mutans were impregnated into human dentin blocks, and each primer was applied to dentin to test its ability to kill bacteria in dentinal tubules. Bacteria in dentin were collected via a sonication method, and the colony-forming units (CFU) and inhibition zones were measured. The bacterial inhibition zone of P+10% DMADDM was 10 times that of control primer (P<0.05). CFU in dentin with P+10% DMADDM was reduced by three orders of magnitude, compared with control. DMADDM had a much stronger antibacterial effect than QADM, and antibacterial efficacy increased with increasing DMADDM concentration. Dentin shear bond strengths were similar among all groups (P>0.1). In conclusion, antibacterial DMADDM-containing primer was validated to kill bacteria inside dentin blocks, possessing a much stronger antibacterial potency than the previous QADM. DMADDM-containing bonding agent was effective in eradicating bacteria in dentin, and its efficacy was directly proportional to DMADDM mass fraction. Therefore, DMADDM may be promising for use in bonding agents as well as in other restorative and preventive materials to inhibit bacteria. PMID:27811846

  10. Study of the water structure in poly(methyl methacrylate-block-2-hydroxyethyl methacrylate) and its relationship to platelet adhesion on the copolymer surface.

    PubMed

    Mochizuki, Akira; Namiki, Takahiro; Nishimori, Yusuke; Ogawa, Haruki

    2015-01-01

    The water structure and platelet compatibility of poly(methyl methacrylate (MMA)-block-2-hydroxyethyl methacrylate (HEMA)) were investigated. The molecular weight (Mn) of the polyHEMA segment was kept constant (average: 9600), while the Mn of the polyMMA segment was varied from 1340 to 7390. The equilibrium water content of the copolymers was found to be mainly governed by the HEMA content. The water structure in the copolymers was characterized in terms of the amounts of non-freezing and freezing water (abbreviated as Wnf and Wfz, respectively) using differential scanning calorimetry. It was found that the Wnf for the copolymers were higher than those estimated from the Wnf for the HEMA and MMA homopolymers and that the amount of excess non-freezing water depended on the polyMMA segment length. In addition, X-ray diffraction analysis revealed that some of the copolymers had cold-crystallizable water. These facts suggested that the polyMMA segments were involved in determining the water structures in the copolymers. Furthermore, the platelet compatibility of the copolymers was improved as compared to that of the HEMA homopolymer. It was therefore concluded that the platelet compatibility of the copolymer was related to the amount of excess non-freezing water.

  11. Effects of block copolymer self-assembly on optical anisotropy in azobenzene-containing PS-b-PMMA films.

    PubMed

    Orofino, A B; Camezzana, M F; Galante, M J; Oyanguren, P A; Zucchi, I A

    2012-03-23

    Polystyrene-b-polymethylmethacrylate (PS-b-PMMA) was selected as the host for 4-(4-nitrophenylazo)aniline (Disperse Orange 3, DO3) based on a previous study of DO3/PMMA and DO3/PS binary blends. Selective location of DO3 into the PMMA block of the copolymer was expected during self-assembly of the block copolymer since a preferential interaction of DO3 with PMMA has been demonstrated. However, surface segregation of DO3 was found during the thermal annealing used to nanostructure the copolymer. To avoid this, a thermoplastic polymer (Azo-TP) was synthesized from the bulk reaction of DO3 and diglycidyl ether of bisphenol A (DGEBA). The choice of DGEBA as a co-reactant was an attempt to encourage the selective location of azo groups in the PMMA phase of PS-b-PMMA. An inspection of solutions of Azo-TP in PS and PMMA, corroborates the preferential affinity of Azo-TP for PMMA. The Azo-TP could be satisfactorily dissolved in PS-b-PMMA. We have investigated the growth and decay processes of the optically induced birefringence in films of PS-b-PMMA containing 12 wt% Azo-TP. The resulting materials showed a good photoinduced time response, high maximum birefringence and an elevated fraction of remnant anisotropy.

  12. Evaluation of different nonspecific binding blocking agents deposited inside poly(methyl methacrylate) microfluidic flow-cells.

    PubMed

    Le, Nam Cao Hoai; Gubala, Vladimir; Gandhiraman, Ram P; Daniels, Stephen; Williams, David E

    2011-07-19

    Poly(methyl methacrylate) (PMMA) flow-cells containing microwells were deposited with different nonspecific binding blocking agents, namely, bovine serum albumin (BSA), cationic lipid (DOTAP:DOPE) and diethylene glycol dimethyl ether (DEGDME). Water contact angle (WCA) and atomic force microscope (AFM) measurements were carried out to confirm the successful depositions of BSA, DOTAP, and DEGDME onto the PMMA surfaces. Fluorescent intensity measurements were performed to evaluate the degree of nonspecific adsorption of Cy5-labeled anti-IgG proteins onto plain and oxygen plasma-treated (PT) PMMA flow-cells as well as PMMA flow-cells deposited with different above-mentioned blocking agents. We then employed a label-free detection method called total internal reflection ellipsometry (TIRE) to evaluate the stability of the deposited blocking agents inside the PMMA flow-cells. It was found that, while DOTAP:DOPE was the best agent for blocking the nonspecific adsorption, it could be removed from the PMMA surfaces of the flow-cells upon rinsing with phosphate buffered saline (PBS) and later deposited back onto the Au-coated glass sensing substrate of the TIRE. The removal of the blocking agents from PMMA surfaces and their deposition onto the sensing substrate were further manifested by measuring the kinetics and the amount of adsorbed anti-α-hCG proteins. Overall, the dry DEGDME coating by plasma-enhanced chemical vapor deposition (PECVD) showed very good blocking and excellent stability for subsequent assay inside the microwells. Our results could be useful when one considers what blocking agents should be used for PMMA-based microfluidic immunosensor or biosensor devices by looking at both the blocking efficiency and the stability of the blocking agent.

  13. Photocontrol over the disorder-to-order transition in thin films of polystyrene-block-poly(methyl methacrylate) block copolymers containing photodimerizable anthracene functionality.

    PubMed

    Chen, Wei; Wang, Jia-Yu; Zhao, Wei; Li, Le; Wei, Xinyu; Balazs, Anna C; Matyjaszewski, Krzysztof; Russell, Thomas P

    2011-11-02

    Reversible photocontrol over the ordering transition of block copolymers (BCPs) from a disordered state to an ordered state, namely the disorder-to-order transition (DOT), can be used to create long-range ordered nanostructures in self-assembled BCPs over macroscopic distances by photocombing, similar to the classic zone refining used to produce highly pure, large single crystals. Here, we have designed and synthesized an anthracene-functionalized tri-BCP containing deuterated polystyrene (d(8)-PS) and poly(methyl methacrylate) (PMMA) blocks, as well as a short middle block of poly(2-hydroxyethyl methacrylates) (PHEMA) that is randomly functionalized by anthracene. This tri-BCP maintains the order-to-disorder transition-type phase behavior of its parent d(8)-PS-b-PMMA di-BCPs. Under 365 nm UV irradiation, the junction between d(8)-PS and PMMA blocks is photocoupled through the anthracene photodimers, leading to a significant increase in the total molecular weight of the tri-BCP. As a consequence, when the tri-BCP is phase-mixed but close to the boundary of the ordering transition, it undergoes the DOT, as evidenced by small-angle neutron scattering and transmission electron microscopy. The tri-BCP could be reversibly brought through the DOT in thin films by taking advantage of photodimerization and thermal dissociation of anthracene. Currently, anthracene-functionalized d(8)-PS-b-PMMA BCP is one of the most promising candidates for the photocombing process to promote long-range laterally ordered nanostructures over macroscopic distances in a noninvasive manner.

  14. Fabrication of nanopatterned poly(ethylene glycol) brushes by molecular transfer printing from poly(styrene-block-methyl methacrylate) films to generate arrays of Au nanoparticles.

    PubMed

    Onses, M Serdar

    2015-01-27

    This article presents a soft lithographic approach using block copolymer (BCP) films to fabricate functional chemically patterned polymer brushes on the nanoscale. Hydroxyl-terminated poly(ethylene glycol) (PEG-OH) was transfer printed from the poly(methyl methacrylate) (PMMA) domains of self-assembled poly(styrene-block-methyl methacrylate) films to a substrate in conformal contact with the film to generate patterned PEG brushes mirroring the pattern of BCP domains. A key point in the study is that the chemistry of the functional transferred brushes is different from the chemistry of either block of the copolymer; PEG-OH is miscible only in the PMMA block and therefore transferred only from PMMA domains. The functionality of the PEG brushes was demonstrated by the selective immobilization of citrate-stabilized Au NPs (15 nm) and validated the generation of high-quality chemical patterns with sub-30-nm feature sizes.

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

    SciTech Connect

    Hansen, Ryan R; Hinestrosa Salazar, Juan P; Shubert, Katherine R; Morrell, Jennifer L.; Pelletier, Dale A; Messman, Jamie M; Kilbey, II, S Michael; Lokitz, Bradley S; Retterer, Scott T

    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.

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

    PubMed

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

    2015-07-13

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

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

    NASA Astrophysics Data System (ADS)

    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.

  18. UV-Curable Polyurethane-Methacrylate Co-Networks and Interpenetrating Networks

    DTIC Science & Technology

    1989-05-30

    were: methyl methacrylate (MMA), ethyl methacrylate (EMA), hydroxyethyl methacrylate ( HEMA ), butyl methacrylate (BMA), lauryl methacrylate (LMA), and...ACCESSION NO. 11. TITLE (include Security Classification) UV’V-Curable Polyurethane- Methacrylate Co-Networks and Interpenetrating Networks 12. PERSONAL...by block number 4 Castor oil was reacted in varying ratios with 6-isocyanatoethyl methacrylate to form a liquid urethane- methacrylate prepolymer. This

  19. Facile Synthesis of Novel Polyethylene-Based A-B-C Block Copolymers Containing Poly(methyl methacrylate) Using a Living Polymerization System.

    PubMed

    Song, Xiangyang; Ma, Qiong; Cai, Zhengguo; Tanaka, Ryo; Shiono, Takeshi; Grubbs, Robert B

    2016-02-01

    Ethylene-propylene-methyl methacrylate (MMA) and ethylene-hexene-MMA A-B-C block copolymers with high molecular weight (>100,000) are synthesized using fluorenylamide-ligated titanium complex activated by modified methylaluminoxane and 2,6-di-tert-butyl-4-methylphenol for the first time. After diblock copolymerization of olefin is conducted completely, MMA is added and activated by aluminum Lewis acid to promote anionic polymerization. The length of polyolefin and poly (methyl methacrylate) (PMMA) is controllable precisely by the change of the additive amount of olefin and polymerization time, respectively. A soft amorphous polypropylene or polyhexene segment is located between two hard segments of semicrystalline polyethylene and glassy PMMA blocks.

  20. The effect of hydrophilic and hydrophobic block length on the rheology of amphiphilic diblock Polystyrene-b-Poly(sodium methacrylate) copolymers prepared by ATRP.

    PubMed

    Raffa, Patrizio; Stuart, Marc C A; Broekhuis, Antonius A; Picchioni, Francesco

    2014-08-15

    Following our previous investigation on the effect of molecular architecture on the rheology of Polystyrene-b-Poly(sodium methacrylate) copolymers (PS-b-PMAA), we consider here diblock PS-b-PMAA copolymers characterized by a different length of either the hydrophilic or the hydrophobic block. Various copolymers characterized by different PS or PMAA block length have been prepared by ATRP (kinetics is also discussed) and studied from the point of view of their rheological behaviour in water. To the best of our knowledge, this is the first systematic investigation concerning the effect of block length on the rheology of diblock polyelectrolytes. We found that the hydrophobic block length has small influence on the rheology. Surprisingly, the polymers with shortest PMAA blocks yield the strongest gels at high concentration. A simple model based on the classical theories of self-assembly and percolation of amphiphilic polymers has been here developed in order to explain the observed data.

  1. Acrylic AB and ABA block copolymers based on poly(2-ethylhexyl acrylate) (PEHA) and poly(methyl methacrylate) (PMMA) via ATRP.

    PubMed

    Haloi, Dhruba J; Ata, Souvik; Singha, Nikhil K; Jehnichen, Dieter; Voit, Brigitte

    2012-08-01

    Acrylic block copolymers have several advantages over conventional styrenic block copolymers, because of the presence of a saturated backbone and polar pendant groups. This investigation reports the preparation and characterization of di- and triblock copolymers (AB and ABA types) of 2-ethylhexyl acrylate (EHA) and methyl methacrylate (MMA) via atom transfer radical polymerization (ATRP). A series of block copolymers, PEHA-block-PMMA(AB diblock) and PMMA-block-PEHA-block-PMMA(ABA triblock) were prepared via ATRP at 90 °C using CuBr as catalyst in combination with N,N,N',N″,N″-pentamethyl diethylenetriamine (PMDETA) as ligand and acetone as additive. The chemical structure of the macroinitiators and molar composition of block copolymers were characterized by (1)H NMR analysis, and molecular weights of the polymers were analyzed by GPC analysis. DSC analysis showed two glass transition temperatures (T(g)), indicating formation of two domains, which was corroborated by AFM analysis. Small-angle X-ray scattering (SAXS) analysis of AB and ABA block copolymers showed scattering behavior inside the measuring limits indicating nanophase separation. However, SAXS pattern of AB diblock copolymers indicated general phase separation only, whereas for ABA triblock copolymer an ordered or mixed morphology could be deduced, which is assumed to be the reason for the better mechanical properties achieved with ABA block copolymers than with the AB analogues.

  2. Synthesis of poly(poly(ethylene glycol) methacrylate)-polyisobutylene ABA block copolymers by the combination of quasiliving carbocationic and atom transfer radical polymerizations.

    PubMed

    Szabó, Ákos; Szarka, Györgyi; Iván, Béla

    2015-01-01

    Systematic investigations are carried out on the synthesis of a series of new, unique ABA-type triblock copolymers consisting of the hydrophobic and chemically inert polyisobutylene (PIB) inner and the hydrophilic comb-shaped poly(poly(ethylene glycol) methacrylate) (PPEGMA) polymacromonomer as an outer block. Telechelic PIB macroinitiators with narrow molecular weight distributions (MWD) are synthesized by quasiliving carbocationic polymerization of isobutylene with a bifunctional initiator followed by quantitative chain end derivatizations. Atom transfer radical polymerization (ATRP) of PEGMAs with various molecular weights is investigated by using these macroinitiators. It is found that CuBr is an inefficient ATRP catalyst, while CuCl leads to high, nearly complete conversions of the PEGMA macromonomers. Gel permeation chromatography (GPC) analyses reveal slow initiation of PEGMA at relatively high PIB/PEGMA ratios or with PEGMAs of higher molecular weights due to steric hindrance between the macroinitiator and macromonomer. The occurrence of slow initiation, and not permanent termination, is proven by highly efficient ATRP of a low-molecular-weight monomer, methyl methacrylate, with the block copolymers as macroinitiators. Successful synthesis of PPEGMA-PIB-PPEGMA ABA block copolymers is obtained by using either low-molecular-weight PEGMA or relatively low macroinitiator/macromonomer ratios. Differential scanning calorimetry (DSC) indicates phase separation and significant suppression of the crystallinity of the pendant poly(ethylene glycol) (PEG) chains in these new block copolymers.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

    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.

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

    PubMed

    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.

  6. Thermodynamics of Polymer Adsorption onto Nanoporous Silica and its Application in the Large Scale Purification of Poly(styrene)-block-Poly(alkyl methacrylate) Diblock Copolymers

    NASA Astrophysics Data System (ADS)

    Abdulahad, Asem Irfan

    As a result of unavoidable inconsistencies in their synthesis via controlled radical polymerization techniques, block copolymers inherently have distributions in chemical composition and molecular weight in each block that can have significant impact on their viscoelastic properties as well as their ability to self-assemble into ordered phases. High performance liquid chromatography is routinely utilized for determining the average molecular weight distribution that exist in synthetic polymers and is becoming increasingly popular for the fractionation and purification of chemically diverse complex polymer materials such as diblock copolymers. However, the inability of HPLC fractionation to provide meaningful quantities of purified complex polymers makes this method extremely inefficient and limits the ability to characterize purified fractions further. Overall, this dissertation work can be digested in two distinct parts. In the first part, high performance liquid chromatography was used as a tool for studying the influential parameters affecting the critical adsorption point of poly(styrene) and poly(alkyl methacrylate) homopolymers. The understanding gained in the first portion was depended on for the development of large scale fractionation procedures. In the second part, a chemically diverse variety of poly(alkyl methacrylate)-block-poly(styrene) diblock copolymers synthesized by atom transfer radical polymerization and anionic polymerization were purified by large scale adsorption-based fractionation procedures that included chromatographic filtration and the sequential adsorption/desorption of bulk diblock copolymer materials. The impact of diblock copolymer purification is addressed by comparing the molecular weight distribution, chemical composition distribution, viscoelastic properties, and small-angle X-ray scattering profiles.

  7. Reduced hydrophobic interaction of polystyrene surfaces by spontaneous segregation of block copolymers with oligo (ethylene glycol) methyl ether methacrylate blocks: force measurements in water using atomic force microscope with hydrophobic probes.

    PubMed

    Zhang, Rui; Seki, Akiko; Ishizone, Takashi; Yokoyama, Hideaki

    2008-05-20

    Reduction of hydrophobic interaction in water is important in biological interfaces. In our previous work, we have found that poly(styrene- b-triethylene glycol methyl ether methacrylate) (PS-PME3MA) segregates the PME3MA block to the surface in hydrophobic environment, such as in air or in a vacuum, and shows remarkable resistance against adsorption or adhesion of proteins, platelets, and cells in water. In this paper, we report that atomic force microscopy (AFM) with hydrophobic probes can directly monitor the reduced hydrophobic interaction of the PS surfaces modified by poly(styrene- b-origoethylene glycol methyl ether methacrylate) (PS-PME NMA), where N is the number of ethylene glycol units. The pull-off forces between the hydrophobic probes that are coated with octyltrichlorosilane (OLTS) and the PS-PME NMA modified polystyrene (PS) surfaces in water were measured. The absolute spring constants and tip-curvatures of the AFM cantilevers were measured to compute the work of adhesion by the Johnson, Kendall, and Roberts (JKR) theory, which relates the pull-off force at which the separation occurs between a hemisphere and a plane to the work of adhesion. The hydrophobic interactions between the hydrophobic tip and polymer surfaces in water were greatly reduced with the segregated PME NMA blocks. The hydrophobic interactions decrease with increasing N of the series of PS-PME NMA and show a correlation with the amount of protein adsorbed.

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

    PubMed

    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.

  9. Mesoscale simulation of the formation and dynamics of lipid-structured poly(ethylene oxide)-block-poly(methyl methacrylate) diblock copolymers.

    PubMed

    Mu, Dan; Li, Jian-Quan; Feng, Sheng-Yu

    2015-05-21

    Twelve poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) copolymers with lipid-like structures were designed and investigated by MesoDyn simulation. Spherical and worm-like micelles as well as bicontinuous, lamellar and defected lamellar phases were obtained. A special structure, designated B2412, with two lipid structures connected by their heads, was found to undergo four stages prior to forming a spherical micelle phase. Two possible assembly mechanisms were found via thermodynamic and dynamic process analyses; namely, the fusion and fission of micelles in dynamic equilibrium during the adjustment stage. Water can be encapsulated into these micelles, which can affect their size, particularly in low concentration aqueous solutions. The assignment of weak negative charges to the hydrophilic EO blocks resulted in a clear effect on micelle size. Surprisingly, the largest effect was observed with EO blocks with -0.5 e, wherein an ordered perfect hexagonal phase was formed. The obtained results can be applied in numerous fields of study, including adsorption, catalysis, controlled release and drug delivery.

  10. Reduced excimer formation in polyfluorenes by introducing coil-like poly[penta(ethylene glycol) methyl ether methacrylate] block segments

    NASA Astrophysics Data System (ADS)

    Noh, Seung Ju; Heo, Seong Ik; Jang, Se Hyun; Ahn, Haeng Hee; Han, Jin Young; Suk, Min Gyun; Jin, Sun Jin; Kwon, Yong Ku

    2012-09-01

    The formation of the aggregate and excimer in light-emitting polyfluorenes during annealing at high temperatures was reduced by adding coil-like block segments through atom transfer radical polymerization (ATRP), initialized by 2- bromoisobutyrate end-capped PF macroinitiator using CuBr/N,N,N',N',N''-pentamethyldiethylenetriamine (PMDETA) catalyst system. The rod-like macroinitiator was synthesized by the Yamamoto-type coupling using a Ni(COD)2 catalyst. The structure and physical properties were characterized by 1H NMR, thermal analysis, GPC, photoluminescence, small angle X-ray scattering and transmission electron microscopy. The addition of the coil-like block segments to the rod-like block segment resulted in the microphase separation between the component blocks which decreased the effective conjugation length of the conjugated moieties. The photoluminescence spectra measured from the thin films of the block copolymers revealed that the coil-like endblocks, attached to the conjugated block segments, suppressed the excimer formation of the PF molecules during annealing at high temperature.

  11. Custom CAD-CAM healing abutment and impression coping milled from a poly(methyl methacrylate) block and bonded to a titanium insert.

    PubMed

    Proussaefs, Periklis

    2016-11-01

    This article describes a technique in which a custom-made computer-aided design and computer-aided manufacturing (CAD-CAM) healing abutment milled from a poly(methyl methacrylate) (PMMA) block is fabricated and bonded to a titanium metal insert. An impression is made during dental implant surgery, and the CAD-CAM custom-made healing abutment is fabricated before second-stage surgery while appropriate healing time is allowed for the dental implant to osseointegrate. The contours of the healing abutment are based on the contours of a tentatively designed definitive prosthesis. The healing tissue obtains contours that will be compatible with the contours of the definitive prosthesis. After the milling process is complete, a titanium metal insert is bonded to the healing abutment. Placement of the custom-made CAD-CAM healing abutment at second-stage surgery allows the tissue to obtain contours similar to those of the definitive prosthesis. A custom-made CAD-CAM impression coping milled from a PMMA block and with a titanium insert is used for the definitive impression after the soft tissue has healed. This technique allows guided soft tissue healing by using a custom-made CAD-CAM healing abutment and impression coping.

  12. Methyl methacrylate

    Integrated Risk Information System (IRIS)

    TOXICOLOGICAL REVIEW of METHYL METHACRYLATE ( CAS No . 80 - 62 - 6 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) January 1998 U.S . Environmental Protection Agency Washington , DC TABLE OF CONTENTS DISCLAIMER . . . . . . . . . . . . . . . . . . . . . . . . .

  13. Synthesis and self-assembly of brush-type poly[poly(ethylene glycol)methyl ether methacrylate]-block-poly(pentafluorostyrene) amphiphilic diblock copolymers in aqueous solution.

    PubMed

    Tan, B H; Hussain, H; Liu, Y; He, C B; Davis, T P

    2010-02-16

    Well-defined fluorinated brush-like amphiphilic diblock copolymers of poly[poly(ethylene glycol)methyl ether methacrylate] (P(PEGMA)) and poly(pentafluorostyrene) (PPFS) have been successfully synthesized via atom transfer radical polymerization (ATRP). The self-assembly behavior of these polymers in aqueous solutions was studied using (1)H NMR, fluorescence spectrometry, static and dynamic light scattering and transmission electron microscopy techniques. The micellar structure comprised of PPFS as the core and brush-like (hydrophobic main chain and hydrophilic branches) polymers as the coronas. The hydrodynamic radius (R(h)) of the micelles in aqueous solution was in the nanometer range, independent of the polymer concentration, consistent with a closed association model. Diblock copolymers with a longer P(PEGMA) block formed micelles with smaller R(h) and lower aggregation numbers consistent with an improved solubilization of the core. The micelles possessed a thick hydration layer as verified by the ratio of the radius of gyration, R(g) to the hydrodynamic radius, R(h). The aggregation number and ratio of R(g) to R(h) were observed to increase with temperature (20-50 degrees C), while the R(h) of the micelle decreased slightly over the same temperature range. An increase in temperature induced the brush-like PEG segments in the corona to dehydrate and shrink while forming micelles with larger aggregation numbers.

  14. Water-stable diblock polystyrene-block-poly(2-vinyl pyridine) and diblock polystyrene-block-poly(methyl methacrylate) cylindrical patterned surfaces inhibit settlement of zoospores of the green alga Ulva.

    PubMed

    Grozea, Claudia M; Gunari, Nikhil; Finlay, John A; Grozea, Daniel; Callow, Maureen E; Callow, James A; Lu, Zheng-Hong; Walker, Gilbert C

    2009-04-13

    Nanopatterned surfaces with hydrophobic and hydrophilic domains were produced using the diblock copolymer polystyrene-block-poly(2-vinyl pyridine) (PS-b-P2VP) and polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA). The PS-b-P2VP diblock copolymer, mixed with the cross-linker benzophenone and spin-coated onto silicon wafers, showed self-assembled cylindrical structures, which were retained after UV treatment for cross-linking. The thin films displayed cylindrical domains after immersion in water. This study shows that pattern retention in water is possible for a long period of time, at least for two weeks in pure water and three weeks in artificial seawater. The PS-b-PMMA diblock showed self-assembled cylindrical structures. PS-b-P2VP and PS-b-PMMA cylindrical patterned surfaces showed reduced settlement of zoospores of the green alga Ulva compared to unpatterned surfaces. The copolymers were investigated using atomic force microscopy and X-ray photoelectron spectroscopy.

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

    DOE PAGES

    Jiang, Xingmao; Liu, Nanguo; Assink, Roger A.; ...

    2011-01-01

    Azobenzene ligands were uniformly anchored to the pore surfaces of nanoporous silica particles with single crystal NaCl using 4-(3-triethoxysilylpropylureido)azobenzene (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 switchablemore » pore size. TGA, XRD, FTIR, and NMR techniques were used to characterize the structures.« less

  16. Structure control for fine tuning fluorescence emission from side-chain azobenzene polymers.

    PubMed

    Smitha, P; Asha, S K

    2007-06-14

    New fluorescent azobenzene dyes and side-chain polymers have been synthesized and characterized and their photophysical properties studied. A series of azobenzene dyes having different fluorophores such as phenol (S1), phenylphenol (S2) and naphthol (S3) incorporated in them were synthesized. S2 had unusually high fluorescence with a quantum yield of phi f = 0.2 recorded in dichloromethane (DCM), whereas S1 and S3 were found to be weakly fluorescent. The azobenzene dyes were converted into methacrylate monomers having short ethyleneoxy spacers and then free radically polymerized. Phenylphenol-based azobenzene polymer (P2) continued to show fluorescence, whereas fluorescence was completely quenched in the case of phenol (P1)- and naphthol (P3)-based polymers. Phenylphenol, though twisted in the ground state is known to have a more planar geometry in the excited state--a factor that enables it to retain its fluorescence behavior even when it is incorporated as part of an azobenzene unit. In contrast, naphthol, which is a better fluorophore compared to phenylphenol, loses much of its emissive behavior upon coupling to the azobenzene unit. The extent of trans to cis photoisomerization in solution was very low (approximately 17%) for P2 after 30 min of continuous irradiation using 365 nm light, in contrast to approximately 40% for P1 under identical conditions. This is attributed to the steric repulsion brought about by the bulky phenylphenol units that restrict rotation. A 2-fold enhancement in fluorescence emission was observed for P2 upon irradiation by UV light at 360 nm, which relaxed to the original intensity in about 7 day's time. The higher emission of the cis azobenzenes is generally attributed to an inhibition of photoinduced electron transfer (PET) mechanism. The emission of P2 showed a concentration dependence which increased initially and then decreased in intensity with the formation of a new red-shifted peak at higher concentration due to aggregation

  17. Ammonium methacrylate

    Integrated Risk Information System (IRIS)

    Ammonium methacrylate ; CASRN 16325 - 47 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcin

  18. Removal of azobenzene from water by kaolinite.

    PubMed

    Zhang, Xiaoling; Hong, Hanlie; Li, Zhaohui; Guan, Junfang; Schulz, Laura

    2009-10-30

    The use of natural kaolinite clay to remove azobenzene from aqueous solutions under different pHs, ionic strengths, initial solid mass used, and initial solution concentrations was investigated. Batch kinetic experiments showed that the adsorption of azobenzene onto kaolinite followed a pseudo-second-order kinetics with an initial rate of 7.2 mg/g-h and a rate constant of 0.19 g/mg-h. The equilibrium azobenzene adsorption on kaolinite was well described by the Langmuir and Freundlich isotherms with an adsorption capacity of 11 mg/g, or 60 mmol/kg, corresponding to a monolayer adsorption on the surface of kaolinite. Adsorption increased with decreases in solution pH and increases in solution ionic strength. The enthalpy change of adsorption was -38 kJ/mol, suggesting that both physical and chemical adsorption was responsible for the retention of azobenzene on kaolinite. The high affinity of azobenzene for siloxane and gibbsite surfaces was attributed to the attractive Coulombic and van der Waals' forces between the surface and the planar structure of the organic molecule.

  19. Photo-induced deformation of azobenzene polymers: theory and simulations

    NASA Astrophysics Data System (ADS)

    Saphiannikova, Marina; Toshchevikov, Vladimir; Ilnytskyi, Jaroslav; Heinrich, Gert

    2011-11-01

    A microscopic theory is developed to describe light-induced deformation of azobenzene polymers of different chemical structures: uncross-linked low-molecular-weight azobenzene polymers and cross-linked azobenzene polymers (azobenzene elastomers) bearing azobenzene chromophores in their strands. According to the microscopic theory the light-induced deformation is caused by reorientation of azobenzene chromophores with respect to the electric vector of the linearly polarized light, E. Theoretical calculations of the order parameter of short azobenzene molecules (oligomers) affected by the light show that the sign of the light-induced deformation (expansion / contraction along the vector E) depends strongly on the chemical structure of the oligomers. The conclusion of the theory about different signs of the light-induced deformation of low-molecular-weight azobenzene polymers is in an agreement with performed series of molecular dynamics simulations. Using the microscopic theory it is shown that cross-linked azobenzene polymers demonstrate the same light-induced deformation (expansion / contraction) as their low-molecular-weight analogues, i.e. polymers consisting of short azobenzene molecules whose chemical structure is the same as chain fragments of the elastomers.

  20. Enantiopure sulfinyl azobenzenes as chiroptical switches.

    PubMed

    Carreño, M Carmen; García, Isabel; Ribagorda, María; Merino, Estíbaliz; Pieraccini, Silvia; Spada, Gian Piero

    2005-07-07

    [reaction: see text] Photoswitchable enantiopure sulfinyl azo compounds have been synthesized. A remarkable perturbation of the azo system by the stereogenic sulfinyl moiety has been observed by CD in both the trans and the cis azobenzenes resulting by photoisomerization. After five irradiation cycles, the configurational integrity of these chiral switches remains unchanged.

  1. 76 FR 69659 - Methacrylic Acid-Methyl Methacrylate-Polyethylene Glycol Monomethyl Ether Methacrylate Graft...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-11-09

    ... AGENCY 40 CFR Part 180 Methacrylic Acid-Methyl Methacrylate-Polyethylene Glycol Monomethyl Ether... residues of methacrylic acid-methyl methacrylate- polyethylene glycol monomethyl ether methacrylate graft... permissible level for residues of methacrylic acid-methyl methacrylate-polyethylene glycol monomethyl...

  2. Photoswitching in nanoporous, crystalline solids: an experimental and theoretical study for azobenzene linkers incorporated in MOFs.

    PubMed

    Wang, Zhengbang; Heinke, Lars; Jelic, Jelena; Cakici, Murat; Dommaschk, Marcel; Maurer, Reinhard J; Oberhofer, Harald; Grosjean, Sylvain; Herges, Rainer; Bräse, Stefan; Reuter, Karsten; Wöll, Christof

    2015-06-14

    In this article, we use the popular photoswitchable molecule, azobenzene, to demonstrate that the embedding in a nanoporous, crystalline solid enables a precise understanding of light-induced, reversible molecular motion. We investigate two similar azobenzene-containing, pillared-layer metal-organic frameworks (MOFs): Cu2(AzoBPDC)2(BiPy) and Cu2(NDC)2(AzoBiPy). Experimental results from UV-vis spectroscopy and molecular uptake experiments as well as theoretical results based on density-functional theory (DFT) show that in the Cu2(AzoBPDC)2(BiPy) MOF structure, the azobenzene side groups undergo photoisomerization when irradiated with UV or visible light. In a very similar MOF structure, Cu2(NDC)2(AzoBiPy), the experimental studies show an unexpected absence of photoisomerization. The DFT calculations reveal that in both MOFs the initial and final states of the photoswitching process (the trans and the cis conformation) have similar energies, which strongly suggests that the reason for the effective blocking of photoswitching in the AzoBiPy-based MOFs must be related to the switching process itself. More detailed calculations show that in Cu2(NDC)2(AzoBiPy) a naphthalene linker from the molecular framework blocks the photoisomerization trajectory which leads from the trans to the cis conformation. For Cu2(AzoBPDC)2(BiPy), as a result of the different geometry, such a steric hindrance is absent.

  3. DNA compaction by azobenzene-containing surfactant

    SciTech Connect

    Zakrevskyy, Yuriy; Kopyshev, Alexey; Lomadze, Nino; Santer, Svetlana

    2011-08-15

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

  4. Cooperative Switching in Nanofibers of Azobenzene Oligomers

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    Theamdee, Pawinee; Traiphol, Rakchart; Rutnakornpituk, Boonjira; Wichai, Uthai; Rutnakornpituk, Metha

    2011-10-01

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

  6. Multidetector thermal field-flow fractionation as a unique tool for the tacticity-based separation of poly(methyl methacrylate)-polystyrene block copolymer micelles.

    PubMed

    Greyling, Guilaume; Pasch, Harald

    2015-10-02

    Poly(methyl methacrylate)-polystyrene (PMMA-PS) micelles with isotactic and syndiotactic coronas are prepared in acetonitrile and subjected to thermal field-flow fractionation (ThFFF) analysis at various conditions of increasing temperature gradients. It is shown for the first time that multidetector ThFFF provides comprehensive information on important micelle characteristics such as size (Dh), shape (Rg/Rh), aggregation number (Z), thermal diffusion (DT) and Soret coefficients (ST) as a function of temperature from a single injection. Moreover, it is found that micelles exhibit a unique decreasing trend in DT as a function of temperature which is independent of the tacticity of the corona and the micelle preparation method used. It is also demonstrated that ThFFF can monitor micelle to vesicle transitions as a function of temperature. In addition to ThFFF, it is found from DLS analysis that the tacticity of the corona influences the critical micelle concentration and the magnitude to which micelles expand/contract with temperature. The tacticity does not, however, influence the critical micelle temperature. Furthermore, the separation of micelles based on the tacticity of the corona highlight the unique capabilities of ThFFF.

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

    SciTech Connect

    Cheng Liang; Torres, Yanira; Oates, William S.; Lee, Kyung Min; McClung, Amber J.; Baur, Jeffery; White, Timothy J.

    2012-07-01

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

  8. Mesoscopic simulation of the self-assembly of the weak polyelectrolyte poly(ethylene oxide)-block-poly(methyl methacrylate) diblock copolymers.

    PubMed

    Mu, Dan; Li, Jian-Quan; Feng, Sheng-Yu

    2015-06-14

    We designed twelve types of weak polyelectrolytes (i.e., PEO-b-PMMA copolymers (BCP) in multi-arm structures, where six include EO blocks as joint points and the other six have MMA blocks as joint points). All of the BCPs with EO as the joint points form disordered phases with the exception of long-chained and four-armed BCP. The main mesophases of all of the BCPs with MMA as joint points are micelle-like and bicontinuous phases. In particular, the short-chained BCP with four-arms and EO segments outside form a new phase type (i.e., crossed lamellar phase). Using MesoDyn, we provide a comprehensive representation of the micelle and crossed lamellar phase formation mechanisms based on both thermodynamic and dynamic analyses. A shear force on a micelle-like phase could promote a hexagonal columnar phase, which is a good technique for generating an ordered arrangement of nanotube arrays. Blending homopolymers with the same constituents could promote uniformity of the micelle size and decrease the polydispersity, especially for blends with a high BCP concentration, which may provide a new approach for regulating the properties of materials.

  9. Molecular mechanics modeling of azobenzene-based photoswitches.

    PubMed

    Duchstein, Patrick; Neiss, Christian; Görling, Andreas; Zahn, Dirk

    2012-06-01

    We present an extension of the generalized amber force field to allow the modeling of azobenzenes by means of classical molecular mechanics. TD-DFT calculations were employed to derive different interaction models for 4-hydroxy-4'-methyl-azobenzene, including the ground (S(0)) and S(1) excited state. For both states, partial charges and the -N = N- torsion potentials were characterized. On this basis, we pave the way to large-scale model simulations involving azobenzene molecular switches. Using the example of an isolated molecule, the mechanics of cyclic switching processes are demonstrated by classical molecular dynamics simulations.

  10. Graphene-modulated photo-absorption in adsorbed azobenzene monolayers.

    PubMed

    Fu, Qiang; Cocchi, Caterina; Nabok, Dmitrii; Gulans, Andris; Draxl, Claudia

    2017-02-22

    The impact of graphene on the photo-absorption properties of trans- and cis-azobenzene monolayers is studied in the framework of density-functional theory and many-body perturbation theory. We find that, despite the weak hybridization between the electronic bands of graphene and those of the azobenzene monolayers, graphene remarkably modulates the absorption spectra of the adsorbates. The excitation energies are affected via two counteracting mechanisms: substrate polarization reduces the band-gap of azobenzene, and enhanced dielectric screening weakens the attractive interaction between electrons and holes. The competition between these two effects gives rise to an overall blueshift of peaks stemming from intramolecular excitations, and a redshift of peaks from intermolecular ones. Even more interesting is that excitations corresponding to intermolecular electron-hole pairs, which are dark in the isolated monolayers, are activated by the graphene substrate. Our results demonstrate that the photoisomerization process of weakly adsorbed azobenzene undergoes notable changes on a carbon-based substrate.

  11. Theoretical study of the isomerization mechanism of azobenzene and disubstituted azobenzene derivatives.

    PubMed

    Crecca, Christina R; Roitberg, Adrian E

    2006-07-06

    A series of azobenzenes was studied using ab initio methods to determine the substituent effects on the isomerization pathways. Energy barriers were determined from three-dimensional potential energy surfaces of the ground and electronically excited states. In the ground state (S(0)), the inversion pathway was found to be preferred. Our results show that electron donating substituents increase the isomerization barrier along the inversion pathway, whereas electron withdrawing substituents decrease it. The inversion pathway of the first excited state (S(1)) showed trans --> cis barriers with no curve crossing between S(0) and S(1). In contrast, a conical intersection was found between the ground and first excited states along the rotation pathway for each of the azobenzenes studied. No barriers were found in this pathway, and we therefore postulate that after n --> pi (S(1) <-- S(0)) excitation, the rotation mechanism dominates. Upon pi --> pi (S(2) <-- S(0)) excitation, there may be sufficient energy to open an additional pathway (concerted-inversion) as proposed by Diau. Our potential energy surface explains the experimentally observed difference in trans-to-cis quantum yields between S(1) and S(2) excitations. The concerted inversion channel is not available to the remaining azobenzenes, and so they must employ the rotation pathway for both n --> pi and pi --> pi excitations.

  12. Photo-responsive and thermoreversible networks from the self-assembly of azobenzene-containing liquid crystal triblock copolymers (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Kurji, Zuleikha; Kornfield, Julia A.; Kuzyk, Mark G.

    2016-09-01

    We report the synthesis of azobenzene-containing coil-liquid crystal-coil triblock copolymers that can serve as mechano-optic actuators for applications that include non-invasively steering fiber optics. The coil (polystyrene) end-blocks phase segregate from the liquid crystal midblock forming of uniform and uniformly-spaced physical crosslinks, resulting in highly reproducible and thermoreversible networks by self-assembly. These polymers are elastic in the melt (at room temperature) and can be easily spun, coated or molded. Mechanical stretching results in a temporary monodomain alignment. Starting from identical triblock prepolymers (with polystyerene end blocks and 1,2-polybutadiene midblocks), a matched pair (azobenzene-containing, and non-azobenzene-containing) of liquid crystal triblock copolymers was synthesized. These triblocks were then be blended to prepare a series of elastomers with 0 to 5% azobenzene groups, while matching in nearly all other physical properties (cross-link density, modulus, birefringence, etc.), allowing the effect of concentration of photo-responsive groups to be unambiguously determined. Results will be presented that demonstrate this approach to independent control of optical density and photo-mechanical sensitivity.

  13. Holographic data storage using azobenzene polymer

    NASA Astrophysics Data System (ADS)

    Wang, Michael R.; Yang, Jianwen; Yan, Xingzhong; DeMasi, Ralph

    2001-10-01

    It is well known that holographic data storage can significantly increase data storage capacity. However, the technological maturity of holographic data storage is believed to be impeded by the lack of good holographic material that can be erased and recorded optically with almost unlimited rewriting cycles, large index modulation for large capacity multiplexed data recording, long lifetime, and immunity to destructive readout for archival applications. The performance of an azobenzene polymer is presented for holographic data storage applications. Initial experiments demonstrated that it is capable of satisfying many of above requirements. Recording of holograms without follow-up processing and being stable in application environment are its most attractive features. Applications of such material to other adaptive structures are possible.

  14. Acrylates and Methacrylates,

    DTIC Science & Technology

    1987-09-15

    of ethylene and hydrocyanic acid through ethylene cyanohydrin. In the presence of basic catalysts ethylene oxide easily adds hydrocyanic acid with the...of synthesis of methacrylates. At present methacrylates are obtained in the industry by continuous method from acetone and hydrocyanic acid through...acetone cyanohydrin. The addition/connection to it of hydrocyanic acid with the formation of acetone cyanohydrin is one of the most important reactions

  15. Review of the recent progress in photoresponsive molecularly imprinted polymers containing azobenzene chromophores.

    PubMed

    Wei, Yu-bo; Tang, Qian; Gong, Cheng-bin; Lam, Michael Hon-Wah

    2015-11-05

    Photoresponsive molecularly imprinted polymers (PMIPs) containing azobenzene have received wide research attention in recent years and made notable achievements. This article reviews the recent developments on PMIPs containing azobenzene. Topics include the following: (i) brief introduction of azobenzene, molecularly imprinted polymers, and PMIPs containing azobenzene; (ii) progress in functional monomers, cross-linkers, and polymerization conditions; (iii) preparation methods, properties, applications, as well as advantages and disadvantages of conventional PMIPs; (iv) substrate, preparation method, and applications of photoresponsive surface molecularly imprinted polymers; and (v) some perspectives for further development of PMIPs containing azobenzene.

  16. Nonlinear dynamics and thermodynamics of azobenzene polymer networks

    NASA Astrophysics Data System (ADS)

    Oates, William S.; Bin, Jonghoon

    2013-04-01

    The nonlinear photomechanics and thermodynamics of azobenzene liquid crystal polymer networks is studied to quantify interactions between wavelength dependent molecular conformation changes that occur within a polymer network. The transfer of energy from light to liquid crystals to a polymer network strongly depends on the wavelength and polarization of light where trans or rod shaped azobenzene chromophores convert to a cis or kinked conformation and simultaneously may relax back to the trans state but in a different orientation. This behavior requires an understanding of the dynamic interactions between light and azobenzene molecules and thermodynamics of light-matter interactions. We investigate this behavior by quantifying transmission and absorption of electro-magnetic energy with stored energy within the solid material. This is conducted by introducing a set of optical order parameters coupled to photochemistry that evolve as a function of electro-magnetic radiation.

  17. Electron attachment to trans-azobenzene.

    PubMed

    Modelli, Alberto; Burrow, Paul D

    2009-10-14

    The temporary anion states of gas-phase trans-azobenzene are characterised by means of electron transmission spectroscopy (ETS) in the 0-6 eV range. The measured energies of vertical electron attachment are compared with the energies of the pi* virtual orbitals of the neutral molecule supplied by HF (at MP2 optimized geometries) and B3LYP calculations. The calculated energies, scaled with empirical equations, reproduce quantitatively the energies of the corresponding spectral features and predict a positive vertical electron affinity of 0.83 eV. The total anion current at the walls of the collision chamber and the mass-selected molecular anion current are also reported as a function of the impact electron energy. In agreement with previous data, long-lived (>1 mus) parent molecular anions are detected at zero eV and near 1 eV. The close similarity of the electron transmission spectrum with the derivatives with respect to energy of the anion currents suggests strongly that shape resonances produced by electron capture into empty pi* orbitals are the initial step in formation of the long lived molecular anions. This appears to rule out mechanisms in which direct formation of core-excited anion states are invoked. However, according to DFT calculations, conversion of the shape resonances around 1 eV to longer-lived sigma-pi* core-excited doublet anion states is possible on energetic grounds.

  18. Approximate photochemical dynamics of azobenzene with reactive force fields

    SciTech Connect

    Li, Yan; Hartke, Bernd

    2013-12-14

    We have fitted reactive force fields of the ReaxFF type to the ground and first excited electronic states of azobenzene, using global parameter optimization by genetic algorithms. Upon coupling with a simple energy-gap transition probability model, this setup allows for completely force-field-based simulations of photochemical cis→trans- and trans→cis-isomerizations of azobenzene, with qualitatively acceptable quantum yields. This paves the way towards large-scale dynamics simulations of molecular machines, including bond breaking and formation (via the reactive force field) as well as photochemical engines (presented in this work)

  19. Approximate photochemical dynamics of azobenzene with reactive force fields

    NASA Astrophysics Data System (ADS)

    Li, Yan; Hartke, Bernd

    2013-12-01

    We have fitted reactive force fields of the ReaxFF type to the ground and first excited electronic states of azobenzene, using global parameter optimization by genetic algorithms. Upon coupling with a simple energy-gap transition probability model, this setup allows for completely force-field-based simulations of photochemical cis→trans- and trans→cis-isomerizations of azobenzene, with qualitatively acceptable quantum yields. This paves the way towards large-scale dynamics simulations of molecular machines, including bond breaking and formation (via the reactive force field) as well as photochemical engines (presented in this work).

  20. Immobilization of enzymes on 2-hydroxyethyl methacrylate and glycidyl methacrylate copolymer brushes.

    PubMed

    Ren, Tanchen; Mao, Zhengwei; Moya, Sergio Enrique; Gao, Changyou

    2014-08-01

    The immobilization of enzymes is of paramount importance to maintain their activity and stability. In this study, surface-initiated atom-transfer radical polymerization was applied to prepare poly(2-hydroxyethyl methacrylate)-block-poly(2-hydroxyethyl methacrylate-co-glycidyl methacrylate) brushes on glass slides. The polymerization kinetics was followed by using a quartz crystal microbalance with dissipation monitoring and ellipsometry in terms of mass and thickness growth, respectively. The surface chemical compositions of the obtained polymer brushes were characterized by X-ray photoelectron spectroscopy. Their mass, thickness, and enzyme-immobilization ability could be easily tuned by the initiator reaction time, monomer ratio, and polymerization time. The antibacterial activity and stability of the immobilized lysozymes were studied by fluorescent staining and bacteria lysis assay, which revealed that the lysozymes on the copolymer brushes had good stability during storage at 4 °C for up to 30 days.

  1. Thermoforming polymethyl methacrylate.

    PubMed

    Jagger, R G; Okdeh, A

    1995-11-01

    This study characterized a range of commercially available polymethyl methacrylate sheets with respect to molecular weight, residual monomer content, and glass transition temperature and then developed a thermoforming procedure that produced visually satisfactory thermoformed polymethyl methacrylate specimens. Molecular weight values of Perspex material were considerably greater than those of the other materials. All materials but Diakon had residual monomer concentrations of less than 1% and glass transition temperature values greater than 100 degrees C. Perspex material was selected for further investigation. It was necessary to preheat Perspex sheets in an oven at 160 degrees C for at least 30 minutes before heating and forming on the thermoforming apparatus to obtain acceptable specimens.

  2. Injectible bodily prosthetics employing methacrylic copolymer gels

    DOEpatents

    Mallapragada, Surya K.; Anderson, Brian C.

    2007-02-27

    The present invention provides novel block copolymers as structural supplements for injectible bodily prosthetics employed in medical or cosmetic procedures. The invention also includes the use of such block copolymers as nucleus pulposus replacement materials for the treatment of degenerative disc disorders and spinal injuries. 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.

  3. Kinetics of oxidation of azobenzene nitrene with molecular oxygen in amorphous polymers

    SciTech Connect

    Kondratenko, E.V.; Bolshakov, B.V.; Tolkatchev, V.A.

    1996-12-31

    Kinetics of disappearance of azobenzene nitrene at 115-120 K in polymethyl methacrylate, poly styrene, polycarbonate and polysulfone films saturated with oxygen has been studied. For condition of oxygen excess the disappearance of nitrous is shown to be a result only of the reaction with the dissolved gas. Kinetics of the process is identical to that of the oxidation of macro radicals in the same polymer. The nonexponential character of kinetic curves is shown to be related with the existence of the rate constant distribution. The values of the width of distribution range in the narrow interval being practically the same for various polymers. The data about the width of the distribution function for the oxidation of macro radicals in amorphous polymers known from literature also fit into this interval. All the particles participating in the reaction with the experimental accuracy have the same dependence of the rate constant on temperature. The activation energies of reactions in various amorphous polymers have very close values.

  4. Synthesis of azobenzenes from quinone acetals and arylhydrazines.

    PubMed

    Carreño, M Carmen; Mudarra, Gerardo Fernández; Merino, Estíbaliz; Ribagorda, María

    2004-05-14

    Direct reaction between quinone bisacetals and arylhydrazines gives azobenzenes. The presence of catalytic amounts of cerium ammonium nitrate strongly accelerates the reaction. When the bisacetal has a substituent at the 2,5-cyclohexadiene framework, only one regioisomer is formed. The method represents a simple, mild, and novel synthetic access to differently substituted azocompounds in high to excellent yield.

  5. Cooperative light-induced molecular movements of highly ordered azobenzene self-assembled monolayers.

    PubMed

    Pace, Giuseppina; Ferri, Violetta; Grave, Christian; Elbing, Mark; von Hänisch, Carsten; Zharnikov, Michael; Mayor, Marcel; Rampi, Maria Anita; Samorì, Paolo

    2007-06-12

    Photochromic systems can convert light energy into mechanical energy, thus they can be used as building blocks for the fabrication of prototypes of molecular devices that are based on the photomechanical effect. Hitherto a controlled photochromic switch on surfaces has been achieved either on isolated chromophores or within assemblies of randomly arranged molecules. Here we show by scanning tunneling microscopy imaging the photochemical switching of a new terminally thiolated azobiphenyl rigid rod molecule. Interestingly, the switching of entire molecular 2D crystalline domains is observed, which is ruled by the interactions between nearest neighbors. This observation of azobenzene-based systems displaying collective switching might be of interest for applications in high-density data storage.

  6. Cooperative light-induced molecular movements of highly ordered azobenzene self-assembled monolayers

    PubMed Central

    Pace, Giuseppina; Ferri, Violetta; Grave, Christian; Elbing, Mark; von Hänisch, Carsten; Zharnikov, Michael; Mayor, Marcel; Rampi, Maria Anita; Samorì, Paolo

    2007-01-01

    Photochromic systems can convert light energy into mechanical energy, thus they can be used as building blocks for the fabrication of prototypes of molecular devices that are based on the photomechanical effect. Hitherto a controlled photochromic switch on surfaces has been achieved either on isolated chromophores or within assemblies of randomly arranged molecules. Here we show by scanning tunneling microscopy imaging the photochemical switching of a new terminally thiolated azobiphenyl rigid rod molecule. Interestingly, the switching of entire molecular 2D crystalline domains is observed, which is ruled by the interactions between nearest neighbors. This observation of azobenzene-based systems displaying collective switching might be of interest for applications in high-density data storage. PMID:17535889

  7. Photoresponsive ionic liquid crystals based on azobenzene guanidinium salts.

    PubMed

    Wuckert, Eugen; Harjung, Marc D; Kapernaum, Nadia; Mueller, Carsten; Frey, Wolfgang; Baro, Angelika; Giesselmann, Frank; Laschat, Sabine

    2015-04-07

    The use of non-ionic LC phases as anisotropic matrices for E/Z-isomerization of azo-guest molecules is often restricted due to limited solubilities and demixing effects. In this study we therefore employed an ionic liquid crystal (ILC) matrix to follow the photo-induced E/Z-isomerization of ionic mesogenic azobenzene guanidinium guests. The latter were prepared from 4-hydroxy-4'-(octyloxy)azobenzene, which was first treated with N-(bromoalkyl)phthalimides to introduce the spacer with varying chain length. Removal of phthalimide and final reaction with a formamidinium salt linked the ionic head group to the photoisomerizable azobenzene unit. Investigation of the mesomorphic behaviour revealed for all azobenzene ILCs smectic A mesophases with high translational order parameters and partial bilayers, as could be stated by layer spacing d. Similar packing behaviour was found for the solid state by X-ray crystal structure analysis. E/Z-isomerization of azobenzene ILCs which were completely miscible with the ionic LC phase of C12MIM-Br as anisotropic host was induced by irradiation with UV light and the reisomerization observed by time-resolved UV-Vis spectroscopy. For comparison, water was used as isotropic host. Z/E-reisomerization activation energies exhibited similar values of 97-100 kJ mol(-1) irrespective of spacer lengths and the type of host. The results demonstrate that a proper match of steric requirements of host and guest as well as layer spacings are needed for a decreased activation energy.

  8. Nanodimple Arrays Fabricated on SiO2 Surfaces by Wet Etching through Block Copolymer Thin Films

    NASA Astrophysics Data System (ADS)

    Watanabe, Ryoko; Kamata, Kaori; Iyoda, Tomokazu

    2008-06-01

    Block copolymer thin films are promising nanotemplates because highly ordered periodic structures are spontaneously formed through microphase separation on a deca-nanometer scale and over a large area. An amphiphilic block copolymer, which consists of poly(ethylene oxide) (PEO) and poly(methacrylate) (PMA) with azobenzene mesogens and is denoted by PEOm-b-PMA(Az)n, indicates a strong chemical contrast between the corresponding microdomains, which offer structurally reliable nanotemplates for fabricating nanostructured materials. Thermally annealing a PEOm-b-PMA(Az)n thin film provides hexagonally arranged, perpendicularly oriented PEO cylinders, which perform as ion-conductive nanochannels. In this study, a SiO2 layer on a silicon wafer substrate is etched by NH4F through a PEO114-b-PMA(Az)54 thin film as a nanomask. The SiO2 layer is patterned with a 24-nm-periodic hexagonally arranged nanodimple array. Atomic force microscope (AFM), field emission scanning electron microscope (FESEM), and cross-sectional transmission electron microscope (TEM) observations reveal that the nanodimple array has a 2-nm depth and is spread over the entire SiO2 surface on centimeter scale.

  9. Predicting photoisomerization profile of the highly polymerized nematic azobenzene liquid crystal network: First principle calculation

    NASA Astrophysics Data System (ADS)

    Yun, J.; Li, C.; Chung, H.; Choi, J.; Cho, M.

    2015-05-01

    The cis profile of azobenzene is a key factor in predicting the photodeformation of the nematic azobenzene liquid crystal network (LCN). An ab initio based method for predicting the photoisomerization profile of azobenzene is developed by coupling the stimulated Raman adiabatic passage (STIRAP) method with non-linear Beers law, and compared with experimental data. Using this combined method, we calculate the photoisomerization profile of azobenzene with various light input conditions. We identify the cis profile of the nematic LCN structure evolves into a step-like decaying shape when the direction of polarized light is parallel to the nematic direction.

  10. Mesogenic linear azobenzene polymer-stabilized nematic liquid crystals

    SciTech Connect

    Bagramyan, Arutyun; Thibault-Maheu, Olivier; Galstian, Tigran; Bessette, Andre; Zhao, Yue

    2011-03-15

    We describe the detailed study of a polymer stabilized liquid crystal compound, which was created by using a reactive (monofunctional) azobenzene mesogenic guest and a nematic liquid crystal host. The resonant interaction of light with the azobenzene segment of the guest and the mesogenic nature of the latter enable the optical alignment of host molecules and the permanent fixing of that orientation by means of UV polymerization of the guest. We use dynamic spectral, polarimetric, and scattering techniques to study the orientational ordering and interaction of the guest-host system. We show that the uniform UV polymerization of this compound results in a low scattering material system with dielectric and elastic properties that are relatively close to those of the host, while still providing the capacity for optical configuration of its morphology.

  11. Threshold collision induced dissociation experiment for azobenzene and its derivatives

    NASA Astrophysics Data System (ADS)

    Rezaee, Mohammadreza; Compton, Robert

    In this study we investigated protonated azobenzene cation and properties of trans 2,2',6,6'-tetrafluoroazobenzene anion using the collision induced dissociation method and the results are compared with the results from ab initio electronic structure calculations. We measured the bond dissociation energies experimentally and found which theoretical quantum chemistry methods yield best results. Several high accuracy multi-level calculations such as CBS-QB3, G3 and G4 had been carried out to obtain reliable thermochemical information for azobenzene and several of its derivatives and their anion or cation. We also performed other experiments such as Raman spectroscopy to study these light sensitive molecules with promising applications such as photo-switching.

  12. Azobenzene Modified Polymer Electrolyte Membrane for Ion Gating

    NASA Astrophysics Data System (ADS)

    Piedrahita, Camilo; Mballa, Mireille; He, Ruixuan; Kyu, Thein

    By virtue of ion concentration gradient across cell membranes, neuron cells are highly polarized driving electrical potential difference (e.g., Gibbs law). To regulate and control ion movement, living cells have specific channels with gates that are permeable to cations, enabling or excluding them via charge polarity and size. This mechanism for generating and transmitting signals from one neuron to another controls body movement via brain function. By virtue of trans-cis isomerization, azobenzene derivative (AZO) has been heavily sought for ion-gating in biological cells as a means of signal generation and transmission through nervous systems. In this work, PEM consisted of PEGDA/SCN/LiTFSI was modified with AZO derivatives for gating of lithium ions. At low concentrations of azobenzene of 3 wt Supported by NSF-DMR 1502543.

  13. Ordering of azobenzenes by two-photon isomerization

    SciTech Connect

    Ishitobi, Hidekazu; Sekkat, Zouheir; Kawata, Satoshi

    2006-10-28

    We report on light induced orientation by two-photon isomerization of azobenzenes in films of polymer. The dynamics of isomerization and orientation by one-photon absorption and two-photon absorption (TPA) are similar, and TPA creates a degree of molecular orientation which is comparable to that achieved by single-photon isomerization, in agreement with the theoretical predictions of two-photon isomeric orientation.

  14. Swimming photochromic azobenzene single crystals in triacrylate solution.

    PubMed

    Milam, Kenneth; O'Malley, Garrett; Kim, Namil; Golovaty, Dmitry; Kyu, Thein

    2010-06-17

    Self-motion of a growing single crystal of azobenzene chromophore in triacrylate solution (TA) is investigated in relation to the solid-liquid phase diagram bound by the solidus and liquidus lines. Upon thermal quenching from the isotropic melt to the crystal + liquid gap, various single crystals develop in a manner dependent on concentration and supercooling depth. During the crystal growth, TA solvent is rejected from the growing faceted fronts, enriching with TA in close proximity to the crystal-solution interface. The concentration gradient that formed as the result of TA expulsion induces convective flows in the solution and generates spatial variability of surface tension usually responsible for Marangoni effect. Either or both of these phenomena may have contributed to the observed self-motion including swimming, sinking, and floating of the azobenzene rhomboidal crystal in TA solution. A stationary rhomboidal crystal is also shown to swim upon irradiation with the UV light because of a mechanical torque generated by the trans-cis isomerization. Judging from the sinking or floating behavior of the azobenzene crystal, it may be inferred that the nucleation occurs at the solution-air interface.

  15. Light-controllable reflection wavelength of blue phase liquid crystals doped with azobenzene-dimers.

    PubMed

    Chen, Xingwu; Wang, Ling; Li, Chenyue; Xiao, Jiumei; Ding, Hangjun; Liu, Xin; Zhang, Xiaoguang; He, Wanli; Yang, Huai

    2013-10-03

    A new series of azobenzene-dimers were synthesized and doped into the blue phase liquid crystals to broaden the temperature range of BPs. It is found that not only can the reflection wavelength of BPI be reversibly controlled but BPI can also be transformed into the cholesteric phase owing to isomerization of azobenzene induced by light.

  16. An azobenzene unit embedded in a cyclopeptide as a type-specific and spatially directed switch.

    PubMed

    Haberhauer, Gebhard; Kallweit, Christine; Wölper, Christoph; Bläser, Dieter

    2013-07-22

    By embedding an azobenzene unit into a chiral scaffold, switching of azobenzene from the trans-(P) isomer to the cis-(P) isomer and back was achieved (black arrows in picture). The embedding leads to a flipping process in which the phenyl rings can only move directly towards one another in the switching process.

  17. Reversible switching of electrical conductivity in an AOT-isooctane-water microemulsion via photoisomerization of azobenzene.

    PubMed

    Bufe, Markus; Wolff, Thomas

    2009-07-21

    The electrical conductivity of microemulsions composed of aerosol OT (AOT), isooctane, and water as a function of temperature was studied in the absence and presence of azobenzene, and consequences of an in situ trans-cis photoisomerization of azobenzene were investigated. A conductivity onset upon raising the temperature of a water-in-oil microemulsion indicates percolation. Small amounts (0.1-5% w/w) of solubilized azobenzene induce higher percolation temperatures T(p) (by up to 19 K), and photoisomerization of azobenzene shifts T(p) back to values that may be below T(p) in the absence of azobenzene. Consequently, the microemulsion can be switched from nonconducting to conducting by exposing samples to UV-light at lambda > 310 nm, without varying temperature or composition. The effect reverts within several minutes after turning off the irradiation lamp through thermal reisomerization. By that, reversible switching of electrical conductivity is brought about.

  18. Polarization holographic data storage using azobenzene polyster as storage material

    NASA Astrophysics Data System (ADS)

    Loerincz, Emoeke; Szarvas, Gabor; Koppa, Pal; Ujhelyi, Ferenc; Erdei, Gabor; Sueto, Attila; Varhegyi, Peter; Sajti, Sz.; Kerekes, A.; Ujvari, T.; Ramanujam, P. S.

    2003-07-01

    Polarization holographic read/write and read only demonstrator systems have been developed using ~2 ´m thick azobenzene polyester on a card form media. The thin-film holographic system has practical advantages, e.g. high diffraction efficiency, no cross talk between the holograms, reading in reflection mode, no hardware servo, different wavelengths for writing and reading (non-volatile storage), data encryption possibility, no problem with material shrinkage, etc. The candidate azobenzene polyester has good thermal, room temperature and ambient light stability and good optical properties for the purpose of thin film application. Using thin-film holography the possibilities of multiplexing are limited, however, raw data density as high as 2.77 bit/´m2 has been achieved in an optimized Fourier holographic system using high numerical aperture (NAþ 0.74) objective in a 8f arrangement with sparse code modulation and Fourier-filtering at 532 nm. High density polarization holographic demonstrator systems have been developed using ~2μm thick azobenzene polyesters on reflective card form media. FFT computer simulation of the system including saturation model of the material allows optimization of system components including data density and capacity. A raw density as high as 2.77 bit/μm2 has been achieved without multiplexing in a compact, portable read/write sytem at 532 nm allowing more than 1000 readout without data loss. A separate read only system working at 635 nm realizes non-volatile readout and allows card exchange at a data density of 1.3 bit/μm2. Security level of the presents holographic optical card systems can be further increased by using phase encoded reference beam. Advantageous applications of the proposed encrypted holographic card system are also outlined.

  19. Modification of nucleic acids by azobenzene derivatives and their applications in biotechnology and nanotechnology.

    PubMed

    Li, Jing; Wang, Xingyu; Liang, Xingguo

    2014-12-01

    Azobenzene has been widely used as a photoregulator due to its reversible photoisomerization, large structural change between E and Z isomers, high photoisomerization yield, and high chemical stability. On the other hand, some azobenzene derivatives can be used as universal quenchers for many fluorophores. Nucleic acid is a good candidate to be modified because it is not only the template of gene expression but also widely used for building well-organized nanostructures and nanodevices. Because the size and polarity distribution of the azobenzene molecule is similar to a nucleobase pair, the introduction of azobenzene into nucleic acids has been shown to be an ingenious molecular design for constructing light-switching biosystems or light-driven nanomachines. Here we review recent advances in azobenzene-modified nucleic acids and their applications for artificial regulation of gene expression and enzymatic reactions, construction of photoresponsive nanostructures and nanodevices, molecular beacons, as well as obtaining structural information using the introduced azobenzene as an internal probe. In particular, nucleic acids bearing multiple azobenzenes can be used as a novel artificial nanomaterial with merits of high sequence specificity, regular duplex structure, and high photoregulation efficiency. The combination of functional groups with biomolecules may further advance the development of chemical biotechnology and biomolecular engineering.

  20. Shapeshifting photoswitchable azobenzene compounds and their biological applications

    NASA Astrophysics Data System (ADS)

    Peddie, Victoria; Heng, Sabrina; Mustafa, Sanam; Thomas, Jacob; Hutchinson, Mark R.; Abell, Andrew D.

    2016-11-01

    The photoisomerisation of azobenzenes between trans and cis results in well-defined changes in geometry and a considerable change of polarity. Thus, incorporating an azobenezene into a bioactive compound provides an opportunity to control biological activity, with ideally one configuration being active and the other inactive. This can allow the role of a specific biomolecule to be probed in its native environment by controlling activity both spatially and temporally using light. Incorporating such a photoswitchable moiety into the structure of a known GRK2 inhibitor can generate photoswitchable inhibitors, which can be used to reversibly regulate the activity of GRK2, and hence GPRCs.

  1. Deuterium isotope effects in 13C NMR spectra of trans-azobenzene

    NASA Astrophysics Data System (ADS)

    Vikić-Topić, Draz̆en; Novak, Predrag; Smrec̆ki, Vilko; Meić, Zlatko

    1997-06-01

    Deuterium isotope effects on 13C chemical shifts have been determined in a series of deuteriated trans-azobenzene isotopomers. The longest effect observed is the one over ten bonds ( 10Δ) in 4- 2H-isotopomer at C-4' atom amounting to 3.3 ppb. The magnitude and the extent of isotope effects in trans-azobenzene are related to those observed in isoelectronic and conformationally similar trans-stilbene. The sign alternation pattern of the long-range isotope effects in trans-azobenzene parallels that in isoelectronic trans-stilbene, cis-stilbene and trans-N-benzylideneaniline.

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

    PubMed

    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.

  3. Photoelectrical properties of indandione fragment containing azobenzene compounds

    NASA Astrophysics Data System (ADS)

    Latvels, Janis; Grzibovskis, Raitis; Pudzs, Kaspars; Vembris, Aivars; Blumberga, Dagnija

    2014-05-01

    Organic materials are becoming more popular due to their potential application in electronics. Low molecular weight materials possible produce from solution are in special consideration. It gives the possibility to avoid both thermal evaporation in vacuum, and use of polymers in thin film preparation process. Indandione fragment containing azobenzene compounds are one of such materials. These compounds are good candidates for use in design of novel molecular electronic devices due to their possibility to form amorphous structure from solution thus allowing developing flexible, small size systems with low production costs. In this work three indandione fragment containing azobenzene compounds were investigated. Difference between these compounds is bulky groups which assist formation of amorphous thin film. Absorption spectra of the investigated compounds are similar to P3HT but with higher absorption coefficient. Molecule ionization and electron affinity levels of these compounds are around -5.45eV and -3.80eV, respectively. Combining PCBM with investigated compounds could lead to difference between electron affinity levels maximum of 0.15eV. It is several times less compared to ~1eV for P3HT:PCBM system. Higher difference between the donor ionization level and the acceptor affinity level could also be obtained which should lead to the higher open circuit voltage.

  4. From Macromolecular to Small-Molecular Triggers: Facile Method toward Photoinduced LCST Phase Behavior of Thermoresponsive Polymers in Mixed Ionic Liquids Containing an Azobenzene Moiety.

    PubMed

    Wang, Caihong; Ma, Xiaofeng; Kitazawa, Yuzo; Kobayashi, Yumi; Zhang, Shiguo; Kokubo, Hisashi; Watanabe, Masayoshi

    2016-12-01

    Instead of the reported photoinduced lower critical solution temperature (LCST) phase transition behavior in ionic liquids (ILs) achieved by photofunctional polymers, this study reports the facile photoinduced LCST phase behavior of nonfunctionalized polymers (poly(benzyl methacrylate) (PBnMA) and poly(2-phenylethyl methacrylate) (PPhEtMA)) in mixed ILs (1,3-dimethylimidazolium bis(trifluoromethanesulfonyl)amide; [C1 mim][NTf2 ] and a newly designed functionalized IL containing an azobenzene moiety (1-butyl-3-(4-phenylazobenzyl)imidazolium bis(trifluoromethanesulfonyl)amide; [Azo][NTf2 ])) as a small-molecular photo trigger. Interestingly, the length of the alkyl spacer between the ester and aryl groups, which is the only structural difference between the two polymers, leads to two different photoresponsive LCST phase transition behaviors. On the basis of spectroscopic studies, the different phase transition behaviors of PBnMA and PPhEtMA may attribute to the different cooperative interactions between the polymers and [C1 mim][NTf2 ].

  5. Azobenzene C-Nucleosides for Photocontrolled Hybridization of DNA at Room Temperature.

    PubMed

    Goldau, Thomas; Murayama, Keiji; Brieke, Clara; Asanuma, Hiroyuki; Heckel, Alexander

    2015-12-01

    Herein, we report the reversible light-regulated destabilization of DNA duplexes by using azobenzene C-nucleoside photoswitches. The incorporation of two different azobenzene residues into DNA and their photoswitching properties are described. These new residues demonstrate a photoinduced destabilization effect comparable to the widely applied D-threoninol-linked azobenzene switch, which is currently the benchmark. The photoswitches presented herein show excellent photoswitching efficiencies in DNA duplexes - even at room temperature - which are superior to commonly used azobenzene-based nucleic acid photoswitches. In addition, these photoswitching residues exhibit high thermal stability and excellent fatigue resistance, thus rendering them one of the most efficient candidates for the regulation of duplex stability with light.

  6. Precise Actuation of Bilayer Photomechanical Films Coated with Molecular Azobenzene Chromophores.

    PubMed

    Liu, Ziyi; Tang, Rong; Xu, Dandan; Liu, Jian; Yu, Haifeng

    2015-06-01

    Bilayer photomechanical films are fabricated by depositing one layer of molecular azobenzene chromophores onto flexible low-density polyethylene substrates. The photoinduced bending and unbending behavior of five azobenzene derivatives including azobenzene, 4-hydroxy-azobenzene, 4-((4-hydroxyphenyl)diazenyl)bezoitrile, 4-((4-methoxyph-enyl)diazenyl)phenol, and 4-(phenyldiazenyl)phenol is systematically studied by considering the incident light intensity and the thickness of the coated chromophore layers. Precise control of photoinduced curling of the bilayer film is successfully achieved upon irradiation with two beams of UV light, and the curled films can be recovered by thermal relaxation in the dark. The easily fabricated bilayer films show fast photomechanical response, strong photoinduced stress, and stability similar to crosslinked polymeric films.

  7. Irradiance and Temperature Dependence of Photo-Induced Orientation in Two Azobenzene-Based Polymers

    DTIC Science & Technology

    1998-06-23

    and Almeria Natansohn* Department of Chemistry, Queen’s University, Kingston, Ontario, K7L 3N6 Paul Rochon Department of Physics, Royal Military...1. IRRADIANCE AND TEMPERATURE DEPENDENCE OF PHOTO-INDUCED ORIENTATION IN TWO AZOBENZENE-BASED POLYMERS Dennis Hore and Almeria Natansohn...IRRADIANCE AND TEMPERATURE DEPENDENCE OF PHOTO-INDUCED ORIENTATION IN TWO AZOBENZENE-BASED POLYMERS Dennis Hore and Almeria Natansohn Department of

  8. Direct Fabrication of Micro/Nano-Patterned Surfaces by Vertical-Directional Photofluidization of Azobenzene Materials.

    PubMed

    Choi, Jaeho; Cho, Wonhee; Jung, Yeon Sik; Kang, Hong Suk; Kim, Hee-Tak

    2017-02-28

    Anisotropic movement of azobenzene materials (i.e., azobenzene molecules incorporated in polymer, glass, or supramolecules) has provided significant opportunities for the fabrication of micro/nanoarchitectures. The examples include circular holes, line gaps, ellipsoidal holes, and nanofunnels. However, all of the previous studies have only focused on the lateral directional movement for the structural shaping of azobenzene materials. Herein, we propose structural shaping based on a vertical directional movement of azobenzene materials. To do this, light with oblique incidence, containing normal direction light polarization, was illuminated onto azobenzene materials film contact with patterned elastomeric molds (i.e., PDMS) so that the resulting vertical directional movement of azobenzene materials fills in the cavities of the molds and results in pattern formation. As a result, a range of patterns with sizes of features from micro- to sub-100 nm scale was successfully fabricated in a large area (few cm(2)), and the structural height was deterministically controlled by simply adjusting irradiation time. In addition to the notable capability of fabricating the single-scale structures, the technique provides a facile way to fabricate complex hierarchical multiscale structures, ensuring its versatility and wide applicability to various applications. As a selected exemplary application of the multiscale structures, a superhydrophobic surface has been successfully demonstrated.

  9. Fluorinated Azobenzenes for Shape-Persistent Liquid Crystal Polymer Networks.

    PubMed

    Iamsaard, Supitchaya; Anger, Emmanuel; Aßhoff, Sarah Jane; Depauw, Alexis; Fletcher, Stephen P; Katsonis, Nathalie

    2016-08-16

    Liquid crystal polymer networks respond with an anisotropic deformation to a range of external stimuli. When doped with molecular photoswitches, these materials undergo complex shape modifications under illumination. As the deformations are reversed when irradiation stops, applications where the activated shape is required to have thermal stability have been precluded. Previous attempts to incorporate molecular switches into thermally stable photoisomers were unsuccessful at photogenerating macroscopic shapes that are retained over time. Herein, we show that to preserve photoactivated molecular deformation on the macroscopic scale, it is important not only to engineer the thermal stability of the photoswitch but also to adjust the cross-linking density in the polymer network and to optimize the molecular orientations in the material. Our strategy resulted in materials containing fluorinated azobenzenes that retain their photochemical shape for more than eight days, which constitutes the first demonstration of long-lived photomechanical deformation in liquid-crystal polymer networks.

  10. Photochromic switching of the DNA helicity induced by azobenzene derivatives

    PubMed Central

    Deiana, Marco; Pokladek, Ziemowit; Olesiak-Banska, Joanna; Młynarz, Piotr; Samoc, Marek; Matczyszyn, Katarzyna

    2016-01-01

    The photochromic properties of azobenzene, involving conformational changes occurring upon interaction with light, provide an excellent tool to establish new ways of selective regulation applied to biosystems. We report here on the binding of two water-soluble 4-(phenylazo)benzoic acid derivatives (Azo-2N and Azo-3N) with double stranded DNA and demonstrate that the photoisomerization of Azo-3N leads to changes in DNA structure. In particular, we show that stabilization and destabilization of the B-DNA secondary structure can be photochemically induced in situ by light. This photo-triggered process is fully reversible and could be an alternative pathway to control a broad range of biological processes. Moreover, we found that the bicationic Azo-3N exhibited a higher DNA-binding constant than the monocationic Azo-2N pointing out that the number of positive charges along the photosensitive polyamines chain plays a pivotal role in stabilizing the photochrome-DNA complex. PMID:27339811

  11. Photochromic switching of the DNA helicity induced by azobenzene derivatives

    NASA Astrophysics Data System (ADS)

    Deiana, Marco; Pokladek, Ziemowit; Olesiak-Banska, Joanna; Młynarz, Piotr; Samoc, Marek; Matczyszyn, Katarzyna

    2016-06-01

    The photochromic properties of azobenzene, involving conformational changes occurring upon interaction with light, provide an excellent tool to establish new ways of selective regulation applied to biosystems. We report here on the binding of two water-soluble 4-(phenylazo)benzoic acid derivatives (Azo-2N and Azo-3N) with double stranded DNA and demonstrate that the photoisomerization of Azo-3N leads to changes in DNA structure. In particular, we show that stabilization and destabilization of the B-DNA secondary structure can be photochemically induced in situ by light. This photo-triggered process is fully reversible and could be an alternative pathway to control a broad range of biological processes. Moreover, we found that the bicationic Azo-3N exhibited a higher DNA-binding constant than the monocationic Azo-2N pointing out that the number of positive charges along the photosensitive polyamines chain plays a pivotal role in stabilizing the photochrome-DNA complex.

  12. Antimicrobial azobenzene compounds and their potential use in biomaterials

    NASA Astrophysics Data System (ADS)

    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.

  13. Azobenzene-based supramolecular polymers for processing MWCNTs

    NASA Astrophysics Data System (ADS)

    Maggini, Laura; Marangoni, Tomas; Georges, Benoit; Malicka, Joanna M.; Yoosaf, K.; Minoia, Andrea; Lazzaroni, Roberto; Armaroli, Nicola; Bonifazi, Davide

    2012-12-01

    Photothermally responsive supramolecular polymers containing azobenzene units have been synthesised and employed as dispersants for multi-walled carbon nanotubes (MWCNTs) in organic solvents. Upon triggering the trans-cis isomerisation of the supramolecular polymer intermolecular interactions between MWCNTs and the polymer are established, reversibly affecting the suspensions of the MWCNTs, either favouring it (by heating, i.e. cis --> trans isomerisation) or inducing the CNTs' precipitation (upon irradiation, trans --> cis isomerisation). Taking advantage of the chromophoric properties of the molecular subunits, the solubilisation/precipitation processes have been monitored by UV-Vis absorption spectroscopy. The structural properties of the resulting MWCNT-polymer hybrid materials have been thoroughly investigated via thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and atomic force microscopy (AFM) and modelled with molecular dynamics simulations.Photothermally responsive supramolecular polymers containing azobenzene units have been synthesised and employed as dispersants for multi-walled carbon nanotubes (MWCNTs) in organic solvents. Upon triggering the trans-cis isomerisation of the supramolecular polymer intermolecular interactions between MWCNTs and the polymer are established, reversibly affecting the suspensions of the MWCNTs, either favouring it (by heating, i.e. cis --> trans isomerisation) or inducing the CNTs' precipitation (upon irradiation, trans --> cis isomerisation). Taking advantage of the chromophoric properties of the molecular subunits, the solubilisation/precipitation processes have been monitored by UV-Vis absorption spectroscopy. The structural properties of the resulting MWCNT-polymer hybrid materials have been thoroughly investigated via thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and atomic force microscopy

  14. Dual-Responsive pH and Temperature Sensitive Nanoparticles Based on Methacrylic Acid and Di(ethylene glycol) Methyl Ether Methacrylate for the Triggered Release of Drugs.

    PubMed

    Khine, Yee Yee; Jiang, Yanyan; Dag, Aydan; Lu, Hongxu; Stenzel, Martina H

    2015-08-01

    A series of thermo-and pH-responsive poly(methyl methacrylate)-block-poly[methacrylic acid-co-di(ethylene glycol) methyl ether methacrylate] PMMA-b-P[MAA-co-DEGMA] block copolymers were synthesized by RAFT polymerization and self-assembled into micelles. The molar ratio of MAA was altered from 0-12% in order to modulate the lower critical solution temperature (LCST) of PDEGMA. The release of the drug albendazole from the micelle was strongly dependent on the temperature and the LCST value of the polymer. Systems below the LCST released the drug slowly while increasing the temperature above the LCST or decreasing the pH value to 5 resulted in the burst-like release of the drug. ABZ delivered in this pH-responsive drug carrier had a higher toxicity than the free drug or the drug delivered in a non-responsive drug carrier.

  15. Synthesis of three different galactose-based methacrylate monomers for the production of sugar-based polymers.

    PubMed

    Desport, Jessica S; Mantione, Daniele; Moreno, Mónica; Sardón, Haritz; Barandiaran, María J; Mecerreyes, David

    2016-09-02

    Glycopolymers, synthetic sugar-containing macromolecules, are attracting ever-increasing interest from the chemistry community. Glycidyl methacrylate (GMA) is an important building block for the synthesis of sugar based methacrylate monomers and polymers. Normally, glycidyl methacrylate shows some advantages such as reactivity against nucleophiles or milder synthetic conditions such as other reactive methacrylate monomers. However, condensation reactions of glycidyl methacrylate with for instance protected galactose monomer leads to a mixture of two products due to a strong competition between the two possible pathways: epoxide ring opening or transesterification. In this paper, we propose two alternative routes to synthesize regiospecific galactose-based methacrylate monomers using the epoxy-ring opening reaction. In the first alternative route, the protected galactose is first oxidized to the acid in order to make it more reactive against the epoxide of GMA. In the second route, the protected sugar was first treated with epichlorohydrin followed by the epoxy ring opening reaction with methacrylic acid, to create an identical analogue of the ring-opening product of GMA. These two monomers were polymerized using conventional radical polymerization and were compared to the previously known galactose-methacrylate one. The new polymers show similar thermal stability but lower glass transition temperature (Tg) with respect to the known galactose methacrylate polymer.

  16. 78 FR 55644 - Styrene, Copolymers with Acrylic Acid and/or Methacrylic Acid; Tolerance Exemption

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-09-11

    ... methacrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and/or hydroxyethyl acrylate; and its sodium... methacrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and/or hydroxyethyl acrylate; and its sodium... methacrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and/or hydroxyethyl acrylate, and its...

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

    PubMed

    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.

  18. A Unified Material Description for Light Induced Deformation in Azobenzene Polymers

    PubMed Central

    Bin, Jonghoon; Oates, William S.

    2015-01-01

    Complex light-matter interactions in azobenzene polymers have limited our understanding of how photoisomerization induces deformation as a function of the underlying polymer network and form of the light excitation. A unified modeling framework is formulated to advance the understanding of surface deformation and bulk deformation of polymer films that are controlled by linear or circularly polarized light or vortex beams. It is shown that dipole forces strongly respond to polarized light in contrast to higher order quadrupole forces that are often used to describe surface relief grating deformation through a field gradient constitutive law. The modeling results and comparisons with a broad range of photomechanical data in the literature suggest that the molecular structure of the azobenzene monomers dramatically influences the photostrictive behavior. The results provide important insight for designing azobenzene monomers within a polymer network to achieve enhanced photo-responsive deformation. PMID:26437598

  19. Light-driven strong spin valve effects in an azobenzene-based spin optoelectronic device

    NASA Astrophysics Data System (ADS)

    Zeng, Jing; Chen, Ke-Qiu; Deng, Xiaohui; Long, Mengqiu

    2016-10-01

    A photoswitched single-molecule junction, a stable and reversible single-molecule electrical switch, has been successfully prepared by means of molecular engineering (2016 Science 352 1443). In this work we use a first-principles computational approach to investigate the spin valve effect of an azobenzene-based spin optoelectronic device. Our results demonstrate that the magnetoresistive ratio of the spin optoelectronic device is only about 65% when the azobenzene is in cis configuration, which is a low performance for practical applications. However, the magnetoresistive ratio of the device can be enhanced to about 2775% when the cis configuration of the azobenzene is changed into the trans configuration by applying a pulse of light. As a consequence, photoexcitation provides an effective way to obtain a high-performance spin optoelectronic device.

  20. Time-dependent density functional study on the photoisomerization mechanism of azobenzene

    NASA Astrophysics Data System (ADS)

    Oyama, Norihisa; Tateyama, Yoshitaka; Miyamoto, Yoshiyuki; Ohno, Takahisa

    2004-03-01

    Photochemical reactions in organic molecules have attracted considerable attention in semiconductor physics and also in bioscience. Azobenzene is a simple molecule which shows the reversible photoisomerization at high quantum yields, and can be used as a light-driven molecular switch and so on. However, the photoisomerization process of azobenzene is still an open question because of its femtosecond ultra-fast reaction. In this talk, we present time-dependent density functional calculations for the azobenzene molecule, and discuss the mechanism of photoisomerization induced by S1 and S2 excitations. This research is partially supported by ACT-JST, and also by FSIS and Special Coordination Funds of MEXT of Japanese Government. The calculations were carried out partly using the Numerical Materials Simulator in National Institute for Materials Science, and partly using the NEC-SX5 at Cybermedia Center of Osaka University.

  1. Orthogonal light-induced self-assembly of nanoparticles using differently substituted azobenzenes.

    PubMed

    Manna, Debasish; Udayabhaskararao, Thumu; Zhao, Hui; Klajn, Rafal

    2015-10-12

    Precise control of the self-assembly of selected components within complex mixtures is a challenging goal whose realization is important for fabricating novel nanomaterials. Herein we show that by decorating the surfaces of metallic nanoparticles with differently substituted azobenzenes, it is possible to modulate the wavelength of light at which the self-assembly of these nanoparticles is induced. Exposing a mixture of two types of nanoparticles, each functionalized with a different azobenzene, to UV or blue light induces the selective self-assembly of only one type of nanoparticles. Irradiation with the other wavelength triggers the disassembly of the aggregates, and the simultaneous self-assembly of nanoparticles of the other type. By placing both types of azobenzenes on the same nanoparticles, we created unique materials ("frustrated" nanoparticles) whose self-assembly is induced irrespective of the wavelength of the incident light.

  2. Nanoparticle assembly of a photo- and pH-responsive random azobenzene copolymer.

    PubMed

    Feng, Ning; Han, Guoxiang; Dong, Jie; Wu, Hao; Zheng, Yudong; Wang, Guojie

    2014-05-01

    Stimuli-responsive polymeric nanoparticles with a core of hydrophobic azobenzene-containing acrylate units and a shell of hydrophilic acrylic acid units were prepared from a novel photo- and pH-responsive amphiphilic random azobenzene copolymer. Upon UV light irradiation, the trans azobenzene changed to the cis form and thus the water contact angle and the absorption of water on the polymer film could be changed, while little effect was exerted on the morphology of the nanoparticles although the polarity of the core of nanoparticles increased. Adjusting pH of the nanoparticle solution could exert a strong effect on the morphology of the nanoparticles. The prime nanoparticles (pH 6) changed to nanoparticle aggregates at pH 3, and to swollen nanoparticles at pH 11. The controlled release of Nile Red from the nanoparticles under the stimuli was demonstrated.

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

    PubMed

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

    2016-08-04

    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.

  4. Thermomechanical behavior of amorphous tactic methacrylate polymers

    NASA Technical Reports Server (NTRS)

    Kiran, E.; Gillham, J. K.; Gipstein, E.

    1974-01-01

    Dynamic mechanical spectra of amorphous stereoregular poly(methyl methacrylate)s and poly(t-butyl methacrylate)s with assigned microtacticities are presented and discussed. An intermolecular argument is invoked to account for the higher glass transition temperature of syndiotactic vis a vis isotactic PMMA, in spite of the higher density of the latter at 30 C. An argument is presented to show that the ratio of glassy-region relaxation temperature to glass transition temperature is not only a measure of the degree of coupling of the beta and glass transition processes, but also of the degree to which intermolecular factors influence these processes. The greater extent of the low-temperature irreversibilities observed in the thermomechanical spectra of poly(t-butyl methacrylate)s is attributed to the brittle character induced by the bulky side groups which presumably weaken cohesive forces.

  5. Optically Reconfigurable Monolayer of Azobenzene Donor Molecules on Oxide Surfaces.

    PubMed

    McElhinny, Kyle M; Huang, Peishen; Joo, Yongho; Kanimozhi, Catherine; Lakkham, Arunee; Sakurai, Kenji; Evans, Paul G; Gopalan, Padma

    2017-03-07

    The structural configuration of molecules assembled at organic-inorganic interfaces within electronic materials strongly influences the functional electronic and vibrational properties relevant to applications ranging from energy storage to photovoltaics. Controlling and characterizing the structural state of an interface and its evolution under external stimuli is crucial both for the fundamental understanding of the factors influenced by molecular structure and for the development of methods for material synthesis. It has been challenging to create complete molecular monolayers that exhibit external reversible control of the structure and electronic configuration. We report a monolayer/inorganic interface consisting of an organic monolayer assembled on an oxide surface, exhibiting structural and electronic reconfiguration under ultraviolet illumination. The molecular monolayer is linked to the surface through a carboxylate link, with the backbone bearing an azobenzene functional group and the head group consisting of a rhenium-bipyridine group. Optical spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and X-ray reflectivity show that closely packed monolayers are formed from these molecules via the Langmuir-Blodgett technique. Reversible photoisomerization is observed in solution and in monolayers assembled on Si and quartz substrates. The reconfiguration of these monolayers provides additional means to control excitation and charge transfer processes that are important in applications in catalysis, molecular electronics, and solar energy conversion.

  6. Contactless, photoinitiated snap-through in azobenzene-functionalized polymers

    PubMed Central

    Shankar, M. Ravi; Smith, Matthew L.; Tondiglia, Vincent P.; Lee, Kyung Min; McConney, Michael E.; Wang, David H.; Tan, Loon-Seng; White, Timothy J.

    2013-01-01

    Photomechanical effects in polymeric materials and composites transduce light into mechanical work. The ability to control the intensity, polarization, placement, and duration of light irradiation is a distinctive and potentially useful tool to tailor the location, magnitude, and directionality of photogenerated mechanical work. Unfortunately, the work generated from photoresponsive materials is often slow and yields very small power densities, which diminish their potential use in applications. Here, we investigate photoinitiated snap-through in bistable arches formed from samples composed of azobenzene-functionalized polymers (both amorphous polyimides and liquid crystal polymer networks) and report orders-of-magnitude enhancement in actuation rates (approaching 102 mm/s) and powers (as much as 1 kW/m3). The contactless, ultra-fast actuation is observed at irradiation intensities <<100 mW/cm2. Due to the bistability and symmetry of the snap-through, reversible and bidirectional actuation is demonstrated. A model is developed to elucidate the underlying mechanics of the snap-through, specifically focusing on isolating the role of sample geometry, mechanical properties of the materials, and photomechanical strain. Using light to trigger contactless, ultrafast actuation in an otherwise passive structure is a potentially versatile tool to use in mechanical design at the micro-, meso-, and millimeter scales as actuators, as well as switches that can be triggered from large standoff distances, impulse generators for microvehicles, microfluidic valves and mixers in laboratory-on-chip devices, and adaptive optical elements. PMID:24190994

  7. Photoinduced conformational switch of enantiopure azobenzenes controlled by a sulfoxide.

    PubMed

    Carreño, M Carmen; García, Isabel; Núñez, Irene; Merino, Estíbaliz; Ribagorda, María; Pieraccini, Silvia; Spada, Gian Piero

    2007-06-06

    Two series of enantiopure azobenzenes with a p-tolylsulfoxide at the ortho or meta position with respect to the azo group, have been regioselectively synthesized. Both can act as enantiopure molecular switches showing different structural features owing to the presence of the stereogenic sulfur. The photoisomerization process, studied by UV-vis, circular dichroism (CD), NMR, and chiral HPLC evidenced a double role of the sulfoxide. A transfer of chirality from the sulfoxide to the azo system was observed by CD in both cis and trans-isomers of the meta sulfinyl derivatives 3, whereas this perturbation was evident for the ortho sulfinyl series 7 only in the cis isomer. The NMR study evidenced that the s-cis rigid conformation of the bisaromatic sulfoxide was fixing a different orientation of the overall system in each series both in the trans and cis isomers, by forcing a final U-shaped structure in cis-3 and an S-shaped structure in cis-7. Very different values of specific optical rotations were measured in both trans and cis isomers, also reflecting the existence of distinct chiral entities in the photostationary states. The easy and reversible changes occurring between different conformational states could find applications in the photocontrol of several molecular switches.

  8. Photomechanical response of azobenzene/organophilic mica complexes

    SciTech Connect

    Fujita, T.; Iyi, N.; Klapyta, Z.; Fujii, K.; Kaneko, Y.; Kitamura, K

    2003-12-10

    To clarify whether photomechanical response is limited to the special combination of azobenzene (AzBz)/organophilic tetrasilicic mica (TSM) complexes, another swelling synthetic fluoro-mica, lithium taeniolite, was used as a starting host for AzBz/organophilic mica complexes. Basal spacings of organophilic taeniolites (o-TNs) prepared by the intercalation of trimethylalkylammonium (TMAA) into the TN increased linearly as alkyl chain length in TMAA increased from 2.44 to 2.86 nm. This indicates paraffin-type arrangement of TMAA in the TN gallery. Intercalation of AzBz to o-TN was performed via the gas phase at 100 deg. C. Photoresponses of AzBz/o-TN complexes were examined by XRD measurement under alternate UV and visible light irradiation. A decrease in basal spacing was observed under UV irradiation, and an increase was under visible light irradiation. Basal spacing change was 0.09-0.18 nm, which corresponds to 3-5% of the AzBz/o-TN basal spacing. These results indicate that reversible photomechanical response is a general phenomenon for AzBz/organophilic mica complexes.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Optically-tunable beam steering grating based n azobenzene doped cholesteric liquid crystal.

    PubMed

    Jau, Hung-Chang; Lin, Tsung-Hsien; Fung, Ri-Xin; Huang, San-Yi; Liu, J-H; Fuh, Andy Y-G

    2010-08-02

    This work proposes an optically controllable beam-steering device, fabricated using cholesteric liquid crystals (CLCs) that are doped with azobenzene. The trans-cis photoisomerization of azobenzene changes the pitch of the CLC fingerprint structure and shifts the diffraction angle. The diffraction angle increases when the cell is irradiated with UV light, and restored when it is irradiated with green light. Combining the photoisomerization effect with electrical effect, the CLC beam-steering device provides a steering angle of approximately 19 degrees. The tuning is continuous and could be completed within a few seconds.

  11. 40 CFR 721.10153 - Modified methyl methacrylate, 2-hydroxyethyl methacrylate polymer (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...-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...

  12. 40 CFR 721.10153 - Modified methyl methacrylate, 2-hydroxyethyl methacrylate polymer (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-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...

  13. 40 CFR 721.9492 - Polymers of styrene, cyclohexyl methacrylate and substituted methacrylate.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Polymers of styrene, cyclohexyl... Significant New Uses for Specific Chemical Substances § 721.9492 Polymers of styrene, cyclohexyl methacrylate... generically as polymers of styrene, cyclohexyl methacrylate and substituted methacrylate (PMNs...

  14. 40 CFR 721.10153 - Modified methyl methacrylate, 2-hydroxyethyl methacrylate polymer (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-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...

  15. 40 CFR 721.10153 - Modified methyl methacrylate, 2-hydroxyethyl methacrylate polymer (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-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...

  16. 40 CFR 721.10153 - Modified methyl methacrylate, 2-hydroxyethyl methacrylate polymer (generic).

    Code of Federal Regulations, 2010 CFR

    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...

  17. Orientation dynamics of azobenzene-based self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Fang, Guanjiu

    2007-12-01

    Self-assembled monolayers (SAMs) synthesized on glass and incorporating azobenzene are illuminated with actinic light to study the effect of photo-isomerization on in-plane molecular orientation. Measurements of the monolayer birefringence show that the SAM orientation dynamics are non-first-order kinetics, characterized by an exponential relaxation with a distribution of relaxation times. The orientational birefringence decays as a power law with an exponent that decreases with increasing initial writing intensity, indicative of orientational trapping wells with a distribution of depths. The distribution of trapping well depths, resulting from the distribution of free volumes among the SAM molecules, is modified by exposure to light. This depth modification indicates that photoisomerization is a collective process depending on neighboring molecules. Increasing the light intensity enhances the collective effect so that the orientation dynamics are changed from fractal to normal diffusion. With a further increase in light intensity, the collective effect does not change any more so that the mean width of the trapping well depth distribution, characterized by the power law exponent, becomes constant. The liquid crystal alignment in a photo-buffed SAM/rubbed nylon twisted nematic cell is very stable at room temperature, but it is lost upon cooling if the liquid crystal is heated into the isotropic phase, which is attributed to the thermal orientational relaxation of the SAM molecules. The liquid crystal response to reorienting the SAM with polarized light depends on the initial SAM writing time: the harder the initial writing, the slower subsequent reorientation, which is similar to the behavior of bare SAMs. The reorientation of the liquid crystals shows hysteresis compared with that of bare SAMs, with a larger dose required at higher intensity.

  18. Azobenzene-based surface patterns revisited: New insights with new materials? (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Priimagi, Arri

    2016-09-01

    This contribution focuses on a relatively old topic of azobenzene photomechanics, namely the photoinduced surface patterning. The phenomenon was demonstrated alreay in 1995, yet it has not redeemed its promise as a simple, one-step patterning method that could challenge the more conventional microfabrication techniques. However, inspired by recent advances in fabrication techniques, materials development, and theoretical modelling, the field is going through a revival from both fundamental and applied perspectives. (i) How much (or how little) azobenzene needed in order to create the surface patterns? (ii) What is the maximum size of objects that can be moved with light? (iii) Can one pattern crystalline materials? (iv) Under what conditions ss the patterning process light-reversible? These questions will herein be addressed via four case studies, all employing supramolecular materials where non-covalent intermolecular interactions are used to attach the azobenzenes into a passive host matrix. All azobenzene-based material movements are triggered by photoisomerization and are therefore inherently related to one another, and therefore we believe our observations to provide useful insights also for photomobile materials and photomechanical actuation.

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

    SciTech Connect

    Yadavalli, Nataraja Sekhar; Santer, Svetlana; Saphiannikova, Marina

    2014-08-04

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

  20. Surface Organization, Light-Driven Surface Changes, and Stability of Semifluorinated Azobenzen Polymers

    SciTech Connect

    Paik,M.; Krishnan, S.; You, F.; Li, X.; Hexemer, A.; Ando, Y.; Kang, S.; Fischer, D.; Kramer, E.; Ober, C.

    2007-01-01

    A series of polymers with 4-perfluoroalkyl-modified azobenzene side groups was investigated for its light-induced changes in surface properties. The ultraviolet (UV) light activated trans to cis isomerization of the azobenzene group, and the influence of molecular order and orientation on this process were studied using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and water contact angle measurements. Light-induced molecular reorganization in the near-surface region was studied by NEXAFS using in situ UV irradiation of polymer thin films. Differential scanning calorimetry and wide-angle X-ray scattering studies showed that sufficiently long fluoroalkyl groups formed well-ordered smectic mesophases in the bulk, as well as on the surface, which was evidenced by NEXAFS. The disruption of mesogen packing by photoisomerization was found to be influenced by the fluoroalkyl segment length. Surfaces with perfluorohexyl and perfluorooctyl groups that showed high orientational order were also highly resistant to light-induced changes. In such cases, the trans-cis isomerization resulted in greater lowering of the azobenzene phenyl ring order parameters than the perfluoroalkyl order parameters. UV exposure caused reorientation of the phenyl rings of the azobenzene group, but the terminal perfluoroalkyl segments remained more or less ordered.

  1. Exposure to volatile methacrylates in dental personnel.

    PubMed

    Hagberg, Stig; Ljungkvist, Göran; Andreasson, Harriet; Karlsson, Stig; Barregård, Lars

    2005-06-01

    Dental personnel are exposed to acrylates due to the acrylic resin-based composites and bonding agents used in fillings. It is well known that these compounds can cause contact allergy in dental personnel. However, in the 1990s, reports emerged on asthma also caused by methacrylates. The main volatile acrylates in dentistry are 2-hydroxyethyl methacrylate and methyl methacrylate. The aim of this study was to quantify the exposure to these acrylates in Swedish dental personnel. We studied the exposure to 2-hydroxyethyl methacrylate and methyl methacrylate in five randomly selected public dental clinics and at the Faculty of Odontology at Göteborg University. In total, 21 whole-day and 46 task-specific short-term (1-18 min) measurements were performed. The median 8-hour time-weighted averages were 2.5 microg/m3 (dentists) and 2.9 microg/m3 (dental nurses) for 2-hydroxyethyl methacrylate, and 0.8 microg/m3 (dentists) and 0.3 microg/m3 (dental nurses) for methyl methacrylate. The maximum short-term exposure levels were 79 microg/m3 for 2-hydroxyethyl methacrylate and 15 microg/m3 for methyl methacrylate, similar in dentists and dental nurses. The observed levels are much lower than in complete denture fabrication. We found only one previous study in dentistry and it showed similar results (though it reported short-term measurements only). Irritant effects would not be expected in healthy people at these levels. Nevertheless, occupational respiratory diseases due to methacrylates may occur in dental personnel, and improvements in the handling of these chemicals in dentistry are warranted. This includes better vials for the bonding agents and avoiding evaporation from discarded materials.

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

    DOEpatents

    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. Photoinduced bending behavior of cross-linked azobenzene liquid-crystalline polymer films with a poly(oxyethylene) backbone.

    PubMed

    Lv, Jiu-an; Wang, Weiru; Xu, Jixiang; Ikeda, Tomiki; Yu, Yanlei

    2014-07-01

    Cross-linked azobenzene liquid-crystalline polymer films with a poly(oxyethylene) backbone are synthesized by photoinitiated cationic copolymerization. Azobenzene moieties in the film surface toward the light source are simultaneously photoaligned during photopolymerization with unpolarized 436 nm light and thus form a splayed alignment in the whole film. The prepared films show reversible photoinduced bending behavior with opposite bending directions when different surfaces of one film face to ultraviolet light irradiation.

  4. 21 CFR 172.775 - Methacrylic acid-divinylbenzene copolymer.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Methacrylic acid-divinylbenzene copolymer. 172.775... Additives § 172.775 Methacrylic acid-divinylbenzene copolymer. Methacrylic acid-divinylbenzene copolymer may... produced by the polymerization of methacrylic acid and divinylbenzene. The divinylbenzene functions as...

  5. Formation of Anisotropic Block Copolymer Gels

    NASA Astrophysics Data System (ADS)

    Liaw, Chya Yan; Shull, Kenneth; Henderson, Kevin; Joester, Derk

    2011-03-01

    Anisotropic, fibrillar gels are important in a variety of processes. Biomineralization is one example, where the mineralization process often occurs within a matrix of collagen or chitin fibers that trap the mineral precursors and direct the mineralization process. We wish to replicate this type of behavior within block copolymer gels. Particularly, we are interested in employing gels composed of cylindrical micelles, which are anisotropic and closely mimic biological fibers. Micelle geometry is controlled in our system by manipulating the ratio of molecular weights of the two blocks and by controlling the detailed thermal processing history of the copolymer solutions. Small-Angle X-ray Scattering and Dynamic Light Scattering are used to determine the temperature dependence of the gel formation process. Initial experiments are based on a thermally-reversible alcohol-soluble system, that can be subsequently converted to a water soluble system by hydrolysis of a poly(t-butyl methacrylate) block to a poly (methacrylic acid) block. MRSEC.

  6. Methacrylated glycol chitosan as a photopolymerizable biomaterial.

    PubMed

    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.

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

    PubMed Central

    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

  8. Multiresponsive chiroptical switch of an azobenzene-containing lipid: solvent, temperature, and photoregulated supramolecular chirality.

    PubMed

    Duan, Pengfei; Li, Yuangang; Li, Liangchun; Deng, Jingen; Liu, Minghua

    2011-04-07

    An azobenzene-containing lipid was designed as a functional organogelator, and its self-assembly as well as the chiroptical properties were investigated. The gelator shows good gelation ability in various organic solvents ranging from polar to nonpolar solvents. Although the molecule did not show a CD signal in the absorption band of azobenzene in solution, supramolecular chirality was observed upon gel formation. Moreover, the supramolecular chirality exhibited a multiresponse to temperature, photoirradiation, and the solvent polarity. Particularly, positive supramolecular chirality was observed in polar solvents, while it inverted to a negative one in nonpolar solvents. All the responses in relating to the supramolecular chirality were reversible and thus produced a multiresponsive chiroptical switch.

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

    PubMed

    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.

  10. Azobenzenes as light-controlled molecular electronic switches in nanoscale metal-molecule-metal junctions.

    PubMed

    Mativetsky, Jeffrey M; Pace, Giuseppina; Elbing, Mark; Rampi, Maria A; Mayor, Marcel; Samorì, Paolo

    2008-07-23

    Conductance switching associated with the photoisomerization of azobenzene-based (Azo) molecules was observed in nanoscopic metal-molecule-metal junctions. The junctions were formed by using a conducting atomic force microscope (C-AFM) approach, where a metallic AFM tip was used to electrically contact a gold-supported Azo self-assembled monolayer. The measured 30-fold increase in conductance is consistent with the expected decrease in tunneling barrier length resulting from the conformational change of the Azo molecule.

  11. Theory of light-induced deformation of azobenzene elastomers: Influence of network structure

    NASA Astrophysics Data System (ADS)

    Toshchevikov, V. P.; Saphiannikova, M.; Heinrich, G.

    2012-07-01

    Azobenzene elastomers have been extensively explored in the last decade as photo-deformable smart materials which are able to transform light energy into mechanical stress. Presently, there is a great need for theoretical approaches to accurately predict the quantitative response of these materials based on their microscopic structure. Recently, we proposed a theory of light-induced deformation of azobenzene elastomers using a simple regular cubic network model [V. Toshchevikov, M. Saphiannikova, and G. Heinrich, J. Phys. Chem. B 116, 913 (2012), 10.1021/jp206323h]. In the present study, we extend the previous theory using more realistic network models which take into account the random orientation of end-to-end vectors of network strands as well as the molecular weight distribution of the strands. Interaction of the chromophores with the linearly polarized light is described by an effective orientation potential which orients the chromophores perpendicular to the polarization direction. We show that both monodisperse and polydisperse azobenzene elastomers can demonstrate either a uniaxial expansion or contraction along the polarization direction. The sign of deformation (expansion/contraction) depends on the orientation distribution of chromophores with respect to the main chains which is defined by the chemical structure and by the lengths of spacers. The degree of cross-linking and the polydispersity of network strands do not affect the sign of deformation but influence the magnitude of light-induced deformation. We demonstrate that photo-mechanical properties of mono- and poly-disperse azobenzene elastomers with random spatial distribution of network strands can be described in a very good approximation by a regular cubic network model with an appropriately chosen length of the strands.

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

    PubMed

    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.

  13. Two-Photon Neuronal and Astrocytic Stimulation with Azobenzene-Based Photoswitches

    PubMed Central

    2015-01-01

    Synthetic photochromic compounds can be designed to control a variety of proteins and their biochemical functions in living cells, but the high spatiotemporal precision and tissue penetration of two-photon stimulation have never been investigated in these molecules. Here we demonstrate two-photon excitation of azobenzene-based protein switches and versatile strategies to enhance their photochemical responses. This enables new applications to control the activation of neurons and astrocytes with cellular and subcellular resolution. PMID:24857186

  14. Photocontrolled Supramolecular Assembling of Azobenzene-Based Biscalix[4]arenes upon Starting and Stopping Laser Trapping.

    PubMed

    Yuyama, Ken-Ichi; Marcelis, Lionel; Su, Pei-Mei; Chung, Wen-Sheng; Masuhara, Hiroshi

    2017-01-24

    Laser trapping in chemistry covers various studies ranging from single molecules, nanoparticles, and quantum dots to crystallization and liquid-liquid phase separation of amino acids. In this work, a supramolecular assembly of azobenzene-based biscalix[4]arene is generated in ethyl acetate using laser trapping; its nucleation and growth are elucidated. No trapping behavior was observed when a 1064 nm laser beam was focused inside of the solution; however, interesting assembling phenomena were induced when it was shined at the air/solution interface. A single disk having two layers was first prepared at the focal point of ∼1 μm and then expanded to the size of a few tens of micrometers, although no optical force was exerted outside of the focal volume. Upon switching the trapping laser off, needles were generated at the outer layer of the assembly, giving a stable sea urchin-like morphology to the generated assembly. At a 30-50% dilution of the initial solution in ethyl acetate, a mushroom-like morphology was also observed. Laser trapping-induced assembly of azobenzene-based biscalix[4]arene was quite different from the sharp-ellipsoidal aggregates obtained by the spontaneous evaporation of the solution. These trapping phenomena were specifically observed for biscalix[4]arene in the trans conformation of azo-benzene moiety but not for the cis-form, suggesting that the laser trapping of this azobenzene-based biscalix[4]arene is photocontrollable. Dynamics and mechanism of the supramolecular assembling are considered, referring to laser trapping-induced nucleation and liquid-liquid phase separation of amino acids.

  15. Alternating photoinduced mass transport triggered by light polarization in azobenzene containing sol-gel films

    NASA Astrophysics Data System (ADS)

    Fabbri, F.; Lassailly, Y.; Lahlil, K.; Boilot, J. P.; Peretti, J.

    2010-02-01

    Combined shear-force and near-field optical microscopies are used for real-time monitoring of the formation of photoinduced surface relief gratings in photochromic thin films containing azobenzene derivatives. The correlated optical and topographical images provide evidence that the direction of the photoinduced matter migration is defined by the light polarization pattern and that, for a given light intensity pattern, modulating the polarization between two orthogonal states gives rise to alternating mass transport.

  16. Light-induced noncentrosymmetry in acceptor-donor-substituted azobenzene solutions

    NASA Astrophysics Data System (ADS)

    Zhao, Jiang; Si, Jinhai; Wang, Yougui; Ye, Peixian; Fu, Xingfa; Qiu, Ling; Shen, Yuquan

    1995-10-01

    Light-induced noncentrosymmetry was achieved experimentally in acceptor-donor-substituted azobenzene solutions and observed by phase-matched nondegenerate six-wave mixing. The microscopic origin of the induced noncentrosymmetry was found to be orientational hole burning, which was distinguished directly with net orientation of molecules by experimental observations. The decay time of the induced noncentrosymmetry depended on the rotational orientation time of the sample's molecule, which varied linearly with the viscosity of the solvent.

  17. 40 CFR 721.9492 - Polymers of styrene, cyclohexyl methacrylate and substituted methacrylate.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 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...

  18. 40 CFR 721.9492 - Polymers of styrene, cyclohexyl methacrylate and substituted methacrylate.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 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...

  19. 40 CFR 721.9492 - Polymers of styrene, cyclohexyl methacrylate and substituted methacrylate.

    Code of Federal Regulations, 2010 CFR

    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...

  20. 40 CFR 721.9492 - Polymers of styrene, cyclohexyl methacrylate and substituted methacrylate.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 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...

  1. Molecularly Engineered Azobenzene Derivatives for High Energy Density Solid-State Solar Thermal Fuels.

    PubMed

    Cho, Eugene N; Zhitomirsky, David; Han, Grace G D; Liu, Yun; Grossman, Jeffrey C

    2017-03-15

    Solar thermal fuels (STFs) harvest and store solar energy in a closed cycle system through conformational change of molecules and can release the energy in the form of heat on demand. With the aim of developing tunable and optimized STFs for solid-state applications, we designed three azobenzene derivatives functionalized with bulky aromatic groups (phenyl, biphenyl, and tert-butyl phenyl groups). In contrast to pristine azobenzene, which crystallizes and makes nonuniform films, the bulky azobenzene derivatives formed uniform amorphous films that can be charged and discharged with light and heat for many cycles. Thermal stability of the films, a critical metric for thermally triggerable STFs, was greatly increased by the bulky functionalization (up to 180 °C), and we were able to achieve record high energy density of 135 J/g for solid-state STFs, over a 30% improvement compared to previous solid-state reports. Furthermore, the chargeability in the solid state was improved, up to 80% charged from 40% charged in previous solid-state reports. Our results point toward molecular engineering as an effective method to increase energy storage in STFs, improve chargeability, and improve the thermal stability of the thin film.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  3. Tuning the optical emission of MoS{sub 2} nanosheets using proximal photoswitchable azobenzene molecules

    SciTech Connect

    Li, Juan; Wierzbowski, Jakob; Ceylan, Özlem; Klein, Julian; Anh, Tuan Le; Meggendorfer, Felix; Finley, Jonathan J.; Margapoti, Emanuela; Nisic, Filippo; Dragonetti, Claudia; Palma, Carlos-Andres; Barth, Johannes V.

    2014-12-15

    We report photoluminescence measurements performed on monolayer- and two-layer-MoS{sub 2} placed on two types of mixed self-assembled monolayers (mSAMs) of photoswitchable azobenzene molecules. The two mSAMs differ via the electronegative character of the azobenzene derivatives. Thin layers of a transition metal dichalcogenide—MoS{sub 2}—were mechanically exfoliated on mSAM to allow for direct interaction between the molecules and the MoS{sub 2} layers. When the MoS{sub 2} nanosheet is in contact with the electropositive azobenzene molecules in trans configuration, an emission side band at lower energies and at low excitation powers suggest n-type doping. The photoisomerization of the molecules from trans to cis configuration lowers the doping, quenching the side band and enhancing the overall PL efficiency by a factor of ∼3. Opposite results were observed with the chlorinated, more electronegative molecules, exhibiting a reversed trend in the PL efficiency between trans and cis, but with an overall larger intensity. The type of doping induced by the two types of mSAMs was determined by Kelvin probe force microscopy technique.

  4. Kinetics of light-induced ordering and deformation in LC azobenzene-containing materials.

    PubMed

    Toshchevikov, Vladimir; Petrova, Tatiana; Saphiannikova, Marina

    2017-04-12

    Azobenzene-containing smart materials are able to transform the energy of light into directional mechanical stress. We develop a theory of time-dependent light-induced ordering and deformation in azobenzene materials starting from the kinetic equations of photoisomerization. The liquid crystalline (LC) interactions between rod-like trans-isomers are taken into account. Angular selectivity of the photoisomerization known as an "angular hole burning" or the Weigert effect leads to the light-induced ordering and deformation of the azobenzene materials. The time evolution of ordering and deformation is found as a function of intensity of light depending on the opto-mechanical characteristics of the materials, such as probabilities of the optical excitation of trans- and cis-isomers, angular jump during the single isomerization event, viscosity of the materials, strength of the LC interactions in both the isotropic and LC materials, and the angular distribution of chromophores in polymer chains. Established structural-property relationships are in agreement with a number of experiments and can be used for the construction of light-controllable smart materials for practical applications.

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

    PubMed Central

    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

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

    PubMed

    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.

  7. Photoinduced anisotropy of second-harmonic generation from azobenzene-modified alkylsiloxane monolayers

    NASA Astrophysics Data System (ADS)

    Yi, Y. W.; Furtak, T. E.; Farrow, M. J.; Walba, D. M.

    2003-09-01

    Noncontact alignment of liquid crystal displays offers the advantage of reduced contamination and minimal surface charging. This approach also provides a means of reversible alignment after a device has been assembled. With this objective we have synthesized self-assembled monolayers based on dimethylaminoazobenzene units covalently attached to a glass surface by means of a short alkylsiloxane anchor, a derivatized version of methyl red (d-MR). The resulting architecture favors an orientation in which the axis of the azobenzene group should be nearly parallel to the surface with an isotropic azimuthal distribution. Under illumination with polarized light the trans-cis isomerization and subsequent relaxation serves to wiggle the molecule into an orientation perpendicular to the treatment polarization. We have tested this scenario using optical second harmonic generation and supporting optical techniques. We are able to identify a surface order parameter that characterizes the photoalignment of the azobenzene group, and have shown that the treatment illumination promotes the formation of H aggregates of the azobenzene species. We have also demonstrated that the treated d-MR layer successfully aligns a nematic liquid crystal.

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

    NASA Astrophysics Data System (ADS)

    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. A comparative study of photoinduced deformation in azobenzene containing polymer films.

    PubMed

    Yadavalli, Nataraja Sekhar; Loebner, Sarah; Papke, Thomas; Sava, Elena; Hurduc, Nicolae; Santer, Svetlana

    2016-03-07

    In this paper two groups supporting different views on the mechanism of light induced polymer deformation argue about the respective underlying theoretical conceptions, in order to bring this interesting debate to the attention of the scientific community. The group of Prof. Nicolae Hurduc supports the model claiming that the cyclic isomerization of azobenzenes may cause an athermal transition of the glassy azobenzene containing polymer into a fluid state, the so-called photo-fluidization concept. This concept is quite convenient for an intuitive understanding of the deformation process as an anisotropic flow of the polymer material. The group of Prof. Svetlana Santer supports the re-orientational model where the mass-transport of the polymer material accomplished during polymer deformation is stated to be generated by the light-induced re-orientation of the azobenzene side chains and as a consequence of the polymer backbone that in turn results in local mechanical stress, which is enough to irreversibly deform an azobenzene containing material even in the glassy state. For the debate we chose three polymers differing in the glass transition temperature, 32 °C, 87 °C and 95 °C, representing extreme cases of flexible and rigid materials. Polymer film deformation occurring during irradiation with different interference patterns is recorded using a homemade set-up combining an optical part for the generation of interference patterns and an atomic force microscope for acquiring the kinetics of film deformation. We also demonstrated the unique behaviour of azobenzene containing polymeric films to switch the topography in situ and reversibly by changing the irradiation conditions. We discuss the results of reversible deformation of three polymers induced by irradiation with intensity (IIP) and polarization (PIP) interference patterns, and the light of homogeneous intensity in terms of two approaches: the re-orientational and the photo-fluidization concepts. Both agree

  10. Organophosphazenes.22 Copolymerization of (Alpha-Methylethenylphenyl) Penta-fluorocyclotriphosphazenes with Styrene and Methyl Methacrylate.

    DTIC Science & Technology

    1988-03-15

    pennultimate effects , 19. BSTRACT (Continue on reverse it necessary and identify by block number) i ., i. Both 3- and 4- (l-Methylethenylphenyl...parameters for theA, styrene system show that the major perturbation produced by the phosphazene is a polar6 electron withdrawing effect . The methyl...methacrylate system was found to exhibit significant penultimate effects in its reactivity behavior. The copolymers were characteri-zed using elemental

  11. The aniline-to-azobenzene oxidation reaction on monolayer graphene or graphene oxide surfaces fabricated by benzoic acid.

    PubMed

    Lee, Myungjin; Kim, Kijeong; Lee, Hangil

    2013-09-02

    The oxidation of aniline to azobenzene was conducted in the presence of either monolayer graphene (EG) or graphene-oxide-like surface, such as GOx, under ultra-high vacuum conditions maintaining a 365-nm UV light exposure to enhance the oxidation reaction. The surface-bound products were investigated using micro Raman spectroscopy, high-resolution photoemission spectroscopy, and work function measurements. The oxygen carriers present on the GOx surfaces, but not on the EG surfaces, acted as reaction reagents to facilitate the oxidation reaction from aniline to azobenzene. Increasing the aniline concentration at 300 K confirmed that the exchange ratio from the aniline to the azobenzene was enhanced, as determined by the intensity ratio between the aniline- and azobenzene-induced N 1 s core-level spectra. The work function changed dramatically as the aniline concentration increased, indicating that the aniline on the GOx surface conveyed n-type doping characteristics at a low coverage level. A higher aniline concentration increased the p-type doping character by increasing the azobenzene concentration on the GOx surface. A comparison of the oxidation reactivity of aniline molecules on the EG or GOx surfaces revealed the role of the oxygen carriers on the GOx surfaces in the context of catalytic oxidation.

  12. The aniline-to-azobenzene oxidation reaction on monolayer graphene or graphene oxide surfaces fabricated by benzoic acid

    PubMed Central

    2013-01-01

    The oxidation of aniline to azobenzene was conducted in the presence of either monolayer graphene (EG) or graphene-oxide-like surface, such as GOx, under ultra-high vacuum conditions maintaining a 365-nm UV light exposure to enhance the oxidation reaction. The surface-bound products were investigated using micro Raman spectroscopy, high-resolution photoemission spectroscopy, and work function measurements. The oxygen carriers present on the GOx surfaces, but not on the EG surfaces, acted as reaction reagents to facilitate the oxidation reaction from aniline to azobenzene. Increasing the aniline concentration at 300 K confirmed that the exchange ratio from the aniline to the azobenzene was enhanced, as determined by the intensity ratio between the aniline- and azobenzene-induced N 1 s core-level spectra. The work function changed dramatically as the aniline concentration increased, indicating that the aniline on the GOx surface conveyed n-type doping characteristics at a low coverage level. A higher aniline concentration increased the p-type doping character by increasing the azobenzene concentration on the GOx surface. A comparison of the oxidation reactivity of aniline molecules on the EG or GOx surfaces revealed the role of the oxygen carriers on the GOx surfaces in the context of catalytic oxidation. PMID:24229051

  13. 21 CFR 882.5300 - Methyl methacrylate for cranioplasty.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... methacrylate for cranioplasty. (a) Identification. Methyl methacrylate for cranioplasty (skull repair) is a self-curing acrylic that a surgeon uses to repair a skull defect in a patient. At the time of...

  14. 21 CFR 882.5300 - Methyl methacrylate for cranioplasty.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... methacrylate for cranioplasty. (a) Identification. Methyl methacrylate for cranioplasty (skull repair) is a self-curing acrylic that a surgeon uses to repair a skull defect in a patient. At the time of...

  15. 21 CFR 882.5300 - Methyl methacrylate for cranioplasty.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... methacrylate for cranioplasty. (a) Identification. Methyl methacrylate for cranioplasty (skull repair) is a self-curing acrylic that a surgeon uses to repair a skull defect in a patient. At the time of...

  16. 21 CFR 882.5300 - Methyl methacrylate for cranioplasty.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... methacrylate for cranioplasty. (a) Identification. Methyl methacrylate for cranioplasty (skull repair) is a self-curing acrylic that a surgeon uses to repair a skull defect in a patient. At the time of...

  17. 21 CFR 882.5300 - Methyl methacrylate for cranioplasty.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... methacrylate for cranioplasty. (a) Identification. Methyl methacrylate for cranioplasty (skull repair) is a self-curing acrylic that a surgeon uses to repair a skull defect in a patient. At the time of...

  18. Mass spectrometric identification of an azobenzene derivative produced by smectite-catalyzed conversion of 3-amino-4-hydroxyphenylarsonic acid

    USGS Publications Warehouse

    Wershaw, R. L.; Rutherford, D.W.; Rostad, C.E.; Garbarino, J.R.; Ferrer, I.; Kennedy, K.R.; Momplaisir, G.-M.; Grange, A.

    2003-01-01

    The compound 3-amino-4-hydroxyphenylarsonic acid (3-amino-HPAA) reacts with smectite to form a soluble azobenzene arsonic acid compound. This reaction is of particular interest because it provides a possible mechanism for the formation of a new type of arsenic compound in natural water systems. 3-Amino-HPAA is a degradation product excreted by chickens that are fed rations amended with roxarsone. Roxarsone is used to control coccidial intestinal parasites in most of the broiler chickens grown in the United States. The structure of the azobenzene arsonic acid compound was first inferred from negative-ion and positive-ion low-resolution mass-spectrometric analyses of the supernatant of the smectite suspension. Elemental composition of the parent ion determined by high-resolution positive-ion mass spectrometric measurements was consistent with the proposed structure of the azobenzene arsonic acid compound. Published by Elsevier Science B.V.

  19. Photo-orientation of azobenzene-containing liquid-crystalline materials by means of domain structure rearrangement.

    PubMed

    Bogdanov, Alexey V; Vorobiev, Andrey Kh

    2013-11-07

    A novel mechanism of photo-orientation of azobenzene-containing liquid-crystalline materials is proposed. This mechanism is based on the notion of photochemically induced domain rearrangement driven by destabilization of liquid-crystalline phase in light absorbing domains due to photochemical formation of non-mesogenic cis-azobenzene moieties. The experimental evidence of photoinduced movement of a domain boundary is presented, and the velocity of this movement is measured. A mathematical model for photo-orientation of a polydomain azobenzene-containing material is formulated. The values of model parameters for a liquid-crystalline azopolymer have been measured in separate experiments. Theoretical predictions demonstrate quantitative agreement with the experimental observations.

  20. Femtosecond pump-probe photoionization-photofragmentation spectroscopy: Photoionization-induced twisting and coherent vibrational motion of azobenzene cation

    NASA Astrophysics Data System (ADS)

    Ho-Wei, Jr.; Chen, Wei-Kan; Cheng, Po-Yuan

    2009-10-01

    We report studies of ultrafast dynamics of azobenzene cation using femtosecond photoionization-photofragmentation spectroscopy. In our experiments, a femtosecond pump pulse first produces an ensemble of azobenzene cations via photoionization of the neutrals. A delayed probe pulse then brings the evolving ionic system to excited 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 cation 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 in this time scale.

  1. Manipulation and assembly of small objects in liquid crystals by dynamical disorganizing effect of push-pull-azobenzene-dye.

    PubMed

    Kurihara, Seiji; Ohta, Kazuhiro; Oda, Takahiro; Izumi, Ryo; Kuwahara, Yutaka; Ogata, Tomonari; Kim, Sun-Nam

    2013-01-01

    The phase transition of a nematic liquid crystal containing a push-pull azobenzene dye could be induced efficiently during irradiation with visible light. The dynamical disorganizing effect of the push-pull azobenzene dye on the liquid crystalline order through its trans-cis-trans photoisomerizaion cycle under visible light was contributed to the efficient phase transition. Then, the effects of light irradiation on the motion of small objects dispersed in the liquid crystals containing the push-pull azobenzene were explored, and the manipulation and assembly of those objects were successfully achieved in the nematic phase but also in the smectic phase. The combination of the photo-controlled dynamical change in the liquid crystalline order and the intrinsic self-assembly property of a liquid crystal is promising for use in technologies that require not only the organization of small objects but also the photo-driving of nano- and micro-sized mechanical materials.

  2. pH-sensitive methacrylic copolymers and the production thereof

    SciTech Connect

    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.

  3. pH-sensitive methacrylic copolymers and the production thereof

    DOEpatents

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

    2006-02-14

    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.

  4. 21 CFR 172.775 - Methacrylic acid-divinylbenzene copolymer.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Methacrylic acid-divinylbenzene copolymer. 172.775... HUMAN CONSUMPTION Other Specific Usage Additives § 172.775 Methacrylic acid-divinylbenzene copolymer. Methacrylic acid-divinylbenzene copolymer may be safely used in food in accordance with the...

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

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Methacrylic acid-divinylbenzene copolymer. 172.775... HUMAN CONSUMPTION Other Specific Usage Additives § 172.775 Methacrylic acid-divinylbenzene copolymer. Methacrylic acid-divinylbenzene copolymer may be safely used in food in accordance with the...

  6. 21 CFR 172.775 - Methacrylic acid-divinylbenzene copolymer.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Methacrylic acid-divinylbenzene copolymer. 172.775... HUMAN CONSUMPTION Other Specific Usage Additives § 172.775 Methacrylic acid-divinylbenzene copolymer. Methacrylic acid-divinylbenzene copolymer may be safely used in food in accordance with the...

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

    NASA Astrophysics Data System (ADS)

    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

  8. Solute solvent interaction in methyl methacrylate and 2-hydroxyethyl methacrylate monomers solutions

    NASA Astrophysics Data System (ADS)

    Al-ghamdi, Attieh A.; Bahattab, M. A.; Farhoud, M.; Al-Dossary, Mishal; Al-Enizi, Abdullah; Al-Deyab, S. S.

    2006-11-01

    Solute-solvent interactions are studied using induced birefringence measurements in monomers solutions of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA), dissolved in ethanol, acetone, ethyl acetate, tetrahydrofuran and dimethyl sulfoxide, over a broad range of concentrations. The data are combined with refractive index and density to calculate the electric, optical and molar Kerr constants. All related microscopic parameters concerning the molecular structure such as nonlinear Kerr constants, anisotropic factors, and optical anisotropy have been calculated.

  9. Substrate-Controlled Transformation of Azobenzenes to Indazoles and Indoles via Rh(III)-Catalysis.

    PubMed

    Cai, Shangjun; Lin, Songyun; Yi, Xiangli; Xi, Chanjuan

    2017-01-06

    Rh(III)-catalyzed substrate-controlled transformation of azobenzenes to indazoles and 2-acyl (NH) indoles is achieved via C-H functionalization. Generally, good functional groups tolerance, satisfying yields, and excellent regio-selectivity are achieved in this reaction. Mechanistically, the reaction with acrylates undergoes β-hydride elimination, while the reaction with vinyl ketones or acrylamides undergoes nucleophilic addition. Copper acetate was supposed to play different roles in the β-hydride elimination to furnish indazoles and nucleophilic addition of C-Rh bond to deliver 2-acyl (NH) indoles.

  10. All-Optical, Photonic Band Gap Modulation in Azobenzene Liquid Crystal Doped Cholesterics (Preprint)

    DTIC Science & Technology

    2006-10-01

    pitch h of the CLC, ~A = hen 11- nJ..)and As = hn, where n IIand nl. are the local principal values of the refractive indices of the CLC and n = (n II...molecule is typically used to affect local LC-ordering. The ability to use this process to effectively (and reversibly) modulate the pitch of a CLC and...via irradiation of microwatt and even nanowatt power light beams due to photoisomerization processes of the azobenzene core. Due to a wide mesophase

  11. Reversible change of birefringence sign by optical and thermal processes in an azobenzene polymethacrylate

    SciTech Connect

    Rodriguez, F.J.; Sanchez, C.; Villacampa, B.; Alcala, R.; Cases, R.; Millaruelo, M.; Oriol, L.

    2005-01-10

    Birefringence ({delta}n) induced in an azobenzene polymethacrylate by combination of biphotonic and thermotropic processes has subsequently been changed in sign by room temperature illumination with linearly polarized blue light. The sign of {delta}n can be reversed again, by simply heating up the film to 100 deg. C. This change of {delta}n between positive and negative values can be repeated several times. Besides, by appropriate choice of film thickness and blue light irradiation conditions the same absolute value for positive and negative {delta}n values can be obtained.

  12. Structure and energetics of azobenzene on Ag(111): benchmarking semiempirical dispersion correction approaches.

    PubMed

    Mercurio, G; McNellis, E R; Martin, I; Hagen, S; Leyssner, F; Soubatch, S; Meyer, J; Wolf, M; Tegeder, P; Tautz, F S; Reuter, K

    2010-01-22

    We employ normal-incidence x-ray standing wave and temperature programed desorption spectroscopy to derive the adsorption geometry and energetics of the prototypical molecular switch azobenzene at Ag(111). This allows us to assess the accuracy of semiempirical correction schemes as a computationally efficient means to overcome the deficiency of semilocal density-functional theory with respect to long-range van der Waals (vdW) interactions. The obtained agreement underscores the significant improvement provided by the account of vdW interactions, with remaining differences mainly attributed to the neglect of electronic screening at the metallic surface.

  13. Azobenzene-functionalized carbon nanotubes as high-energy density solar thermal fuels.

    PubMed

    Kolpak, Alexie M; Grossman, Jeffrey C

    2011-08-10

    Solar thermal fuels, which reversibly store solar energy in molecular bonds, are a tantalizing prospect for clean, renewable, and transportable energy conversion/storage. However, large-scale adoption requires enhanced energy storage capacity and thermal stability. Here we present a novel solar thermal fuel, composed of azobenzene-functionalized carbon nanotubes, with the volumetric energy density of Li-ion batteries. Our work also demonstrates that the inclusion of nanoscale templates is an effective strategy for design of highly cyclable, thermally stable, and energy-dense solar thermal fuels.

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

    PubMed Central

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

    2015-01-01

    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. PMID:26434681

  15. A multifunctional azobenzene-based polymeric adsorbent for effective water remediation

    NASA Astrophysics Data System (ADS)

    Wan, Decheng; Chen, Feng; Geng, Qingrui; Lu, Hang; Willcock, Helen; Liu, Qiuming; Wang, Fangyingkai; Zou, Kaidian; Jin, Ming; Pu, Hongting; Du, Jianzhong

    2014-12-01

    The efficient removal of trace carcinogenic organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs) and ionic dyes, from water is an important technical challenge. We report a highly effective recyclable multifunctional azobenzene (AZ)-based silica-supported polymeric adsorbent which can simultaneously remove both PAHs and anionic dyes from water to below parts per billion (ppb) level based on multiple interactions such as the hydrophobic effect, π-π stacking and electrostatic interactions, thus providing a new strategy for designer water remediation materials.

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

    NASA Astrophysics Data System (ADS)

    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.

  17. A multifunctional azobenzene-based polymeric adsorbent for effective water remediation.

    PubMed

    Wan, Decheng; Chen, Feng; Geng, Qingrui; Lu, Hang; Willcock, Helen; Liu, Qiuming; Wang, Fangyingkai; Zou, Kaidian; Jin, Ming; Pu, Hongting; Du, Jianzhong

    2014-12-03

    The efficient removal of trace carcinogenic organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs) and ionic dyes, from water is an important technical challenge. We report a highly effective recyclable multifunctional azobenzene (AZ)-based silica-supported polymeric adsorbent which can simultaneously remove both PAHs and anionic dyes from water to below parts per billion (ppb) level based on multiple interactions such as the hydrophobic effect, π-π stacking and electrostatic interactions, thus providing a new strategy for designer water remediation materials.

  18. Dendrimer/methyl methacrylate co-polymers: residual methyl methacrylate and degree of conversion.

    PubMed

    Viljanen, Eeva K; Skrifvars, Mikael; Vallittu, Pekka K

    2005-01-01

    Dendrimer/methyl methacrylate co-polymers were studied for use in dental composites. The aim was to determine the effects of methyl methacrylate concentration in the resin mixture and polymerization method on the degree of conversion and residual monomer content of the copolymers. Two dendrimers were studied, D12 with 12 reactive methacrylate groups and D24 with 24 reactive groups. The concentration of methyl methacrylate varied from 20 wt% to 50 wt% of monomers. Camphorquinone (CQ) was used as the light-activation initiator and 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) as the activator, both in the quantity of 3.0 wt%. Three polymerization methods were used: photo-polymerization, photo-polymerized immediately followed by post-polymerization at 120 degrees C for 15 min, and photo-polymerization followed by postpolymerization after 7 days. The degree of conversion was determined using FT-IR. Residual monomers were extracted with tetrahydrofuran and methanol and analyzed with HPLC. The highest degrees of conversion were 65 and 62%, and the lowest residual monomer contents 1.0 and 1.5% for D12 and D24, respectively. These were measured after heat-induced post-polymerization. For D12, increasing the proportion of methyl methacrylate decreased the degree of conversion and increased the residual monomer content after photo-polymerization. Post-polymerization enhanced the polymerization of the dendrimer co-polymers in respect of degree of conversion and residual monomer content. The present study suggested that the tested dendrimer/methyl methacrylate copolymers require heat-induced polymerization to reach the generally accepted levels of degree of conversion and residual monomers.

  19. MASS SPECTROMETRIC IDENTIFICATION OF AN AZOBENZENE DERIVATIVE PRODUCED BY SMECTITE-CATALYZED CONVERSION OF 3-AMINO-4-HYDROXPHENYLARSONIC ACID

    EPA Science Inventory

    We report here the first evidence of a possible mechanism for the formation of an azobenzene arsonic acid compound in the environment The compound was formed when 3-amino-4-hydroxyphenylarsonic acid (3-amino-HPAA) was added to aqueous suspensions of smectite clay The 3-amino-HPAA...

  20. Photoswitching of azobenzene-containing self-assembled monolayers as a tool for control over silicon surface electronic properties.

    PubMed

    Malyar, Ivan V; Titov, Evgenii; Lomadze, Nino; Saalfrank, Peter; Santer, Svetlana

    2017-03-14

    We report on photoinduced remote control of work function and surface potential of a silicon surface modified with a photosensitive self-assembled monolayer consisting of chemisorbed azobenzene molecules (4-nitroazobenzene). It was found that the attachment of the organic monolayer increases the work function by hundreds of meV due to the increase in the electron affinity of silicon substrates. The change in the work function on UV light illumination is more pronounced for the azobenzene jacketed silicon substrate (ca. 250 meV) in comparison to 50 meV for the unmodified surface. Moreover, the photoisomerization of azobenzene results in complex kinetics of the work function change: immediate decrease due to light-driven processes in the silicon surface followed by slower recovery to the initial state due to azobenzene isomerization. This behavior could be of interest for electronic devices where the reaction on irradiation should be more pronounced at small time scales but the overall surface potential should stay constant over time independent of the irradiation conditions.

  1. Light-induced dynamic shaping and self-division of multipodal polyelectrolyte-surfactant microarchitectures via azobenzene photomechanics

    NASA Astrophysics Data System (ADS)

    Martin, Nicolas; Sharma, Kamendra P.; Harniman, Robert L.; Richardson, Robert M.; Hutchings, Ricky J.; Alibhai, Dominic; Li, Mei; Mann, Stephen

    2017-01-01

    Light-induced shape transformations represent a fundamental step towards the emergence of adaptive materials exhibiting photomechanical behaviours. Although a range of covalent azobenzene-based photoactive materials has been demonstrated, the use of dynamic photoisomerization in mesostructured soft solids involving non-covalent co-assembly has received little attention. Here we prepare discrete micrometre-sized hydrated particles of a hexagonally ordered polyelectrolyte-surfactant mesophase based on the electrostatically induced co-assembly of poly(sodium acrylate) (PAA) and trans-azobenzene trimethylammonium bromide (trans-azoTAB), and demonstrate unusual non-equilibrium substrate-mediated shape transformations to complex multipodal microarchitectures under continuous blue light. The microparticles spontaneously sequester molecular dyes, functional enzymes and oligonucleotides, and undergo self-division when transformed to the cis state under UV irradiation. Our results illustrate that weak bonding interactions in polyelectrolyte-azobenzene surfactant mesophases can be exploited for photo-induced long-range molecular motion, and highlight how dynamic shape transformations and autonomous division can be activated by spatially confining azobenzene photomechanics in condensed microparticulate materials.

  2. Light-induced dynamic shaping and self-division of multipodal polyelectrolyte-surfactant microarchitectures via azobenzene photomechanics

    PubMed Central

    Martin, Nicolas; Sharma, Kamendra P.; Harniman, Robert L.; Richardson, Robert M.; Hutchings, Ricky J.; Alibhai, Dominic; Li, Mei; Mann, Stephen

    2017-01-01

    Light-induced shape transformations represent a fundamental step towards the emergence of adaptive materials exhibiting photomechanical behaviours. Although a range of covalent azobenzene-based photoactive materials has been demonstrated, the use of dynamic photoisomerization in mesostructured soft solids involving non-covalent co-assembly has received little attention. Here we prepare discrete micrometre-sized hydrated particles of a hexagonally ordered polyelectrolyte-surfactant mesophase based on the electrostatically induced co-assembly of poly(sodium acrylate) (PAA) and trans-azobenzene trimethylammonium bromide (trans-azoTAB), and demonstrate unusual non-equilibrium substrate-mediated shape transformations to complex multipodal microarchitectures under continuous blue light. The microparticles spontaneously sequester molecular dyes, functional enzymes and oligonucleotides, and undergo self-division when transformed to the cis state under UV irradiation. Our results illustrate that weak bonding interactions in polyelectrolyte-azobenzene surfactant mesophases can be exploited for photo-induced long-range molecular motion, and highlight how dynamic shape transformations and autonomous division can be activated by spatially confining azobenzene photomechanics in condensed microparticulate materials. PMID:28112266

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

    PubMed

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

    2016-05-04

    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.

  4. Photoswitching of azobenzene-containing self-assembled monolayers as a tool for control over silicon surface electronic properties

    NASA Astrophysics Data System (ADS)

    Malyar, Ivan V.; Titov, Evgenii; Lomadze, Nino; Saalfrank, Peter; Santer, Svetlana

    2017-03-01

    We report on photoinduced remote control of work function and surface potential of a silicon surface modified with a photosensitive self-assembled monolayer consisting of chemisorbed azobenzene molecules (4-nitroazobenzene). It was found that the attachment of the organic monolayer increases the work function by hundreds of meV due to the increase in the electron affinity of silicon substrates. The change in the work function on UV light illumination is more pronounced for the azobenzene jacketed silicon substrate (ca. 250 meV) in comparison to 50 meV for the unmodified surface. Moreover, the photoisomerization of azobenzene results in complex kinetics of the work function change: immediate decrease due to light-driven processes in the silicon surface followed by slower recovery to the initial state due to azobenzene isomerization. This behavior could be of interest for electronic devices where the reaction on irradiation should be more pronounced at small time scales but the overall surface potential should stay constant over time independent of the irradiation conditions.

  5. Effect of methacrylic acid:methyl methacrylate monomer ratios on polymerization rates and properties of polymethyl methacrylates.

    PubMed

    Chen, T; Kusy, R P

    1997-08-01

    Five binary formulations were prepared from methyl methacrylate (MMA) and methacrylic acid (MAA) monomers, and six ternary formulations were prepared from polysols of 30% wt polymethyl methacrylate (PMMA)/MMA and MAA. Using thermal analyses (DSC and TGA) the polymerization kinetics, condition of postcuring, relative amount of residual monomers, and glass transition temperature (Tg) were determined. From bar-shaped samples, 25 x 5 x 0.9 mm in dimensions, mechanical properties [flexural moduli (E) and maximum strengths (sigma)] were measured in three-point bending. Polymerization kinetics of binary formulations improved over pure PMMA (from 15 to 4 min) as a result of over a 60-fold increase in propagation-to-termination constants (Kp/Kt) of MAA/MMA. The further addition of PMMA increased the viscosity, slowed down termination, and, consequently, improved the polymerization kinetics twofold. These enhancements occurred without a substantive change in the Tg of the ternary system (ca. 107 degrees C) over pure PMMA (ca. 112 degrees C). Moreover, the Es of the four ternary formulations averaged 2.94 GPa, which was comparable with many values reported in the literature. In contrast the sigma s of these same formulations averaged 97 MPa, which was about 25% better than earlier investigations of pure acrylic. When a thermoplastic material is required for pultruding profiles that cure fast and have good thermal-mechanical properties, ternaries of PMMA/MMA/MAA should be considered.

  6. New insights into mechanistic photoisomerization of ethylene-bridged azobenzene from ab initio multiple spawning simulation.

    PubMed

    Liu, Lihong; Wang, Yating; Fang, Qiu

    2017-02-14

    Ethylene-bridged azobenzene (br-AB) has aroused broad interests due to its unique photoswitching properties. Numerous dynamical simulations have been performed for the br-AB photoisomerization, which focused mainly on the conformational effect and the funnel role of minimum-energy conical intersection (MECI) on the mechanism. In the present work, we use the "full quantum" ab initio multiple spawning method to simulate the br-AB photoisomerization, which provides new insights into the mechanism. Upon irradiation of br-AB to the first excited singlet state (S1), most of the excess energies are trapped in the azo-moiety. Since the intramolecular vibrational energy redistribution is slower than the S1 relaxation processes, the nonadiabatic transition from S1 to the ground state (S0) occurs in the vicinity of high-energy crossing seam and even the largest probabilities of the S1 → S0 transition are not distributed in the MECI regions. Once decaying to the S0 state through the high-energy region, the subsequent isomerization and re-formation of the initial isomer are ultrafast processes in the S0 state. It is the nonergodic behavior of the S1 and S0 dynamics that is mainly responsible for the unique photoswitching properties of the ethylene-bridged azobenzene, which will be discussed in detail.

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

    PubMed Central

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

    2016-01-01

    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. PMID:26953168

  8. Theory and computer simulation of photo induced deformations in liquid crystal azobenzene polymers

    NASA Astrophysics Data System (ADS)

    Saphiannikova, Marina; Toshchevikov, Vladimir; Petrova, Tatiana; Ilnytskyi, Jaroslav

    2016-09-01

    Light-controllable azobenzene materials have a remarkable potential for micro- and nanotechnologies as patterning templates, sensors, micropumps and actuators. The photoisomerization between trans and cis states of azo-chromophores is the primary source of photodeformation in azo-polymers. The direction of deformation can be controlled by the light polarization. In our analytical and computer simulation studies, description of the light-induced anisotropy is simplified by applying effective orientation potential to the trans isomers orienting them perpendicular to the light polarization. Using coarse-grained modelling we proved that effective potential approximates well the reorientation of trans isomers under linearly polarized light. The proposed orientation approach is quite promising. It allows not only the explanation of the sign and magnitude of photodeformation in azo-polymers with diverse chemical architecture and topology, but also the prediction of new effects, such as appearance of biaxial deformation in liquid crystal (LC) azo-polymers. A rich behavior is predicted for two-component polymer networks containing azobenzenes and non-chromophoric LC mesogens. Whether such two-component network expands or contracts with respect to the light polarization, depends on the art of attachment of the mesogens to the network strands.

  9. Fluorescence modulation of cadmium sulfide quantum dots by azobenzene photochromic switches.

    PubMed

    Javed, Hina; Fatima, Kalsoom; Akhter, Zareen; Nadeem, Muhammad Arif; Siddiq, Muhammad; Iqbal, Azhar

    2016-02-01

    We have investigated the attachment of azobenzene photochromic switches on the modified surface of cadmium sulfide (CdS) quantum dots (QDs). The modification of CdS QDs is done by varying the concentration of the capping agent (mercaptoacetic acid) and NH3 in order to control the size of the QDs. The X-ray diffraction studies revealed that the crystallite size of CdS QDs ranged from 6 to 10 nm. The azobenzene photochromic derivatives bis(4-hydroxybenzene-1-azo)4,4'(1,1' diphenylmethane) (I) and 4,4'-diazenyldibenzoic acid (II) were synthesized and attached with surface-modified CdS QDs to make fluorophore-photochrome CdS-(I) and CdS-(II) dyad assemblies. Upon UV irradiation, the photochromic compounds (I) and (II) undergo a reversible trans-cis isomerization. The photo-induced trans-cis transformation helps to transfer photo-excited electrons from the conduction band of the CdS QDs to the lowest unoccupied molecular orbital of cis isomer of photochromic compounds (I) and (II). As a result, the fluorescence of CdS-(I) and CdS-(II) dyads is suppressed approximately five times compared to bare CdS QDs. The fluorescence modulation in such systems could help to design luminescent probes for bioimaging applications.

  10. New insights into mechanistic photoisomerization of ethylene-bridged azobenzene from ab initio multiple spawning simulation

    NASA Astrophysics Data System (ADS)

    Liu, Lihong; Wang, Yating; Fang, Qiu

    2017-02-01

    Ethylene-bridged azobenzene (br-AB) has aroused broad interests due to its unique photoswitching properties. Numerous dynamical simulations have been performed for the br-AB photoisomerization, which focused mainly on the conformational effect and the funnel role of minimum-energy conical intersection (MECI) on the mechanism. In the present work, we use the "full quantum" ab initio multiple spawning method to simulate the br-AB photoisomerization, which provides new insights into the mechanism. Upon irradiation of br-AB to the first excited singlet state (S1), most of the excess energies are trapped in the azo-moiety. Since the intramolecular vibrational energy redistribution is slower than the S1 relaxation processes, the nonadiabatic transition from S1 to the ground state (S0) occurs in the vicinity of high-energy crossing seam and even the largest probabilities of the S1 → S0 transition are not distributed in the MECI regions. Once decaying to the S0 state through the high-energy region, the subsequent isomerization and re-formation of the initial isomer are ultrafast processes in the S0 state. It is the nonergodic behavior of the S1 and S0 dynamics that is mainly responsible for the unique photoswitching properties of the ethylene-bridged azobenzene, which will be discussed in detail.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  12. Heart Block

    MedlinePlus

    ... not used to treat first-degree heart block. All types of heart block may increase your risk for other arrhythmias, such as atrial fibrillation (A-tre-al fih-brih-LA-shun). Talk with your doctor ...

  13. Population Blocks.

    ERIC Educational Resources Information Center

    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…

  14. A pre-formed methyl methacrylate cranioplasty.

    PubMed

    Cooper, P R; Schechter, B; Jacobs, G B; Rubin, R C; Wille, R L

    1977-09-01

    The use of a pre-formed methyl methacrylate cranioplasty prosthesis reinforced with stainless steel wire is described. The prosthesis is non-reactive, virtually unbreakable, and undentable. Pre-forming of the prosthesis in the dental laboratory using a mold of the patient's bony defect as a model saves considerable operating time, and when employed for a large cranial defect the three dimensional cosmetic effect is superior to intra-operatively fashioned prostheses.

  15. Reactivity of methacrylates in insertion polymerization.

    PubMed

    Rünzi, Thomas; Guironnet, Damien; Göttker-Schnetmann, Inigo; Mecking, Stefan

    2010-11-24

    Polymerization of ethylene by complexes [{(P^O)PdMe(L)}] (P^O = κ(2)-(P,O)-2-(2-MeOC(6)H(4))(2)PC(6)H(4)SO(3))) affords homopolyethylene free of any methyl methacrylate (MMA)-derived units, even in the presence of substantial concentrations of MMA. In stoichiometric studies, reactive {(P^O)Pd(Me)L} fragments generated by halide abstraction from [({(P^O)Pd(Me)Cl}μ-Na)(2)] insert MMA in a 1,2- as well as 2,1-mode. The 1,2-insertion product forms a stable five-membered chelate by coordination of the carbonyl group. Thermodynamic parameters for MMA insertion are ΔH(++) = 69.0(3.1) kJ mol(-1) and ΔS(++) = -103(10) J mol(-1) K(-1) (total average for 1,2- and 2,1-insertion), in comparison to ΔH(++) = 48.5(3.0) kJ mol(-1) and ΔS(++) = -138(7) J mol(-1) K(-1) for methyl acrylate (MA) insertion. These data agree with an observed at least 10(2)-fold preference for MA incorporation vs MMA incorporation (not detected) under polymerization conditions. Copolymerization of ethylene with a bifunctional acrylate-methacrylate monomer yields linear polyethylenes with intact methacrylate substituents. Post-polymerization modification of the latter was exemplified by free-radical thiol addition and by cross-metathesis.

  16. Dimensional accuracy of thermoformed polymethyl methacrylate.

    PubMed

    Jagger, R G

    1996-12-01

    Thermoforming of polymethyl methacrylate sheet is used to produce a number of different types of dental appliances. The purpose of this study was to determine the dimensional accuracy of thermoformed polymethyl methacrylate specimens. Five blanks of the acrylic resin were thermoformed on stone casts prepared from a silicone mold of a brass master die. The distances between index marks were measured both on the cast and on the thermoformed blanks with an optical comparator. Measurements on the blanks were made again 24 hours after processing and then 1 week, 1 month, and 3 months after immersion in water. Linear shrinkage of less than 1% (range 0.37% to 0.52%) was observed 24 hours after removal of the blanks from the cast. Immersion of the thermoformed specimens in water resulted in an increase in measured dimensions, but after 3 months' immersion these increases were still less than those of the cast (range 0.07% to 0.18%). It was concluded that it is possible to thermoform Perspex polymethyl methacrylate accurately.

  17. Au nanoparticle scaffolds modulating intermolecular interactions among the conjugated azobenzenes chemisorbed on curved surfaces: tuning the kinetics of cis-trans isomerisation

    NASA Astrophysics Data System (ADS)

    Raimondo, Corinna; Kenens, Bart; Reinders, Federica; Mayor, Marcel; Uji-I, Hiroshi; Samorì, Paolo

    2015-08-01

    π-π Intermolecular interactions among adjacent conjugated azobenzenes chemisorbed on (non-)flat Au surfaces can be tuned by varying the curvature of the Au nanoparticles. Here we show that such interactions rule the thermal cis-trans isomerization kinetics, towards a better control on the azobenzene bistability for its optimal integration as a responsive material.π-π Intermolecular interactions among adjacent conjugated azobenzenes chemisorbed on (non-)flat Au surfaces can be tuned by varying the curvature of the Au nanoparticles. Here we show that such interactions rule the thermal cis-trans isomerization kinetics, towards a better control on the azobenzene bistability for its optimal integration as a responsive material. Electronic supplementary information (ESI) available: Physico-chemical characterization of the different sizes of nanoparticles, UV-Vis, Surface Enhanced Raman Spectroscopy (SERS), materials and methods. See DOI: 10.1039/c5nr03688g

  18. Efficient gene carriers composed of 2-hydroxypropyl-β-cyclodextrin, ethanolamine-functionalized poly(glycidyl methacrylate), and poly((2-dimethyl amino)ethyl methacrylate) by combination of ATRP and click chemistry.

    PubMed

    Zhu, Yun; Zheng, Xuefeng; Yu, Bingran; Yang, Wantai; Zhao, Nana; Xu, Fujian

    2014-08-01

    In this work, a simple one-step method is first employed to produce the bromoisobutyryl-terminated 2-hydroxypropyl-β-cyclodextrin (HPCD-Br). The pendant epoxy groups of poly(glycidyl methacrylate) block prepared via ATRP from HPCD-Br can be reacted with ethanolamine to produce HPCD-PGEA which exhibits much lower cytotoxicity and better gene transfection yield than polyethylenimine (25 kDa) in COS7 and HepG2 cell lines. Moreover, poly((2-dimethyl amino)ethyl methacrylate) blocks can be incorporated into low-molecular-weight HPCD-PGEA via "click" reaction to further enhance the gene transfection efficiency in HepG2 cell lines.

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

    PubMed

    Nielsen, Birthe V; Nevell, Thomas G; Barbu, Eugen; Smith, James R; Rees, Gareth D; Tsibouklis, John

    2011-02-01

    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.

  20. Azobenzene-based organic salts with ionic liquid and liquid crystalline properties

    SciTech Connect

    Stappert, Kathrin; Muthmann, Johanna; Spielberg, Eike T.; Mudring, Anja -Verena

    2015-07-23

    Two sets of new azobenzene-based bromide salts are synthesized, and their thermal photochromic properties are studied. Both sets are based on the imidazolium cation. The first set (1) features a symmetric biscation where two imidazolium head groups (Im) with different alkyl chains (Cn) are connected to a central azobenzene unit (Azo): [Azo(C1-Im-Cn)2]; n = 6, 8, 10, 12, 14. The other one contains an n-alkyl-imidazolium cation (Cn-Im) bearing a terminal azobenzene unit (C1-Azo) substituted with an alkoxy chain (O-Cm) of either two (2) or six (3) carbon atoms: [C1-Azo-O-Cm-Im-Cn]; m = 2, n = 8, 10, 12 and m = 6, n = 8, 10, 12, 14, 16. For both cation classes, the influence of alkyl chains of varying length on the thermal phase behavior was investigated by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). For five compounds (Azo(-C1-Im-C12)2 (1d), Azo(-C1-Im-C12)2 (1e), C1-Azo-O-C2-Im-C10 (2b), C1-Azo-O-C2-Im-C12 (2c), and C1-Azo-O-C6-Im-C16 (3e)), the formation of a liquid crystalline phase was observed. The biscationic salts (1) are all comparatively high melting organic salts (180–240 °C), and only the two representatives with long alkylchains (C12 and C14) exhibit liquid crystallinity. The monocationic salts with an O–C2 bridge (2) melt between 140 and 170 °C depending on the alkyl chain length, but from an alkyl chain of 10 and more carbon atoms on they form a smectic A liquid crystalline phase. The representatives of the third set with a O–C6 bridge qualify as ionic liquids with melting points less than 100 °C. However, only the representative with a hexadecyl chain forms a liquid crystalline phase. Representative single crystals for all sets of cations could be grown that allowed for single crystal structure analysis. Together with small-angle X-ray scattering experiments they allow for a more detailed understanding of the thermal properties. As a result, through irradiation with UV

  1. Azobenzene-based organic salts with ionic liquid and liquid crystalline properties

    DOE PAGES

    Stappert, Kathrin; Muthmann, Johanna; Spielberg, Eike T.; ...

    2015-07-23

    Two sets of new azobenzene-based bromide salts are synthesized, and their thermal photochromic properties are studied. Both sets are based on the imidazolium cation. The first set (1) features a symmetric biscation where two imidazolium head groups (Im) with different alkyl chains (Cn) are connected to a central azobenzene unit (Azo): [Azo(C1-Im-Cn)2]; n = 6, 8, 10, 12, 14. The other one contains an n-alkyl-imidazolium cation (Cn-Im) bearing a terminal azobenzene unit (C1-Azo) substituted with an alkoxy chain (O-Cm) of either two (2) or six (3) carbon atoms: [C1-Azo-O-Cm-Im-Cn]; m = 2, n = 8, 10, 12 and m =more » 6, n = 8, 10, 12, 14, 16. For both cation classes, the influence of alkyl chains of varying length on the thermal phase behavior was investigated by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). For five compounds (Azo(-C1-Im-C12)2 (1d), Azo(-C1-Im-C12)2 (1e), C1-Azo-O-C2-Im-C10 (2b), C1-Azo-O-C2-Im-C12 (2c), and C1-Azo-O-C6-Im-C16 (3e)), the formation of a liquid crystalline phase was observed. The biscationic salts (1) are all comparatively high melting organic salts (180–240 °C), and only the two representatives with long alkylchains (C12 and C14) exhibit liquid crystallinity. The monocationic salts with an O–C2 bridge (2) melt between 140 and 170 °C depending on the alkyl chain length, but from an alkyl chain of 10 and more carbon atoms on they form a smectic A liquid crystalline phase. The representatives of the third set with a O–C6 bridge qualify as ionic liquids with melting points less than 100 °C. However, only the representative with a hexadecyl chain forms a liquid crystalline phase. Representative single crystals for all sets of cations could be grown that allowed for single crystal structure analysis. Together with small-angle X-ray scattering experiments they allow for a more detailed understanding of the thermal properties. As a result, through irradiation with UV-light (320–366 nm) all

  2. Protein-resistant polymer coatings based on surface-adsorbed poly(aminoethyl methacrylate)/poly(ethylene glycol) copolymers.

    PubMed

    Ionov, Leonid; Synytska, Alla; Kaul, Elisabeth; Diez, Stefan

    2010-01-11

    We report on the protein-resistant properties of glass substrates coated with novel copolymers of 2-aminoethyl methacrylate hydrochloride and poly(ethylene glycol) methyl ether methacrylate (AEM-PEG). In comparison to currently available protein-blocking polymer systems, such as poly-l-lysine-poly(ethylene glycol), silane-based poly(ethylene glycol), and poly(ethylene glycol) brushes prepared by surface-initiated polymerization, the proposed AEM-PEG offers the combined advantages of low cost, simplicity of use, and applicability in aqueous solutions. We demonstrate the capability of AEM-PEG to block the surface binding of globular proteins (tubulin), their assemblies (microtubules), and functional motor proteins (kinesin-1). Moreover, we demonstrate the applicability of AEM-PEG for surface patterning of proteins in microfluidic devices.

  3. Periodontal repair in dogs: histologic observations of guided tissue regeneration with a prostaglandin E1 analog/methacrylate composite.

    PubMed

    Trombelli, L; Lee, M B; Promsudthi, A; Guglielmoni, P G; Wikesjö, U M

    1999-06-01

    This report describes observations of healing following guided tissue regeneration (GTR) including surgical implantation of the prostaglandin E1 analog misoprostol with calcium-layered methacrylate particles. Critical size, supra-alveolar periodontal defects were surgically created around the 3rd and 4th mandibular premolar teeth in 4 beagle dogs. Wound management included soaking with a 24 microg/ml misoprostol solution and implantation of the misoprostol/methacrylate composite. One jaw quadrant per animal was prepared for GTR using expanded polytetrafluoroethylene membranes. The gingival flaps were coronally advanced and sutured to submerge the teeth. The tissues covering the surgical sites daily received topical misoprostol in an oral adhesive over the 4-week healing interval. Upon euthanasia, tissue blocks were prepared for histometric analysis of regeneration of alveolar bone and cementum, root resorption and ankylosis. The defect area underneath the membrane and the density of methacrylate particles were recorded for the GTR defects. The methacrylate particles appeared encapsulated in a dense connective tissue without signs of an inflammatory reaction, some in contact to newly formed bone. Alveolar bone regeneration height averaged (+/-SD) 1.2+/-1.0 and 1.0+/-0.6 mm for GTR and non-GTR defects, respectively. Corresponding values for bone regeneration area were 1.3+/-1.0 and 0.7+/-0.5 mm2. Cementum regeneration was confined to the apical aspect of the defects. Small areas of root resorption and ankylosis were observed for all teeth. Bone regeneration area correlated positively to the defect area and negatively to the density of methacrylate particles in the GTR defects. The histologic observations suggest that the methacrylate composite has marginal potential to promote bone and cementum regeneration under provisions for GTR.

  4. Blends of isoprene-styrene/methacrylate monomer systems as denture soft lining material.

    PubMed

    Nazhat, S N; Parker, S; Riggs, P D; Braden, M

    2001-08-01

    This work further develops the concept of using an elastomer gelled with methacrylate monomers to produce a methacrylate-based soft lining material without the use of a plasticizer. An isoprene-styrene (SIS) block copolymer was mixed with methyl methacrylate (MMA) and 1,6-hexandiol dimethacrylate (HDMA). The HDMA was used as a cross-linking agent. The elastomer/monomer ratios were maintained at 50/50 whereas the monomers ranged from 0 to 100%) HDMA. Mechanical properties and water absorption/desorption characteristics were used to assess the effect of varying the monomer compositions. The results indicated that phase separation took place, in particular at high HDMA content. This significantly increased the Young's modulus and decreased the elongation to break. Generally, the water uptake tended to decrease with increasing HDMA content, reflecting the effect of modulus. Second absorption cycles gave higher uptake values compared to the first. Formulations with a high amount of HDMA gave materials with modulus values too high for soft lining applications. This suggests that the optimum formulation requires a compromise between modulus and water uptake.

  5. Synthesis and characterization of functionalized methacrylates for coatings and biomedical applications

    NASA Astrophysics Data System (ADS)

    Shemper, Bianca Sadicoff

    The research presented in this dissertation involves the design of polymers for biomaterials and for coatings applications. The development of non-wettable, hard UV-curing, or reactive coatings is discussed. The biomaterials section involves the syntheses of linear and star-like polymers of the functionalized monomer poly(propylene glycol) monomethacrylate (PPGM) via atom transfer radical polymerization (ATRP) (Chapter II). Its copolymerization with a perfluoroalkyl ethyl methacrylate monomer (1H,1H,2H,2H-heptadecafluorodecyl methacrylate) and the syntheses of linear and star-like amphiphilic copolymers containing the fluorinated monomer and poly(ethyleneglycol) methyl ether methacrylate (MPEGMA) are discussed in Chapter III. The four-arm amphiphilic block copolymer obtained showed unique associative properties leading to micellization in selective solvents. Chapter IV includes research involving the design of films with low surface energy by incorporating fluorine into the polymer. The synthesis, characterization and polymerization of a perfluoroalkylether-substituted methacrylic acid (C8F7) are discussed, and the properties of coatings obtained after its photopolymerization on different substrates are evaluated to confirm formation of low-surface energy polymeric coatings. Subsequently, hard coatings based on methyl (alpha-hydroxymethyl)acrylate (MHMA) were prepared via photopolymerization using UV-light. Firstly, mechanistic investigations into the photopolymerization behavior of (alpha-hydroxymethyl)acrylates (RHMA's) are reported (Chapter V). RHMA derivatives were photopolymerized with various multifunctional acrylates and methacrylates and the effect of crosslinker type and degree of functionality on photopolymerization rates and conversions was investigated. Then, in Chapter VI the synthesis of a series of new crosslinkers is described and their photopolymerization kinetics was investigated in bulk. The effect of these novel crosslinkers on the

  6. On permeability of methyl methacrylate, 2-hydroxyethyl methacrylate and triethyleneglycol dimethacrylate through protective gloves in dentistry.

    PubMed

    Andreasson, Harriet; Boman, Anders; Johnsson, Stina; Karlsson, Stig; Barregård, Lars

    2003-12-01

    Continuous glove use is more common in dentistry than in most other occupations, and the glove should offer protection against blood-borne infections, skin irritants and contact allergens. Methacrylate monomers are potent contact allergens, and it is known that these substances may penetrate the glove materials commonly used. The aim of this study was to assess the permeability of various types of gloves to methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (HEMA) and triethyleneglycol dimethacrylate (TEGDMA) with special reference to combinations with ethanol or acetone. The permeation rate and time lag breakthrough (lag-BT) for MMA (neat, or diluted to 30% in ethanol or acetone), HEMA (30% in water, ethanol, or acetone) and TEGDMA (30% in ethanol or acetone) were investigated for different protective gloves. Nine different types of gloves were tested for one or several of these methacrylates. The lag-BT for neat MMA was

  7. Switching Thin Films of Azobenzene-Containing Metal-Organic Frameworks with Visible Light.

    PubMed

    Müller, Kai; Knebel, Alexander; Zhao, Fangli; Bléger, David; Caro, Jürgen; Heinke, Lars

    2017-04-03

    Stimuli-responsive molecules change their properties when exposed to external signals, such as light, and enable the preparation of smart materials. UV light, which often destroys organic materials, is typically required for activating the desired response of photoswitchable compounds, significantly limiting the potential applications of light-operated smart materials. Herein, we present the first metal-organic framework (MOF), which enables reversible modulation of key properties upon irradiation with visible light only. The fluorinated azobenzene side groups in the MOF structure can be reversibly switched between the trans and cis state by green and violet light, avoiding UV light. It was demonstrated that the uptake of guest molecules by these MOF films can be switched in a fully remote-controlled way. The membrane separation of hydrogen/hydrocarbon mixtures was investigated. The light-induced changes of the MOF pore size result in the switching of the permeation and of the selection factor.

  8. Azobenzene Containing Low-Molecular Weight Organic Glasses for Optical Recording

    NASA Astrophysics Data System (ADS)

    Aleksejeva, J.; Teteris, J.; Tokmakovs, A.

    In this work photoinduced processes and holographic surface relief formation in azobenzene containing low- molecular weight organic glasses were studied. The molecular glasses due to trans-cis isomerisation and photo- orientation of molecules possess high sensitivity to the light irradiation and therefore they are promising media for holographic recording. Electric field of linearly polarized light causes an alignment of molecule dipoles perpendicularly to the electric field vector and this process is accompanied by an appearance of photoinduced optical anisotropy in organic glasses. The photoinduced birefringence and dichroism induced by 532 nm light was studied. Holographic recording in organic molecular glasses was performed with 532 nm solid-state diode-pumped laser Verdi-6. Very rapid holographic grating recording and surface relief formation at small recording beam intensities was observed. The dependence of recorded grating diffraction efficiency and surface relief depth on recording beams polarization state and intensities was studied. The surface relief was studied with AFM.

  9. Zwitterionic Poly(amino acid methacrylate) Brushes

    PubMed Central

    2014-01-01

    A new cysteine-based methacrylic monomer (CysMA) was conveniently synthesized via selective thia-Michael addition of a commercially available methacrylate-acrylate precursor in aqueous solution without recourse to protecting group chemistry. Poly(cysteine methacrylate) (PCysMA) brushes were grown from the surface of silicon wafers by atom-transfer radical polymerization. Brush thicknesses of ca. 27 nm were achieved within 270 min at 20 °C. Each CysMA residue comprises a primary amine and a carboxylic acid. Surface zeta potential and atomic force microscopy (AFM) studies of the pH-responsive PCysMA brushes confirm that they are highly extended either below pH 2 or above pH 9.5, since they possess either cationic or anionic character, respectively. At intermediate pH, PCysMA brushes are zwitterionic. At physiological pH, they exhibit excellent resistance to biofouling and negligible cytotoxicity. PCysMA brushes undergo photodegradation: AFM topographical imaging indicates significant mass loss from the brush layer, while XPS studies confirm that exposure to UV radiation produces surface aldehyde sites that can be subsequently derivatized with amines. UV exposure using a photomask yielded sharp, well-defined micropatterned PCysMA brushes functionalized with aldehyde groups that enable conjugation to green fluorescent protein (GFP). Nanopatterned PCysMA brushes were obtained using interference lithography, and confocal microscopy again confirmed the selective conjugation of GFP. Finally, PCysMA undergoes complex base-catalyzed degradation in alkaline solution, leading to the elimination of several small molecules. However, good long-term chemical stability was observed when PCysMA brushes were immersed in aqueous solution at physiological pH. PMID:24884533

  10. Photoresponsive elastic properties of azobenzene-containing poly(ethylene-glycol)-based hydrogels

    PubMed Central

    Rosales, Adrianne M.; Mabry, Kelly M.; Nehls, Eric Michael; Anseth, Kristi S.

    2015-01-01

    The elastic modulus of the extracellular matrix is a dynamic property that changes during various biological processes, such as disease progression or wound healing. Most cell culture platforms, however, have traditionally exhibited static properties, making it necessary to replate cells to study the effects of different elastic moduli on cell phenotype. Recently, much progress has been made in the development of substrates with mechanisms for either increasing or decreasing stiffness in situ, but there are fewer examples of substrates that can both stiffen and soften, which may be important for simulating the effects of repeated ECM injury and resolution. In the work presented here, poly(ethylene glycol)-based hydrogels reversibly stiffen and soften with multiple light stimuli via photoisomerization of an azobenzene-containing crosslinker. Upon irradiation with cytocompatible doses of 365 nm light (10 mW/cm2, 5 min), isomerization to the azobenzene cis configuration leads to a softening of the hydrogel up to 100-200 Pa (shear storage modulus, G’). This change in gel properties is maintained over a timescale of several hours due to the long half-life of the cis isomer. The initial modulus of the gel can be recovered upon irradiation with similar doses of visible light. With applications in mechanobiology in mind, cytocompatibility with a mechanoresponsive primary cell type is demonstrated. Porcine aortic valvular interstitial cells were encapsulated in the developed hydrogels and shown to exhibit high levels of survival, as well as a spread morphology. The developed hydrogels enable a route to the noninvasive control of substrate modulus independent of changes in the chemical composition or network connectivity, allowing for investigations of the effect of dynamic matrix stiffness on adhered cell behavior. PMID:25629423

  11. Methacrylic resin having a high solar radiant energy absorbing property and process for producing the same

    SciTech Connect

    Abe, K.; Kamada, K.; Nakai, Y.

    1981-10-20

    A methacrylic resin having a high solar radiant energy absorbing property wherein an organic compound (A) containing cupric ion and a compound (B) having at least one p-o-h bond in a molecule are contained into the methacrylic resin selected from poly(Methyl methacrylate) or methacrylic polymers containing at least 50% by weight of a methyl methacrylate unit. A process for producing said methacrylic resin is also disclosed.

  12. Ionic Blocks

    ERIC Educational Resources Information Center

    Sevcik, Richard S.; Gamble, Rex; Martinez, Elizabet; Schultz, Linda D.; Alexander, Susan V.

    2008-01-01

    "Ionic Blocks" is a teaching tool designed to help middle school students visualize the concepts of ions, ionic compounds, and stoichiometry. It can also assist high school students in reviewing their subject mastery. Three dimensional blocks are used to represent cations and anions, with color indicating charge (positive or negative) and size…

  13. DEGRADATION OF POLY(METHYL METHACRYLATE) IN SOLUTION

    EPA Science Inventory

    The rate of degradation of poly(methyl methacrylate) (PMMA) to methyl methacrylate (MMA) was investigated in the liquid phase with toluene as the solvent. The degradation experiments were carried out in a tubular flow reactor at 1000 psig (6.8 MPa) and at four different temperat...

  14. Photoswitching of glass transition temperatures of azobenzene-containing polymers induces reversible solid-to-liquid transitions

    NASA Astrophysics Data System (ADS)

    Zhou, Hongwei; Xue, Changguo; Weis, Philipp; Suzuki, Yasuhito; Huang, Shilin; Koynov, Kaloian; Auernhammer, Günter K.; Berger, Rüdiger; Butt, Hans-Jürgen; Wu, Si

    2016-10-01

    The development of polymers with switchable glass transition temperatures (Tg) can address scientific challenges such as the healing of cracks in high-Tg polymers and the processing of hard polymers at room temperature without using plasticizing solvents. Here, we demonstrate that light can switch the Tg of azobenzene-containing polymers (azopolymers) and induce reversible solid-to-liquid transitions of the polymers. The azobenzene groups in the polymers exhibit reversible cis-trans photoisomerization abilities. Trans azopolymers are solids with Tg above room temperature, whereas cis azopolymers are liquids with Tg below room temperature. Because of the photoinduced solid-to-liquid transitions of these polymers, light can reduce the surface roughness of azopolymer films by almost 600%, repeatedly heal cracks in azopolymers, and control the adhesion of azopolymers for transfer printing. The photoswitching of Tg provides a new strategy for designing healable polymers with high Tg and allows for control over the mechanical properties of polymers with high spatiotemporal resolution.

  15. Regulation of substituent groups on morphologies and self-assembly of organogels based on some azobenzene imide derivatives

    NASA Astrophysics Data System (ADS)

    Jiao, Tifeng; Wang, Yujin; Zhang, Qingrui; Zhou, Jingxin; Gao, Faming

    2013-04-01

    In this paper, new azobenzene imide derivatives with different substituent groups were designed and synthesized. Their gelation behaviors in 21 solvents were tested as novel low-molecular-mass organic gelators. It was shown that the alkyl substituent chains and headgroups of azobenzene residues in gelators played a crucial role in the gelation behavior of all compounds in various organic solvents. More alkyl chains in molecular skeletons in present gelators are favorable for the gelation of organic solvents. Scanning electron microscopy and atomic force microscopy observations revealed that the gelator molecules self-assemble into different aggregates, from wrinkle, lamella, and belt to fiber with the change of solvents. Spectral studies indicated that there existed different H-bond formations between amide groups and conformations of methyl chains. The present work may give some insight to the design and character of new organogelators and soft materials with special molecular structures.

  16. Nanostructure formation by self-assembled monolayers: influence of the isomerization state of azobenzene ligands on monolayer formation

    NASA Astrophysics Data System (ADS)

    Vogel, Florian; Bretthauer, Frauke; Siemeling, Ulrich; Träger, Frank

    2011-03-01

    The monolayer formation of photoswitchable self-assembled monolayers of azobenzene-functionalized molecules was studied in situ and in real time by optical second-harmonic generation. Especially the influence of the isomerization state during the adsorption process was measured in our experiments. As will be shown, the isomerization state has a significant influence on the adsorption process of the investigated molecules. Based on the results of the second-harmonic generation experiments the kinetics of the adsorption process was determined.

  17. From the N-Heterocyclic Carbene-Catalyzed Conjugate Addition of Alcohols to the Controlled Polymerization of (Meth)acrylates.

    PubMed

    Ottou, Winnie Nzahou; Bourichon, Damien; Vignolle, Joan; Wirotius, Anne-Laure; Robert, Fredéric; Landais, Yannick; Sotiropoulos, Jean-Marc; Miqueu, Karinne; Taton, Daniel

    2015-06-22

    Among various N-heterocyclic carbenes (NHCs) tested, only 1,3-bis(tert-butyl)imidazol-2-ylidene (NHC(tBu) ) proved to selectively promote the catalytic conjugate addition of alcohols onto (meth)acrylate substrates. This rather rare example of NHC-catalyzed 1,4-addition of alcohols was investigated as a simple means to trigger the polymerization of both methyl methacrylate and methyl acrylate (MMA and MA, respectively). Well-defined α-alkoxy poly(methyl (meth)acrylate) (PM(M)A) chains, the molar masses of which could be controlled by the initial [(meth)acrylate]0/[ROH]0 molar ratio, were ultimately obtained in N,N-dimethylformamide at 25 °C. A hydroxyl-terminated poly(ethylene oxide) (PEO-OH) macro-initiator was also employed to directly access PEO-b-PMMA amphiphilic block copolymers. Investigations into the reaction mechanism by DFT calculations revealed the occurrence of two competitive concerted pathways, involving either the activation of the alcohol or that of the monomer by NHC(tBu) .

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

    PubMed

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

    2016-02-01

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

  19. Optical Actuation of Inorganic/Organic Interfaces: Comparing Peptide-Azobenzene Ligand Reconfiguration on Gold and Silver Nanoparticles.

    PubMed

    Palafox-Hernandez, J Pablo; Lim, Chang-Keun; Tang, Zhenghua; Drew, Kurt L M; Hughes, Zak E; Li, Yue; Swihart, Mark T; Prasad, Paras N; Knecht, Marc R; Walsh, Tiffany R

    2016-01-13

    Photoresponsive molecules that incorporate peptides capable of material-specific recognition provide a basis for biomolecule-mediated control of the nucleation, growth, organization, and activation of hybrid inorganic/organic nanostructures. These hybrid molecules interact with the inorganic surface through multiple noncovalent interactions which allow reconfiguration in response to optical stimuli. Here, we quantify the binding of azobenzene-peptide conjugates that exhibit optically triggered cis-trans isomerization on Ag surfaces and compare to their behavior on Au. These results demonstrate differences in binding and switching behavior between the Au and Ag surfaces. These molecules can also produce and stabilize Au and Ag nanoparticles in aqueous media where the biointerface can be reproducibly and reversibly switched by optically triggered azobenzene isomerization. Comparisons of switching rates and reversibility on the nanoparticles reveal differences that depend upon whether the azobenzene is attached at the peptide N- or C-terminus, its isomerization state, and the nanoparticle composition. Our integrated experimental and computational investigation shows that the number of ligand anchor sites strongly influences the nanoparticle size. As predicted by our molecular simulations, weaker contact between the hybrid biomolecules and the Ag surface, with fewer anchor residues compared with Au, gives rise to differences in switching kinetics on Ag versus Au. Our findings provide a pathway toward achieving new remotely actuatable nanomaterials for multiple applications from a single system, which remains difficult to achieve using conventional approaches.

  20. Molecular characteristics of a fluorescent chemosensor for the recognition of ferric ion based on photoresponsive azobenzene derivative

    NASA Astrophysics Data System (ADS)

    Chi, Zhen; Ran, Xia; Shi, Lili; Lou, Jie; Kuang, Yanmin; Guo, Lijun

    2017-01-01

    Metal ion recognition is of great significance in biological and environmental detection. So far, there is very few research related to the ferric ion sensing based on photoresponsive azobenzene derivatives. In this work, we report a highly selective fluorescent ;turn-off; sensor for Fe3 + ions and the molecular sensing characteristics based on an azobenzene derivative, N-(3,4,5-octanoxyphenyl)-N‧-4-[(4-hydroxyphenyl)azophenyl]1,3,4-oxadiazole (AOB-t8). The binding association constant was determined to be 6.07 × 103 M- 1 in ethanol and the stoichiometry ratio of 2:2 was obtained from Job's plot and MS spectra. The AOB-t8 might be likely to form the dimer structure through the chelation of ferric ion with the azobenzene moiety. Meanwhile, it was found that the photoisomerization property of AOB-t8 was regulated by the binding with Fe3 +. With the chelation of Fe3 +, the regulated molecular rigidity and the perturbed of electronic state and molecular geometry was suggested to be responsible for the accelerated isomerization of AOB-t8 to UV irradiation and the increased fluorescence lifetime of both trans- and cis-AOB-t8-Fe(III). Moreover, the reversible sensing of AOB-t8 was successfully observed by releasing the iron ion from AOB-t8-Fe(III) with the addition of citric acid.

  1. Ultrafast dynamics of the azobenzene-coumarin complex: investigation of cooling dynamics measured by an integrated molecular thermometer.

    PubMed

    Velate, Suresh; Danilov, Evgeny O; Rodgers, Michael A J

    2005-10-13

    The energy dissipation mechanism from photoexcited azobenzene (Az) was studied by femtosecond time-resolved UV absorption spectroscopy using 7-amino-4-trifluoromethylcoumarin (ATC) as a probe. The distance between the probe molecule and Az was fixed by covalently linking them together through a rigid proline spacer. Picosecond dynamics in THF solutions were studied upon excitation into the S1 state by a 100 fs laser pulse at 480 nm. Transient absorption spectra obtained for Az-Pro-ATC combined the S1 state absorption and vibrationally excited ground-state absorption of ATC. Correction of the transient spectrum of Az-Pro-ATC for the S1 absorption provided the time-resolved absorption spectrum of the ATC hot band. Three major components were observed in the transient kinetics of Az-Pro-ATC vibrational cooling. It is proposed that in ca. 0.25 ps after the excitation, the S1 state of azobenzene decays to form an initial vibrationally excited nonthermalized ground state of Az-Pro-ATC that involves vibrational modes of both azobenzene and coumarin. This hot ground state decays in ca. 0.32 ps to the next, vibrationally equilibrated, transient state by redistributing the energy within the molecule. Subsequently, the latter state cools by transferring its energy to the closest solvent molecules in ca. 5 ps; then, the energy diffuses to the bulk solvent in 13 ps.

  2. Uptake of isoprene, methacrylic acid and methyl methacrylate into aqueous solutions of sulfuric acid and hydrogen peroxide.

    PubMed

    Liu, Ze; Ge, Maofa; Wang, Weigang

    2012-01-01

    Multiphase acid-catalyzed oxidation by hydrogen peroxide has been suggested to be a potential route to secondary organic aerosol formation from isoprene and its gas-phase oxidation products, but the lack of kinetics data significantly limited the evaluation of this process in the atmosphere. Here we report the first measurement of the uptake of isoprene, methacrylic acid and methyl methacrylate into aqueous solutions of sulfuric acid and hydrogen peroxide. Isoprene cannot readily partition into the solution because of its high volatility and low solubility, which hinders its further liquid-phase oxidation. Both methacrylic acid and methyl methacrylate can enter the solutions and be oxidized by hydrogen peroxide, and steady-state uptake was observed with the acidity of solution above 30 wt.% and 70 wt.%, respectively. The steady-state uptake coefficient of methacrylic acid is much larger than that of methyl methacrylate for a solution with same acidity. These observations can be explained by the different reactivity of these two compounds caused by the different electron-withdrawing conjugation between carboxyl and ester groups. The atmospheric lifetimes were estimated based on the calculated steady-state uptake coefficients. These results demonstrate that the multiphase acid-catalyzed oxidation of methacrylic acid plays a role in secondary organic aerosol formation, but for isoprene and methyl methacrylate, this process is not important in the troposphere.

  3. Improvement of holographic thermal stability in phenanthrenequinone-doped poly(methyl methacrylate-co-methacrylic acid) photopolymer

    NASA Astrophysics Data System (ADS)

    Yu, Dan; Liu, Hongpeng; Wang, Heng; Wang, Jian; Jiang, Yongyuan; Sun, Xiudong

    2011-08-01

    Experimental studies of holographic thermal stability in phenanthrenequinone (PQ)-doped poly(methyl methacrylate-co-methacrylic acid) [P(MMA-co-MAA)] photopolymers are presented. A possibility to improve the thermal stability of holograms is demonstrated by doping methacrylic acid (MAA) into the poly(methyl methacrylate) (PMMA) polymer matrix. MAA as a copolymerization monomer can form a more stable polymer matrix with methyl methacrylate (MMA) monomer and increase average molecular weight of photoproducts, which finally depress the diffusion of photoproduct. The optimized MAA concentration copolymerized into P(MMA-co-MAA) polymer matrix can bring nearly a month's lifetime of gratings, which is obviously an improvement over the usual PQ-PMMA material under thermal treatment.

  4. Studies on novel radiopaque methyl methacrylate: glycidyl methacrylate based polymer for biomedical applications.

    PubMed

    Dawlee, S; Jayakrishnan, A; Jayabalan, M

    2009-12-01

    A new class of radiopaque copolymer using methyl methacrylate (MMA) and glycidyl methacrylate (GMA) monomers was synthesized and characterized. The copolymer was made radiopaque by the epoxide ring opening of GMA using the catalyst o-phenylenediamine and the subsequent covalent attachment of elemental iodine. The copolymer was characterized by Fourier transform infrared (FTIR) spectra, energy dispersive X-ray analysis using environmental scanning electron microscope (EDAX), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). X-ray visibility of the copolymer was checked by X-radiography. Blood compatibility and cytotoxicity of the newly synthesized copolymer were also evaluated. The iodinated copolymer was thermally stable, blood compatible, non-cytotoxic, and highly radiopaque. The presence of bulky iodine group created a new copolymer with modified properties for potential use in biomedical applications.

  5. Solid state dye lasers based on 2-hydroxyethyl methacrylate and methyl methacrylate co-polymers

    NASA Astrophysics Data System (ADS)

    Giffin, Shirin M.; McKinnie, Iain T.; Wadsworth, William J.; Woolhouse, Anthony D.; Smith, Gerald J.; Haskell, Tim G.

    1999-03-01

    The laser performance of a range of solid state dye lasers based on rhodamine 590-doped co-polymers of 2-hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) has been investigated. The optimisation of preparation conditions, including polymerisation initiator and solvent for dye delivery is discussed in detail. Laser efficiency is compared for different polymeric hosts and dye concentrations with a range of output couplers, cavity lengths and repetition rates. Passive and dynamic loss have been determined for each host medium. Laser efficiencies of optimised polymers are among the highest reported for rhodamine 590-doped solid state dye lasers under these operating conditions. Highest slope efficiency of 35% and lowest threshold fluence of 0.06 J cm -2 were obtained with dimethyl sulphoxide (DMSO) additive in MPMMA at 10 Hz repetition rate.

  6. Solid-supported block copolymer membranes through interfacial adsorption of charged block copolymer vesicles.

    PubMed

    Rakhmatullina, Ekaterina; Meier, Wolfgang

    2008-06-17

    The properties of amphiphilic block copolymer membranes can be tailored within a wide range of physical parameters. This makes them promising candidates for the development of new (bio)sensors based on solid-supported biomimetic membranes. Here we investigated the interfacial adsorption of polyelectrolyte vesicles on three different model substrates to find the optimum conditions for formation of planar membranes. The polymer vesicles were made from amphiphilic ABA triblock copolymers with short, positively charged poly(2,2-dimethylaminoethyl methacrylate) (PDMAEMA) end blocks and a hydrophobic poly( n-butyl methacrylate) (PBMA) middle block. We observed reorganization of the amphiphilic copolymer chains from vesicular structures into a 1.5+/-0.04 nm thick layer on the hydrophobic HOPG surface. However, this film starts disrupting and dewetting upon drying. In contrast, adsorption of the vesicles on the negatively charged SiO2 and mica substrates induced vesicle fusion and formation of planar, supported block copolymer films. This process seems to be controlled by the surface charge density of the substrate and concentration of the block copolymers in solution. The thickness of the copolymer membrane on mica was comparable to the thickness of phospholipid bilayers.

  7. Synthesis and applications of shell cross-linked thermoresponsive hybrid micelles based on poly(N-isopropylacrylamide-co-3-(trimethoxysilyl)propyl methacrylate)-b-poly(methyl methacrylate).

    PubMed

    Wei, Hua; Cheng, Cheng; Chang, Cong; Chen, Wen-Qin; Cheng, Si-Xue; Zhang, Xian-Zheng; Zhuo, Ren-Xi

    2008-05-06

    Shell cross-linked (SCL) thermoresponsive hybrid micelles consisting of a cross-linked thermoresponsive hybrid hydrophilic shell and a hydrophobic core domain were synthesized from poly(N-isopropylacrylamide-co-3- (trimethoxysilyl)propyl methacrylate)-b-polymethyl methacrylate (P(NIPAAm-co-MPMA)-b-PMMA) amphiphilic block copolymers. Transmission electron microscopy (TEM) images showed that the SCL micelles formed regularly globular nanoparticles. The SCL micelles showed reversible dispersion/aggregation in response to temperature cycles through an outer polymer shell lower critical solution temperature (LCST) for PNIPAAm at around 33 degrees C, observed by turbidity measurements and dynamic light scattering (DLS). The drug loading and in vitro drug release properties of the SCL micelles bearing a silica-reinforced PNIPAAm shell were further studied, which showed that the SCL micelles exhibited a much improved entrapment efficiency (EE) as well as a slower release rate which allowed the entrapped molecules to be slowly released over a much longer period of time as compared with pure PNIPAAm-b-PMMA micelles.

  8. Nonviral Plasmid DNA Carriers Based on N,N'-Dimethylaminoethyl Methacrylate and Di(ethylene glycol) Methyl Ether Methacrylate Star Copolymers.

    PubMed

    Mendrek, Barbara; Sieroń, Łukasz; Żymełka-Miara, Iwona; Binkiewicz, Paulina; Libera, Marcin; Smet, Mario; Trzebicka, Barbara; Sieroń, Aleksander L; Kowalczuk, Agnieszka; Dworak, Andrzej

    2015-10-12

    Star polymers with random and block copolymer arms made of cationic N,N'-dimethylaminoethyl methacrylate (DMAEMA) and nonionic di(ethylene glycol) methyl ether methacrylate (DEGMA) were synthesized via atom transfer radical polymerization (ATRP) and used for the delivery of plasmid DNA in gene therapy. All stars were able to form polyplexes with plasmid DNA. The structure and size of the polyplexes were precisely determined using light scattering and cryo-TEM microscopy. The hydrodynamic radius of a complex of DNA with star was dependent on the architecture of the star arms, the DEGMA content and the number of amino groups in the star compared to the number of phosphate groups of the nucleic acid (N/P ratio). The smallest polyplexes (Rh90°∼50 nm) with positive zeta potentials (∼15 mV) were formed of stars with N/P=6. The introduction of DEGMA into the star structure caused a decrease of polyplex cytotoxicity in comparison to DMAEMA homopolymer stars. The overall transfection efficiency using HT-1080 cells showed that the studied systems are prospective gene delivery agents. The most promising results were obtained for stars with random copolymer arms of high DEGMA content.

  9. Genotoxicity and cytotoxicity of 2-hydroxyethyl methacrylate.

    PubMed

    Pawlowska, Elzbieta; Poplawski, Tomasz; Ksiazek, Dominika; Szczepanska, Joanna; Blasiak, Janusz

    2010-02-01

    Resin-based methacrylate materials are widely used in restorative dentistry. They are viscous substances that are converted into solid material via polymerization. This process, however, may be incomplete, leading to the release of monomers into the oral cavity and the pulp, which can be reached through the dentin micro-channels. This opens the opportunity for the monomers to reach the bloodstream. Monomers can reach concentrations in the millimolar range, high enough to cause cellular damage, so it is justified to study their potential toxic effects. In the present work we investigated the cytotoxicity and genotoxicity of 2-hydroxyethyl methacrylate (HEMA) in human peripheral blood lymphocytes and A549 lung-tumour cells. HEMA at concentrations up to 10mM neither affected the viability of the cells nor interacted with isolated plasmid DNA during a 1h exposure. However, HEMA induced concentration-dependent DNA damage in lymphocytes, as assessed by alkaline and pH 12.1 versions of the comet assay. HEMA did not cause double-strand breaks, as assessed by the neutral version of the comet assay and pulsed-field gel electrophoresis. The use of DNA repair enzymes, spin traps and vitamin C produced results suggesting that HEMA induced oxidative modifications to DNA bases. DNA damage caused by HEMA at 10mM was removed within 120min. HEMA induced apoptosis in a concentration-dependent manner and caused cell-cycle delay at the G0/G1-checkpoint. Methylglycol chitosan displayed a protective effect against the DNA-damaging action of HEMA. The results obtained in this study suggest that HEMA induces adverse biological effects, mainly via reactive oxygen species, which can lead to DNA damage, apoptosis and cell-cycle delay. Chitosan and its derivatives can be considered as additional components of dental restoration to decrease the harmful potency of HEMA.

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

    PubMed

    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.

  11. Neuromuscular block

    PubMed Central

    Bowman, W C

    2006-01-01

    Descriptions of the South American arrow poisons known as curares were reported by explorers in the 16th century, and their site of action in producing neuromuscular block was determined by Claude Bernard in the mid-19th century. Tubocurarine, the most important curare alkaloid, played a large part in experiments to determine the role of acetylcholine in neuromuscular transmission, but it was not until after 1943 that neuromuscular blocking drugs became established as muscle relaxants for use during surgical anaesthesia. Tubocurarine causes a number of unwanted effects, and there have been many attempts to replace it. The available drugs fall into two main categories: the depolarising blocking drugs and the nondepolarising blocking drugs. The former act by complex mixed actions and are now obsolete with the exception of suxamethonium, the rapid onset and brief duration of action of which remain useful for intubation at the start of surgical anaesthesia. The nondepolarising blocking drugs are reversible acetylcholine receptor antagonists. The main ones are the atracurium group, which possess a built-in self-destruct mechanism that makes them especially useful in kidney or liver failure, and the vecuronium group, which are especially free from unwanted side effects. Of this latter group, the compound rocuronium is of especial interest because its rapid onset of action allows it to be used for intubation, and there is promise that its duration of action may be rapidly terminated by a novel antagonist, a particular cyclodextrin, that chelates the drug, thereby removing it from the acetylcholine receptors. PMID:16402115

  12. Neuromuscular block.

    PubMed

    Bowman, W C

    2006-01-01

    Descriptions of the South American arrow poisons known as curares were reported by explorers in the 16th century, and their site of action in producing neuromuscular block was determined by Claude Bernard in the mid-19th century. Tubocurarine, the most important curare alkaloid, played a large part in experiments to determine the role of acetylcholine in neuromuscular transmission, but it was not until after 1943 that neuromuscular blocking drugs became established as muscle relaxants for use during surgical anaesthesia. Tubocurarine causes a number of unwanted effects, and there have been many attempts to replace it. The available drugs fall into two main categories: the depolarising blocking drugs and the nondepolarising blocking drugs. The former act by complex mixed actions and are now obsolete with the exception of suxamethonium, the rapid onset and brief duration of action of which remain useful for intubation at the start of surgical anaesthesia. The nondepolarising blocking drugs are reversible acetylcholine receptor antagonists. The main ones are the atracurium group, which possess a built-in self-destruct mechanism that makes them specially useful in kidney or liver failure, and the vecuronium group, which are specially free from unwanted side effects. Of this latter group, the compound rocuronium is of special interest because its rapid onset of action allows it to be used for intubation, and there is promise that its duration of action may be rapidly terminated by a novel antagonist, a particular cyclodextrin, that chelates the drug, thereby removing it from the acetylcholine receptors.

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

    PubMed Central

    Figueiredo, Andrea G. P. R.; Figueiredo, Ana R. P.; Alonso-Varona, Ana; Fernandes, Susana C. M.; Palomares, Teodoro; Rubio-Azpeitia, Eva; Barros-Timmons, Ana; Silvestre, Armando J. D.; Pascoal Neto, Carlos; 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(2-hydroxyethyl methacrylate) (PHEMA). Finally, BC/PHEMA nanocomposites proved to be nontoxic to human adipose-derived mesenchymal stem cells (ADSCs) and thus are pointed as potential dry dressings for biomedical applications. PMID:24093101

  14. Biocompatible bacterial cellulose-poly(2-hydroxyethyl methacrylate) nanocomposite films.

    PubMed

    Figueiredo, Andrea G P R; Figueiredo, Ana R P; Alonso-Varona, Ana; Fernandes, Susana C M; Palomares, Teodoro; Rubio-Azpeitia, Eva; Barros-Timmons, Ana; Silvestre, Armando J D; Pascoal Neto, Carlos; 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(2-hydroxyethyl methacrylate) (PHEMA). Finally, BC/PHEMA nanocomposites proved to be nontoxic to human adipose-derived mesenchymal stem cells (ADSCs) and thus are pointed as potential dry dressings for biomedical applications.

  15. Quaternary ammonium poly(diethylaminoethyl methacrylate) possessing antimicrobial activity.

    PubMed

    Farah, Shady; Aviv, Oren; Laout, Natalia; Ratner, Stanislav; Beyth, Nurit; Domb, Abraham J

    2015-04-01

    Quaternary ammonium (QA) methacrylate monomers and polymers were synthesized from a N-alkylation of N,N-diethylaminoethyl methacrylate (DEAEM) monomer. Linear copolymers, and for the first time reported crosslinked nanoparticles (NPs), based QA-PDEAEM were prepared by radical polymerization of the quaternized QA-DEAEM monomers with either methyl methacrylate (MMA) or a divinyl monomer. QA-PDEAEM NPs of 50-70 nm were embedded in polyethylene vinyl acetate coating. QA-polymers with N-C8 and N-C18 alkyl chains and copolymers with methyl methacrylate were prepared at different molar ratios and examined for their antimicrobial effectiveness. These coatings exhibited strong antibacterial activity against four representative Gram-positive and Gram-negative bacteria.

  16. Photodynamics and time-resolved fluorescence of azobenzene in solution: a mixed quantum-classical simulation.

    PubMed

    Cusati, Teresa; Granucci, Giovanni; Persico, Maurizio

    2011-04-06

    We have simulated the photodynamics of azobenzene by means of the Surface Hopping method. We have considered both the trans → cis and the cis → trans processes, caused by excitation in the n → π* band (S(1) state). To bring out the solvent effects on the excited state dynamics, we have run simulations in four different environments: in vacuo, in n-hexane, in methanol, and in ethylene glycol. Our simulations reproduce very well the measured quantum yields and the time dependence of the intensity and anisotropy of the transient fluorescence. Both the photoisomerization and the S(1) → S(0) internal conversion require the torsion of the N═N double bond, but the N-C bond rotations and the NNC bending vibrations also play a role. In the trans → cis photoconversion the N═N torsional motion and the excited state decay are delayed by increasing the solvent viscosity, while the cis → trans processes are less affected. The analysis of the simulation results allows the experimental observations to be explained in detail, and in particular the counterintuitive increase of the trans → cis quantum yield with viscosity, as well as the relationship between the excited state dynamics and the solvent effects on the fluorescence lifetimes and depolarization.

  17. Photoisomerization dynamics of azobenzene in solution with S1 excitation: a femtosecond fluorescence anisotropy study.

    PubMed

    Chang, Chih-Wei; Lu, Ying-Chih; Wang, Tsai-Te; Diau, Eric Wei-Guang

    2004-08-18

    Measurements of anisotropy of femtosecond fluorescence after direct excitation of the S1(n,pi*) state of azobenzene in hexane and ethylene glycol solutions have been carried out to address the controversy about inversion and rotation in the mechanism of photoisomerization. The observed anisotropies in hexane decay to a nonzero asymptotic level with a relaxation period the same as that for slow decay of the corresponding biexponential transient; this effect is attributed to involvement of the out-of-plane CNNC-torsional motion on approach to a twisted conical intersection along the "rotation channel" that depolarizes the original in-plane transition moment. In contrast, when the rotational channel becomes substantially hindered in ethylene glycol, the anisotropies show no discernible decay feature, but the corresponding transients show prominent decays attributed to involvement of in-plane symmetric motions; the latter approach a planar-sloped conical intersection along a "concerted inversion channel" for efficient internal conversion through vibronic coupling. The proposed mechanism is consistent with theoretical calculations and rationalizes both results on quantum yields and ultrafast observations.

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

    NASA Astrophysics Data System (ADS)

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

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

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

    PubMed Central

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

    2015-01-01

    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 Ca2+-imaging reports on 2P photoswitching in multiple cells with high temporal resolution. The combination of electrophysiology or Ca2+ imaging with 2P activation by optical wavefront shaping should make second generation PTL-controlled receptors suitable for studies of intact neural circuits. PMID:25653339

  20. Conformal Electroplating of Azobenzene-Based Solar Thermal Fuels onto Large-Area and Fiber Geometries.

    PubMed

    Zhitomirsky, David; Grossman, Jeffrey C

    2016-10-05

    There is tremendous growth in fields where small functional molecules and colloidal nanomaterials are integrated into thin films for solid-state device applications. Many of these materials are synthesized in solution and there often exists a significant barrier to transition them into the solid state in an efficient manner. Here, we develop a methodology employing an electrodepositable copolymer consisting of small functional molecules for applications in solar energy harvesting and storage. We employ azobenzene solar thermal fuel polymers and functionalize them to enable deposition from low concentration solutions in methanol, resulting in uniform and large-area thin films. This approach enables conformal deposition on a variety of conducting substrates that can be either flat or structured depending on the application. Our approach further enables control over film growth via electrodepsition conditions and results in highly uniform films of hundreds of nanometers to microns in thickness. We demonstrate that this method enables superior retention of solar thermal fuel properties, with energy densities of ∼90 J/g, chargeability in the solid state, and exceptional materials utilization compared to other solid-state processing approaches. This novel approach is applicable to systems such as photon upconversion, photovoltaics, photosensing, light emission, and beyond, where small functional molecules enable solid-state applications.

  1. Synthesis of organic-inorganic hybrid azobenzene materials for the preparation of nanofibers by electrospinning

    NASA Astrophysics Data System (ADS)

    Bućko, Aleksandra; Zielińska, Sonia; Ortyl, Ewelina; Larkowska, Maria; Barille, Regis

    2014-12-01

    The new photochromic hybrid materials containing different mole fractions of highly photoactive 4-[(E)-[4-[ethyl(2-hydroxyethyl)amino]phenyl]azo]-N-(4-methylpyrimidin-2-yl)benzenesulfonamide (SMERe) were prepared by a low temperature sol-gel process. The guest-host systems with triethoxyphenylsilane matrix were obtained. These materials were used to form thin transparent films by a spin-coating technique. Then the ability of thin hybrid films to reversible trans-cis photoisomerization under illumination was investigated using ellipsometry and UV-Vis spectroscopy. The reversible changes of refractive index of the films under illumination were in the range of 0.005-0.056. The maximum absorption of these materials was located at 462-486 nm. Moreover, the organic-inorganic azobenzene materials were used to form nanofibers by electrospinning using various parameters of the process. The microstructure of electrospun fibers depended on sols properties (e.g. concentration and viscosity of the sols) and process conditions (e.g. the applied voltage, temperature or type of the collector) at ambient conditions. The morphology of obtained nanofibers was analyzed by an optical microscopy and scanning electron microscopy. In most instances, the beadless fibers were obtained. The wettability of the surface of electrospun fibers deposited on glass substrates was investigated.

  2. Size Switchable Supramolecular Nanoparticle Based on Azobenzene Derivative within Anionic Pillar[5]arene

    PubMed Central

    Zhang, Cai-Cai; Li, Sheng-Hua; Zhang, Cui-Fang; Liu, Yu

    2016-01-01

    A photo/thermal-switchable supramolecular nanoparticles assembly has been constructed based on an inclusion complex between anionic pillar[5]arene 2C-WP5A and azobenzene derivative Azo-py-OMe (G). The novel anionic pillar[5]arene-based host-guest inclusion complexation was investigated by the 1H NMR titration, 2D ROESY and isothermal titration microcalorimetry (ITC) showing high association constant (Ka) of (2.60 ± 0.06) × 104 M−1 with 1:1 binding stoichiometry. Furthermore, the supramolecular nanoparticles assembly can be conveniently obtained from G and a small amount of 2C-WP5A in aqueous solution, which was so-called “host induced aggregating (HIA)”. The size and morphology of the supramolecular nanoparticles assembly were characterized by TEM and DLS. As a result of the photo/thermal-isomerization of G included in the cavity of 2C-WP5A, the size of these nanoparticles could reversibly change from ~800 nm to ~250 nm, which could switch the solution of this assembly from turbid to clear. PMID:27849055

  3. Size Switchable Supramolecular Nanoparticle Based on Azobenzene Derivative within Anionic Pillar[5]arene

    NASA Astrophysics Data System (ADS)

    Zhang, Cai-Cai; Li, Sheng-Hua; Zhang, Cui-Fang; Liu, Yu

    2016-11-01

    A photo/thermal-switchable supramolecular nanoparticles assembly has been constructed based on an inclusion complex between anionic pillar[5]arene 2C-WP5A and azobenzene derivative Azo-py-OMe (G). The novel anionic pillar[5]arene-based host-guest inclusion complexation was investigated by the 1H NMR titration, 2D ROESY and isothermal titration microcalorimetry (ITC) showing high association constant (Ka) of (2.60 ± 0.06) × 104 M‑1 with 1:1 binding stoichiometry. Furthermore, the supramolecular nanoparticles assembly can be conveniently obtained from G and a small amount of 2C-WP5A in aqueous solution, which was so-called “host induced aggregating (HIA)”. The size and morphology of the supramolecular nanoparticles assembly were characterized by TEM and DLS. As a result of the photo/thermal-isomerization of G included in the cavity of 2C-WP5A, the size of these nanoparticles could reversibly change from ~800 nm to ~250 nm, which could switch the solution of this assembly from turbid to clear.

  4. Azobenzene-based photomechanical monolayers as light-addressable nano-engineered structures.

    NASA Astrophysics Data System (ADS)

    Dahdah, J. M.; Furtak, T. E.; Walba, D. M.; Fang, G.; Yi, Y.; Maclennan, J. E.; Clark, N. A.

    2007-03-01

    Azobenzene-based photomechanical monolayers have received a great deal of attention for their potential as platforms for light-addressable nano-engineered structures in bioscience, photonics, and display technologies. We have developed an aminoazobenzene material (d-MR), derived from methyl red, which forms high-quality, covalently anchored monolayers on glass. These monolayers demonstrate unusually high sensitivity to polarized light, which controls the molecular orientation distribution through optical anisotropy of the trans-cis isomerization. In an effort to understand and optimize this phenomenon we are studying the influence of the two-dimensional molecular field on the dynamics of the light-driven reorganization. We have correlated the behavior of d-MR monolayers, as determined by spectral studies of dichroism and differential reflection ellipsometry, to dilute solutions of d-MR in a variety of solvents, as characterized by absorption cross sections, quantum yields, and characteristic time constants. The resulting information has helped to clarify the details of how these molecules respond to light leading to design strategies for even higher performing monolayers.

  5. Methacrylate-based monolithic layers for planar chromatography of polymers.

    PubMed

    Maksimova, E F; Vlakh, E G; Tennikova, T B

    2011-04-29

    A series of macroporous monolithic methacrylate-based materials was synthesized by in situ free radical UV-initiated copolymerization of functional monomers, such as glycidyl methacrylate (GMA), butyl methacrylate (BuMA), 2-aminoethyl methacrylate (AEMA), 2-hydroxyethyl methacrylate (HEMA) and 2-cyanoethyl methacrylate (CEMA), with crosslinking agent, namely, ethylene glycol dimethacrylate (EDMA). The materials obtained were applied as the stationary phases in simple and robust technique - planar chromatography (PLC). The method of separation layer fabrication representing macroporous polymer monolith bound to the specially prepared glass surface was developed and optimized. The GMA-EDMA and BuMA-EDMA matrixes were successfully applied for the separation of low molecular weight compounds (the mixture of several dies), as well as poly(vinylpyrrolidone) and polystyrene homopolymers of different molecular weights using reversed-phase mechanism. The materials based on copolymers AEMA-HEMA-EDMA and CEMA-HEMA-EDMA were used for normal-phase PLC separation of 2,4-dinitrophenyl amino acids and polystyrene standards.

  6. Photo-tuning of lasing from a dye-doped cholesteric liquid crystals by photoisomerization of a sugar derivative having plural azobenzene groups

    NASA Astrophysics Data System (ADS)

    Kurihara, Seiji; Hatae, Yohko; Yoshioka, Teppei; Moritsugu, Masaki; Ogata, Tomonari; Nonaka, Takamasa

    2006-03-01

    Cholesteric liquid crystal (Ch LC) was prepared by mixing a nematic LC, a sugar derivative having plural azobenzene substituents, and a laser dye. Laser emission from the dye-doped Ch LC was observed at the longer edge of the selective reflection band of the Ch LC. Reversible change in the helical pitch of the Ch LC was caused by the trans-cis photoisomerization of the sugar derivative having plural azobenzene substituents. According to the change in the helical pitch of the Ch LC, the lasing properties were simultaneously affected by the UV and visible light irradiation; laser emission wavelength, intensity, singlemode-multimode.

  7. Bound excitons and many-body effects in x-ray absorption spectra of azobenzene-functionalized self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Cocchi, Caterina; Draxl, Claudia

    2015-11-01

    We study x-ray absorption spectra of azobenzene-functionalized self-assembled monolayers (SAMs), investigating excitations from the nitrogen K edge. Azobenzene with H-termination and functionalized with CF3 groups is considered. The Bethe-Salpeter equation is employed to compute the spectra, including excitonic effects, and to determine the character of the near-edge resonances. Our results indicate that core-edge excitations are intense and strongly bound: their binding energies range from about 6 to 4 eV, going from isolated molecules to densely-packed SAMs. Electron-hole correlation rules these excitations, while the exchange interaction plays a negligible role.

  8. Thermally Switchable Thin Films of an ABC Triblock Copolymer of Poly(n-butyl methacrylate)-poly(methyl methacrylate)-poly(2-fluoroethyl methacrylate)

    SciTech Connect

    Zhang, Shanju; Liu, Zhan; Bucknall, David G.; He, Lihong; Hong, Kunlun; Mays, Jimmy; Allen, Mark

    2011-01-01

    The thermo-responsive behavior of polymer films consisting of novel linear triblock copolymers of poly(n-butyl methacrylate)-poly(methyl methacrylate)-poly(2-fluoroethyl methacrylate) (PnBuMA-PMMA-P2FEMA) are reported using differential scanning calorimetry (DSC), atomic forcing microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and contacting angle (CA) measurements. The surface morphology, wettability and chemical structure of thin films of these triblock copolymers on silicon wafers as a function of temperature have been investigated. It has been shown that the wettability of the films is thermally switchable. Detailed structural analysis shows that thermo-responsive surface composition changes are produced. The underlying mechanism of the thermoresponsive behavior is discussed.

  9. Thermally switchable thin films of an ABC triblock copolymer of poly( n -butyl methacrylate)-poly(methyl methacrylate)-poly(2-fluoroethyl methacrylate)

    NASA Astrophysics Data System (ADS)

    Zhang, Shanju; Liu, Zhan; Bucknall, David G.; He, Lihong; Hong, Kunlun; Mays, Jimmy W.; Allen, Mark G.

    2011-09-01

    The thermo-responsive behavior of polymer films consisting of novel linear triblock copolymers of poly( n-butyl methacrylate)-poly(methyl methacrylate)-poly(2-fluoroethyl methacrylate) (PnBuMA-PMMA-P2FEMA) are reported using differential scanning calorimetry (DSC), atomic forcing microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and contacting angle (CA) measurements. The surface morphology, wettability and chemical structure of thin films of these triblock copolymers on silicon wafers as a function of temperature have been investigated. It has been shown that the wettability of the films is thermally switchable. Detailed structural analysis shows that thermo-responsive surface composition changes are produced. The underlying mechanism of the thermoresponsive behavior is discussed.

  10. Chlorhexidine-releasing methacrylate dental composite materials.

    PubMed

    Leung, Danny; Spratt, David A; Pratten, Jonathan; Gulabivala, Kishor; Mordan, Nicola J; Young, Anne M

    2005-12-01

    Light curable antibacterial, dental composite restoration materials, consisting of 80 wt% of a strontium fluoroaluminosilicate glass dispersed in methacrylate monomers have been produced. The monomers contained 40-100 wt% of a 10 wt% chlorhexidine diacetate (CHXA) in hydroxyethylmethacrylate (HEMA) solution and 60-0 wt% of a 50/50 mix of urethane dimethacrylate (UDMA) and triethyleneglycol dimethacrylate (TEGDMA). On raising HEMA content, light cure polymerisation rates decreased. Conversely, water sorption induced swelling and rates of diffusion controlled CHXA release from the set materials increased. Experimental composites with 50 and 90 wt% of the CHXA in HEMA solution in the monomer were shown, within a constant depth film fermentor (CDFF), to have slower rates of biofilm growth on their surfaces between 1 and 7 days than the commercial dental composite Z250 or fluoride-releasing dental cements, Fuji II LC and Fuji IX. When an excavated bovine dentine cylinder re-filled with Z250 was placed for 10 weeks in the CDFF, both bacteria and polymers from the artificial saliva penetrated between the material and dentine. With the 50 wt% experimental HEMA/CHXA formulation, this bacterial microleakage was substantially reduced. Polymer leakage, however, still occurred. Both polymer and bacterial microleakage were prevented with a 90 wt% HEMA/CHXA restoration in the bovine dentine due to swelling compensation for polymerisation shrinkage in combination with antibacterial release.

  11. Furfuryl methacrylate plasma polymers for biomedical applications.

    PubMed

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

    2016-09-08

    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.

  12. Photoresponsive azo-doped aerosil/7CB nematic nanocomposites: the effect from concentration of the azobenzene photoactive agent

    NASA Astrophysics Data System (ADS)

    Hadjichristov, G. B.; Marinov, Y. G.; Petrov, A. G.; Prasad, S. K.

    2017-01-01

    We studied nanomaterials composed from 3 wt.% aerosil nanospheres and the room-temperature nematic liquid crystal 4-n-heptyl cyanobiphenyl (7CB), as doped with the photoactive liquid crystal 4-(4'-ethoxyphenylazo)phenyl hexanoate (EPH). The molecules of the azobenzene photoactive agent EPH were included at concentration ranging from 1 wt.% to 10 wt.%. The object of our interest is the effect of the EPH amount on the photosensitized electro-optical properties of thin films of aerosil/7CB/EPH nematic nanocomposites.

  13. COOH-terminated SAMs on Gold Fabricated from an Azobenzene Derivative with a 1,2-dithiolane Headgroup

    SciTech Connect

    Siemeling, U.; Rittinghaus, S; Weidner, T; Brison, J; Castner, D

    2010-01-01

    Well-defined and homogeneous, contamination-free self-assembled monolayers (SAMs) were fabricated by the chemisorption of lip-NH-p-C{sub 6}H{sub 4}-N {double_bond} N-p-C{sub 6}H{sub 4}-COOH (lip = {alpha}-lipoyl) onto gold. This adsorbate species is composed of a 1,2-dithiolane-based headgroup, an azobenzene-based (and hence photochromic) spacer unit and a carboxylic acid functional group. The SAM constituents are covalently attached to the substrate by the bidentate thiolate anchor groups and exhibit a strongly tilted binding configuration.

  14. Excited-state Raman spectroscopy with and without actinic excitation: S{sub 1} Raman spectra of trans-azobenzene

    SciTech Connect

    Dobryakov, A. L.; Quick, M.; Ioffe, I. N.; Granovsky, A. A.; Ernsting, N. P.; Kovalenko, S. A.

    2014-05-14

    We show that femtosecond stimulated Raman spectroscopy can record excited-state spectra in the absence of actinic excitation, if the Raman pump is in resonance with an electronic transition. The approach is illustrated by recording S{sub 1} and S{sub 0} spectra of trans-azobenzene in n-hexane. The S{sub 1} spectra were also measured conventionally, upon nπ* (S{sub 0} → S{sub 1}) actinic excitation. The results are discussed and compared to earlier reports.

  15. Sequence dependent conformations of glycidyl methacrylate/butyl methacrylate copolymers in the gas phase

    NASA Astrophysics Data System (ADS)

    Baker, Erin Shammel; Gidden, Jennifer; Simonsick, William J.; Grady, Michael C.; Bowers, Michael T.

    2004-11-01

    Sequence dependent conformations of a series of glycidyl methacrylate/butyl methacrylate (GMA/BMA) copolymers cationized by sodium were analyzed in the gas phase using ion mobility methods. GMA and BMA have the same nominal mass but vary in exact mass by 0.036 Da (CH4 versus O). Matrix assisted laser desorption/ionization (MALDI) was used to form Na+(GMA/BMA) copolymer ions and their collision cross-sections were measured in helium using ion mobility methods. The copolymer sequences from Na+(GMA/BMA)3 to Na+(GMA/BMA)5 (i.e. for the trimer to the pentamer) were studied. Analysis by molecular mechanics/dynamics indicates that each copolymer (regardless of sequence) forms a ring around the sodium ions due to Na+/oxygen electrostatic interactions. However, the structures vary in size, since the epoxy oxygen atoms in the glycidyl groups are attracted to the sodium ions while the carbon-composed butyl groups are not. This allows copolymers with more GMA segments to fold tighter (more spherically) around the sodium ion and have smaller cross-sections than copolymers with a larger amount of BMA segments in the sequence. Due to this cross-sectional difference, the GMA/BMA sequence compositions of the trimer and tetramer could be quantified.

  16. Characterization of new acrylic bone cement based on methyl methacrylate/1-hydroxypropyl methacrylate monomer.

    PubMed

    Pascual, B; Goñi, I; Gurruchaga, M

    1999-01-01

    New formulations of acrylic bone cement based on methyl methacrylate/1-hydroxypropyl methacrylate (MMA/HPMA) monomers were developed with the purpose of obtaining more ductile materials with reduced polymerization shrinkage. In this way, the ductility of such materials increased, but the introduction of high percentages of the hydrophilic component produced an important decrease in Young's modulus and strength. To ascertain the reason for the deterioration of the tensile parameters, an analysis by scanning electron microscopy of these formulations was carried out; it revealed poor adhesion between the matrix and poly(MMA) beads. We also observed that the polymerization shrinkage increased as the amount of hydrophilic monomer in the formulation decreased, and the 50% (v/v) HPMA modified bone cement compensated for this volume reduction with its water uptake swelling. Measurements taken on the setting time and polymerization exotherm showed a decrease in the former and an increase in the latter, because of the introduction of a more reactive monomer in the bone cement formulation.

  17. Pentablock copolymers of poly(ethylene glycol), poly((2-dimethyl amino)ethyl methacrylate) and poly(2-hydroxyethyl methacrylate) from consecutive atom transfer radical polymerizations for non-viral gene delivery.

    PubMed

    Xu, Fu-Jian; Li, Hongzhe; Li, Jun; Zhang, Zhongxing; Kang, En-Tang; Neoh, Koon-Gee

    2008-07-01

    Well-defined pentablock copolymers (PBPs) of P(HEMA)-b-P(DMAEMA)-b-PEG-b-P(DMAEMA)-b-P(HEMA) (in which PEG=poly(ethylene glycol), P(DMAEMA)=poly((2-dimethyl amino)ethyl methacrylate), and P(HEMA)=poly(2-hydroxyethyl methacrylate)), with different block lengths of P(DMAEMA), for non-viral gene delivery were prepared via consecutive atom transfer radical polymerizations (ATRPs) from the same di-2-bromoisobutyryl-terminated PEG (Br-PEG-Br) center block. The PBPs demonstrate good ability to condense plasmid DNA (pDNA) into 100-160 nm size nanoparticles with positive zeta potentials of 25-35 mV at PBPs/pDNA weight ratios of 5-25. The PBPs exhibit very low in vitro cytotoxicity and excellent gene transfection efficiency in HEK293 and COS7 cells. In particular, the transfection efficiencies of all the PBPs in HEK293 cells are comparable to, or higher than those of polyethylenimine (PEI, 25 kDa) at most weight ratios. The ability of the copolymers to condense plasmid DNA and the transfection efficiency of the resulting complexes are dependent on the chain length of P(DMAEMA) blocks. In addition to reducing the cytotoxicity and increasing the stability of the plasmid complexes, the PEG center block and the short P(HEMA) end blocks also help to enhance the gene transfection efficiency. Thus, the approach to well-defined block copolymers via ATRP provides a versatile means for tailoring the structure of non-viral gene vectors to meet the requirements of low cytotoxicity, good stability and high transfection capability for gene therapy applications.

  18. An all-optical poling investigation of low absorbing azobenzene side-chain polymer films

    NASA Astrophysics Data System (ADS)

    Jia, Yajie; Wang, Gongming; Guo, Bin; Su, Wei; Zhang, Qijin

    2004-09-01

    All optical poling (AOP) processes of both the typical AOP material disperse red 1 (DR1) copolymer and a low absorbing side-chain poly(2-[4-(4-cyanophenylazo)phenoxy] hexyl methacrylate), called PCN6, were examined and compared. The trade-off between the optical seeding efficiency and the transparency of the nonlinear polymer was considered. Quasi-phase matched (QPM) second harmonic generation (SHG) in PCN6 films was demonstrated. A relaxation retardation effect of the photo-induced khgr(2) was also observed in thick PCN6 films.

  19. Preparation and thermo-optic switch properties based on chiral azobenzene-containing polyurethane

    NASA Astrophysics Data System (ADS)

    Ye, Feiyan; Qiu, Fengxian; Yang, Dongya; Cao, Guorong; Guan, Yijun; Zhuang, Lin

    2013-07-01

    A chiral azo chromophore compound 4-(4'-nitro-phenyl-diazenyl)-phenyl-1,2-propanediol ether (NPDPPE) was prepared with p-nitroaniline, phenol and R(-)-3-chloro-1,2-propanediol by the diazo-coupling reaction. Then, the chromophore molecule NPDPPE was polymerized with isophorone diisocyanate (IPDI) to obtain novel chiral azobenzene-containing polyurethane (CACPU). The chemical structures of chromophore molecule and CACPU were characterized by the FT-IR and UV-visible spectroscopy. The physical properties (thermal conductivity, thermal diffusion coefficient, and specific heat capacity) and mechanical properties (tensile strength, elongation at break and hardness) of CACPU thin films were measured. The refractive index and thermo-optic (TO) coefficient (dn/dT) of CACPU thin film was investigated for TE (transversal electric) polarizations by using an attenuated total reflection (ATR) configuration at the wavelengths of 532, 650 and 850 nm. The transmission loss of film was measured using the charge coupled device (CCD) digital imaging devices. A Y-branch switch and Mach-Zehnder interferometer (MZI) thermo-optic switches based on thermo-optic effect were proposed and the performances of switches were simulated. The results showed that the power consumption of the Y-branch thermo-optic switch was only 3.28 mW. The rising and falling times of Y-branch and MZI switches were 12.0 ms and 2.0 ms, respectively. The conclusion has potential significance to improve and develop new Y-branch digital optical switch (DOS), MZI thermo-optic switch, directional coupler (DC) switch and optical modulators.

  20. Enhanced Release of Molecules upon Ultraviolet (UV) Light Irradiation from Photoresponsive Hydrogels Prepared from Bifunctional Azobenzene and Four-Arm Poly(ethylene glycol).

    PubMed

    Rastogi, Shiva K; Anderson, Hailee E; Lamas, Joseph; Barret, Scott; Cantu, Travis; Zauscher, Stefan; Brittain, William J; Betancourt, Tania

    2017-03-07

    Advances in biosensors and drug delivery are dependent on hydrogels that respond to external stimuli. In this work, we describe the preparation and characterization of photoresponsive hydrogels prepared by cross-linking of di-NHS ester of azobenzoic acid and four-armed, amine-terminated poly(ethylene glycol). The porous structure and composition of the hydrogels were confirmed by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy. The reversible photoisomerization of the azobenzene-containing hydrogel cross-linkers in the gels was confirmed by absorption spectroscopy. Specifically, the photoisomerization of the cross-linkers between their trans and cis configurations was observed by monitoring the absorbance of the hydrogels at the two characteristic peaks of azobenzene (π-π* at 330 nm and n-π* at 435 nm). The effect of photoisomerization on the hydrogel structure was investigated by microscopy. Ultraviolet (UV) irradiation-induced reduction in hydrogel size was observed, which may be a result of the inherently smaller footprint of the cis azobenzene conformation, as well as dipole-dipole interactions between the polar cis azobenzene and the polymer network. The UV-triggered reduction in hydrogel size was accompanied by enhanced release of the near-infrared fluorescent dye Alexa Fluor 750 (AF750). Enhanced release of AF750 was observed in samples irradiated with UV versus dark control. Together, these data demonstrate the potential of these systems as reversible photoresponsive biomaterials.

  1. Osteoblast cell death on methacrylate polymers involves apoptosis.

    PubMed

    Gough, J E; Downes, S

    2001-12-15

    The success of an implant depends on the implant-tissue interface. There are many causes of implant failure, one of which is tissue necrosis. The aim of this in vitro study was to determine whether cell death of primary human osteoblasts (implant site specific cells) occurred by apoptosis (a form of programmed cell death) on two methacrylate polymers. Cells were cultured on poly(ethyl methacrylate)/tetrahydrofurfuryl methacrylate and poly(methyl methacrylate in the form of 13-mm discs, in conditioned medium containing leachable monomer and in the presence of various concentrations of monomer itself in the culture medium. It was found that monomer and leached monomer caused apoptosis of human osteoblast cells in this system. Tetrahydrofurfuryl methacrylate monomer was found to be more toxic than currently used monomer methylmethacrylate. Preincubation of polymers in serum containing medium was found to increase the biocompatibility of the polymers. High levels of apoptosis occurred on polymer used directly after polymerization. Apoptosis levels were decreased after polymer was incubated at 60 degrees C overnight or for 3 days. Apoptosis therefore may occur in cells at the implant site in vivo.

  2. A Light-Responsive Self-Assembly Formed by a Cationic Azobenzene Derivative and SDS as a Drug Delivery System

    NASA Astrophysics Data System (ADS)

    Geng, Shengyong; Wang, Yuzhu; Wang, Liping; Kouyama, Tsutomu; Gotoh, Toshiaki; Wada, Satoshi; Wang, Jin-Ye

    2017-01-01

    The structure of a self-assembly formed from a cationic azobenzene derivative, 4-cholesterocarbonyl-4‧-(N,N,N-triethylamine butyloxyl bromide) azobenzene (CAB) and surfactant sodium dodecyl sulfate (SDS) in aqueous solution was studied by cryo-TEM and synchrotron radiation small-angle X-ray scattering (SAXS). Both unilamellar and multilamellar vesicles could be observed. CAB in vesicles were capable to undergo reversible trans-to-cis isomerization upon UV or visible light irradiation. The structural change upon UV light irradiation could be catched by SAXS, which demonstrated that the interlamellar spacing of the cis-multilamellar vesicles increased by 0.2–0.3 nm. Based on this microstructural change, the release of rhodamine B (RhB) and doxorubicin (DOX) could be triggered by UV irradiation. When incubated NIH 3T3 cells and Bel 7402 cells with DOX-loaded CAB/SDS vesicles, UV irradiation induced DOX release decreased the viability of both cell lines significantly compared with the non-irradiated cells. The in vitro experiment indicated that CAB/SDS vesicles had high efficiency to deliver loaded molecules into cells. The in vivo experiment showed that CAB/SDS vesicles not only have high drug delivery efficiency into rat retinas, but also could maintain high drug concentration for a longer time. CAB/SDS catanionic vesicles may find potential applications as a smart drug delivery system for controlled release by light.

  3. Opposite photo-induced deformations in azobenzene-containing polymers with different molecular architecture: Molecular dynamics study

    SciTech Connect

    Ilnytskyi, Jaroslav M.; Neher, Dieter; Saphiannikova, Marina

    2011-07-28

    Photo-induced deformations in azobenzene-containing polymers (azo-polymers) are central to a number of applications, such as optical storage and fabrication of diffractive elements. The microscopic nature of the underlying opto-mechanical coupling is yet not clear. In this study, we address the experimental finding that the scenario of the effects depends on molecular architecture of the used azo-polymer. Typically, opposite deformations in respect to the direction of light polarization are observed for liquid crystalline and amorphous azo-polymers. In this study, we undertake molecular dynamics simulations of two different models that mimic these two types of azo-polymers. We employ hybrid force field modeling and consider only trans-isomers of azobenzene, represented as Gay-Berne sites. The effect of illumination on the orientation of the chromophores is considered on the level of orientational hole burning and emphasis is given to the resulting deformation of the polymer matrix. We reproduce deformations of opposite sign for the two models being considered here and discuss the relevant microscopic mechanisms in both cases.

  4. Sensitivity of photoelectron diffraction to conformational changes of adsorbed molecules: Tetra-tert-butyl-azobenzene/Au(111)

    PubMed Central

    Schuler, A.; Greif, M.; Seitsonen, A. P.; Mette, G.; Castiglioni, L.; Osterwalder, J.; Hengsberger, M.

    2017-01-01

    Electron diffraction is a standard tool to investigate the atomic structure of surfaces, interfaces, and adsorbate systems. In particular, photoelectron diffraction is a promising candidate for real-time studies of structural dynamics combining the ultimate time resolution of optical pulses and the high scattering cross-sections for electrons. In view of future time-resolved experiments from molecular layers, we studied the sensitivity of photoelectron diffraction to conformational changes of only a small fraction of molecules in a monolayer adsorbed on a metallic substrate. 3,3′,5,5′-tetra-tert-butyl-azobenzene served as test case. This molecule can be switched between two isomers, trans and cis, by absorption of ultraviolet light. X-ray photoelectron diffraction patterns were recorded from tetra-tert-butyl-azobenzene/Au(111) in thermal equilibrium at room temperature and compared to patterns taken in the photostationary state obtained by exposing the surface to radiation from a high-intensity helium discharge lamp. Difference patterns were simulated by means of multiple-scattering calculations, which allowed us to determine the fraction of molecules that underwent isomerization. PMID:28217715

  5. Opposite photo-induced deformations in azobenzene-containing polymers with different molecular architecture: Molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Ilnytskyi, Jaroslav M.; Neher, Dieter; Saphiannikova, Marina

    2011-07-01

    Photo-induced deformations in azobenzene-containing polymers (azo-polymers) are central to a number of applications, such as optical storage and fabrication of diffractive elements. The microscopic nature of the underlying opto-mechanical coupling is yet not clear. In this study, we address the experimental finding that the scenario of the effects depends on molecular architecture of the used azo-polymer. Typically, opposite deformations in respect to the direction of light polarization are observed for liquid crystalline and amorphous azo-polymers. In this study, we undertake molecular dynamics simulations of two different models that mimic these two types of azo-polymers. We employ hybrid force field modeling and consider only trans-isomers of azobenzene, represented as Gay-Berne sites. The effect of illumination on the orientation of the chromophores is considered on the level of orientational hole burning and emphasis is given to the resulting deformation of the polymer matrix. We reproduce deformations of opposite sign for the two models being considered here and discuss the relevant microscopic mechanisms in both cases.

  6. Sensitivity of photoelectron diffraction to conformational changes of adsorbed molecules: Tetra-tert-butyl-azobenzene/Au(111).

    PubMed

    Schuler, A; Greif, M; Seitsonen, A P; Mette, G; Castiglioni, L; Osterwalder, J; Hengsberger, M

    2017-01-01

    Electron diffraction is a standard tool to investigate the atomic structure of surfaces, interfaces, and adsorbate systems. In particular, photoelectron diffraction is a promising candidate for real-time studies of structural dynamics combining the ultimate time resolution of optical pulses and the high scattering cross-sections for electrons. In view of future time-resolved experiments from molecular layers, we studied the sensitivity of photoelectron diffraction to conformational changes of only a small fraction of molecules in a monolayer adsorbed on a metallic substrate. 3,3',5,5'-tetra-tert-butyl-azobenzene served as test case. This molecule can be switched between two isomers, trans and cis, by absorption of ultraviolet light. X-ray photoelectron diffraction patterns were recorded from tetra-tert-butyl-azobenzene/Au(111) in thermal equilibrium at room temperature and compared to patterns taken in the photostationary state obtained by exposing the surface to radiation from a high-intensity helium discharge lamp. Difference patterns were simulated by means of multiple-scattering calculations, which allowed us to determine the fraction of molecules that underwent isomerization.

  7. A Light-Responsive Self-Assembly Formed by a Cationic Azobenzene Derivative and SDS as a Drug Delivery System

    PubMed Central

    Geng, Shengyong; Wang, Yuzhu; Wang, Liping; Kouyama, Tsutomu; Gotoh, Toshiaki; Wada, Satoshi; Wang, Jin-Ye

    2017-01-01

    The structure of a self-assembly formed from a cationic azobenzene derivative, 4-cholesterocarbonyl-4′-(N,N,N-triethylamine butyloxyl bromide) azobenzene (CAB) and surfactant sodium dodecyl sulfate (SDS) in aqueous solution was studied by cryo-TEM and synchrotron radiation small-angle X-ray scattering (SAXS). Both unilamellar and multilamellar vesicles could be observed. CAB in vesicles were capable to undergo reversible trans-to-cis isomerization upon UV or visible light irradiation. The structural change upon UV light irradiation could be catched by SAXS, which demonstrated that the interlamellar spacing of the cis-multilamellar vesicles increased by 0.2–0.3 nm. Based on this microstructural change, the release of rhodamine B (RhB) and doxorubicin (DOX) could be triggered by UV irradiation. When incubated NIH 3T3 cells and Bel 7402 cells with DOX-loaded CAB/SDS vesicles, UV irradiation induced DOX release decreased the viability of both cell lines significantly compared with the non-irradiated cells. The in vitro experiment indicated that CAB/SDS vesicles had high efficiency to deliver loaded molecules into cells. The in vivo experiment showed that CAB/SDS vesicles not only have high drug delivery efficiency into rat retinas, but also could maintain high drug concentration for a longer time. CAB/SDS catanionic vesicles may find potential applications as a smart drug delivery system for controlled release by light. PMID:28051069

  8. A Light-Responsive Self-Assembly Formed by a Cationic Azobenzene Derivative and SDS as a Drug Delivery System.

    PubMed

    Geng, Shengyong; Wang, Yuzhu; Wang, Liping; Kouyama, Tsutomu; Gotoh, Toshiaki; Wada, Satoshi; Wang, Jin-Ye

    2017-01-04

    The structure of a self-assembly formed from a cationic azobenzene derivative, 4-cholesterocarbonyl-4'-(N,N,N-triethylamine butyloxyl bromide) azobenzene (CAB) and surfactant sodium dodecyl sulfate (SDS) in aqueous solution was studied by cryo-TEM and synchrotron radiation small-angle X-ray scattering (SAXS). Both unilamellar and multilamellar vesicles could be observed. CAB in vesicles were capable to undergo reversible trans-to-cis isomerization upon UV or visible light irradiation. The structural change upon UV light irradiation could be catched by SAXS, which demonstrated that the interlamellar spacing of the cis-multilamellar vesicles increased by 0.2-0.3 nm. Based on this microstructural change, the release of rhodamine B (RhB) and doxorubicin (DOX) could be triggered by UV irradiation. When incubated NIH 3T3 cells and Bel 7402 cells with DOX-loaded CAB/SDS vesicles, UV irradiation induced DOX release decreased the viability of both cell lines significantly compared with the non-irradiated cells. The in vitro experiment indicated that CAB/SDS vesicles had high efficiency to deliver loaded molecules into cells. The in vivo experiment showed that CAB/SDS vesicles not only have high drug delivery efficiency into rat retinas, but also could maintain high drug concentration for a longer time. CAB/SDS catanionic vesicles may find potential applications as a smart drug delivery system for controlled release by light.

  9. Fabrication of carbohydrate microarrays on a poly(2-hydroxyethyl methacrylate)-based photoactive substrate.

    PubMed

    Sundhoro, Madanodaya; Wang, Hui; Boiko, Scott T; Chen, Xuan; Jayawardena, H Surangi N; Park, JaeHyeung; Yan, Mingdi

    2016-01-21

    We report the fabrication of carbohydrate microarrays on a photoactive polymer, poly(HEMA-co-HEMA-PFPA), synthesized by RAFT copolymerization of 2-hydroxyethyl methacrylate (HEMA) and perfluorophenyl azide (PFPA)-derivatized HEMA (HEMA-PFPA). PFPA allows the covalent immobilization of carbohydrates whereas the HEMA polymer provides an antifouling surface, thus the microarrays can be used directly without pretreating the array with a blocking agent. The microarrays were prepared by spin-coating the polymer followed by printing the carbohydrates. Subsequent irradiation simultaneously immobilized the carbohydrates and crosslinked the polymer matrix. The obtained 3D carbohydrate microarrays showed enhanced fluorescence signals upon treating with a fluorescent lectin in comparison with a 2D microarray. The signals were acquired at a lower lectin concentration and a shorter incubation time. When treated with E. coli bacteria, the carbohydrate microarray showed results that were consistent with their binding patterns.

  10. Amphiphilic block copolymer-based photonic platform towards efficient protein detection

    NASA Astrophysics Data System (ADS)

    Petropoulou, Afroditi; Gibson, Thomas J.; Themistou, Efrosyni; Pispas, Stergios; Riziotis, Christos

    2016-11-01

    The development of a low complexity fiber optic based protein sensor by functionalizing the surface of silica optical fibers using block copolymers having both hydrophobic poly(methyl methacrylate) (PMMA) and hydrophilic poly[2- (dimethylamino)ethyl methacrylate] (PDMAEMA) blocks is presented here. The amphiphilic thiol-functionalized PMMA117-b-P(DMAEMA17-st-TEMA2) and vinyl-sulfone PMMA117-b-P(DMAEMA17-st-VSTEMA2) block copolymers designed and synthesized in this work contain a cationic hydrophilic PDMAEMA block that can electrostatically bind selected oppositely charged proteins and also appropriate functional groups for reversible or non-reversible protein binding, respectively, leading to a refractive index change of the overlayer and hence, enabling the sensing. The developed PMMA117-b-PDMAEMA16-based platform has been evaluated for bovine serum albumin (BSA) sensing, exhibiting linear response to detected BSA concentrations.

  11. Amphiphilic model conetworks based on cross-linked star copolymers of benzyl methacrylate and 2-(dimethylamino)ethyl methacrylate: synthesis, characterization, and DNA adsorption studies.

    PubMed

    Achilleos, Demetra S; Georgiou, Theoni K; Patrickios, Costas S

    2006-12-01

    Six amphiphilic model conetworks of a new structure, that of cross-linked "in-out" star copolymers, were synthesized by the group transfer polymerization (GTP) of the hydrophobic monomer benzyl methacrylate (BzMA) and the ionizable hydrophilic monomer 2-(dimethylamino)ethyl methacrylate (DMAEMA) in a one-pot preparation. The synthesis took place in tetrahydrofuran (THF) using tetrabutylammonium bibenzoate (TBABB) as the catalyst, 1-methoxy-1-(trimethylsiloxy)-2-methyl-propene (MTS) as the initiator, and ethylene glycol dimethacrylate (EGDMA) as the cross-linker. Three heteroarm star-, two star block-, one statistical copolymer star-, and one homopolymer star-based networks were prepared. The synthesis of these star-based networks involved four to six steps, including the preparation of the linear (co)polymers, the "arm-first" and the "in-out" star copolymers, and finally the network. The precursors and the extractables were characterized using gel permeation chromatography (GPC) and proton nuclear magnetic resonance (1H NMR) spectroscopy. The degrees of swelling (DSs) of all the networks were measured in THF, while the aqueous DSs were measured as a function of pH. The DSs at low pH were higher than those at neutral or high pH because of the protonation of the DMAEMA units and were found to be dependent on the structure of the network. The DSs in THF were higher than those in neutral water and were independent of the structure. Finally, DNA adsorption studies onto the networks indicated that the DNA binding was governed by electrostatics.

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

    PubMed

    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).

  13. Complex microparticulate systems based on glycidyl methacrylate and xanthan.

    PubMed

    Lungan, Maria-Andreea; Popa, Marcel; Desbrieres, Jacques; Racovita, Stefania; Vasiliu, Silvia

    2014-04-15

    Porous microparticles based on glycidyl methacrylate, dimethacrylic monomers [ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate] and xanthan gum were synthesized by aqueous suspension polymerization method in the presence of toluene as diluent using two types of initiators: benzoyl peroxide and ammonium persulfate. The G microparticles based on glycidyl methacrylate and dimethacrylic monomers and X microparticles based on glycidyl methacrylate, xanthan and dimethacrylic monomers were characterized by various techniques including FT-IR spectroscopy, TG analysis, SEM analysis and DVS method. The specific surface areas were determined by DVS method, while the copolymer porosities and pore volume were obtained from the apparent and skeletal densities. The results have indicated that xanthan was included in the crosslinked matrix by means of covalent bonds. X microparticles have a porous structure with higher specific surface area (129-44 m(2)/g) and higher sorption capacities compared with G microparticles (69-31 m(2)/g).

  14. Health and Environmental Effects Profile for ethyl methacrylate

    SciTech Connect

    Not Available

    1986-06-01

    The Health and Environmental Effects Profile for ethyl methacrylate was prepared to support listings of hazardous constituents of a wide range of waste streams under Section 3001 of the Resource Conservation and Recovery Act (RCRA) and to provide health-related limits for emergency actions under Section 101 of the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA). Both published literature and information obtained from Agency program office files were evaluated as they pertained to potential human health, aquatic life and environmental effects. Quantitative estimates are presented provided sufficient data are available. Ethyl methacrylate has been determined to be a systemic toxicant. An acceptable daily intake (ADI) for ethyl methacrylate is 0.086 mg/kg/day for oral exposure.

  15. Protonation of diethylaminoethyl methacrylate by acids in various solvents

    SciTech Connect

    Zhuravleva, I.L.; Bune, E.V.; Bogachev, Yu.S.; Sheinker, A.P.; Teleshov, E.N.

    1988-04-10

    It was established by /sup 1/H and /sup 13/C NMR that diethylaminoethyl methacrylate exists in the unprotonated form in solvents which are not acids. In the presence of an equimolar amount of hydrochloric or trifluoroacetic acids the amino ester is fully protonated, irrespective of the solvent. The diethylaminoethyl methacrylate-acetic acid system exists in the form of a molecular complex with a hydrogen bond and in the protonated form; the proportions of the protonated form were estimated in various solvents. The change in the reactivity of diethylaminoethyl methacrylate and its salts in polymerization was explained by a change in the electronic state of CH/sub 2/ = group of the monomer as a result of its protonation and of the formation of a hydrogen bond between the C = O group of the monomer and the solvent.

  16. Poly(methyl methacrylate)-cellulose nitrate copolymers. I. Preparation

    SciTech Connect

    Badran, B.M.; Sherif, S.; Abu-Sedira, A.A.

    1981-03-01

    Poly(methyl methacrylate)-cellulose nitrate copolymers were prepared in the form of rods and sheets by bulk polymerization using benzoyl peroxide as initiator. Suspension polymerization did not succeed in preparing poly(methyl methacrylate)-cellulose nitrate copolymers, especially when cellulose nitrate of 11.4% nitrogen content was used. The parameters such as cellulose nitrate concentration, nitrogen content of cellulose nitrate, the amount of initiator and the reaction time, and the temperature are discussed. The prepared copolymers were irradiated for specified periods of up to 11.83 Mrad. It was found that poly(methyl methacrylate)-cellulose nitrate copolymers did not dissolve in any conventional solvent, but they swelled. Swelling decreases with increasing cellulose nitrate concentrations, nitrogen content of cellulose nitrate, and irradiation dose, indicating the crosslinked structure of the prepared copolymers.

  17. 40 CFR 721.10523 - Perfluoroalkylethyl methacrylate copolymer with hydroxymethyl acrylamide, vinyl chloride and long...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... copolymer with hydroxymethyl acrylamide, vinyl chloride and long chain fatty alkyl acrylate (generic). 721... Substances § 721.10523 Perfluoroalkylethyl methacrylate copolymer with hydroxymethyl acrylamide, vinyl... methacrylate copolymer with hydroxymethyl acrylamide, vinyl chloride and long chain fatty alkyl acrylate (PMN...

  18. 40 CFR 721.10523 - Perfluoroalkylethyl methacrylate copolymer with hydroxymethyl acrylamide, vinyl chloride and long...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... copolymer with hydroxymethyl acrylamide, vinyl chloride and long chain fatty alkyl acrylate (generic). 721... Substances § 721.10523 Perfluoroalkylethyl methacrylate copolymer with hydroxymethyl acrylamide, vinyl... methacrylate copolymer with hydroxymethyl acrylamide, vinyl chloride and long chain fatty alkyl acrylate (PMN...

  19. Review of Polymerization and Properties of Aminoalkyl Acrylates and Aminoalkyl Methacrylates

    DTIC Science & Technology

    1988-07-01

    to Russian investigators Korshunov, Bodnaryuk, and Kut’in, in 1975.2 The patent concerned the synthesis of methacrylate monomers containing an amino...group through transesterification. These researchers used alkyl methacrylates , mainly methyl methacrylate (MMA), as precursors for the synthesis. For...Ratios (rl, r2) of Aminoalkyl Methacrylates and Other Vinyl Monomers Monomer1 Moromer2 rl r2 DMAEMA MMA 0.717 0.676 DMAEMA BMA 0.705 0.66 BDIMA MMA 0.612

  20. Final report of the safety assessment of methacrylate ester monomers used in nail enhancement products.

    PubMed

    2005-01-01

    Methacrylate ester monomers are used in as artificial nail builders in nail enhancement products. They undergo rapid polymerization to form a hard material on the nail that is then shaped. While Ethyl Methacrylate is the primary monomer used in nail enhancement products, other methacrylate esters are also used. This safety assessment addresses 22 other methacrylate esters reported by industry to be present in small percentages as artificial nail builders in cosmetic products. They function to speed up polymerization and/or form cross-links. Only Tetrahydrofurfuryl Methacrylate was reported to the FDA to be in current use. The polymerization rates of these methacrylate esters are within the same range as Ethyl Methacrylate. While data are not available on all of these methacrylate esters, the available data demonstrated little acute oral, dermal, or i.p. toxicity. In a 28-day inhalation study on rats, Butyl Methacrylate caused upper airway irritation; the NOAEL was 1801 mg/m3. In a 28-day oral toxicity study on rats, t-Butyl Methacrylate had a NOAEL of 20 mg/kg/day. Beagle dogs dosed with 0.2 to 2.0 g/kg/day of C12 to C18 methacrylate monomers for 13 weeks exhibited effects only in the highest dose group: weight loss, emesis, diarrhea, mucoid feces, or salivation were observed. Butyl Methacrylate (0.1 M) and Isobutyl Methacrylate (0.1 M) are mildly irritating to the rabbit eye. HEMA is corrosive when instilled in the rabbit eye, while PEG-4 Dimethacrylate and Trimethylolpropane Trimethacrylate are minimally irritating to the eye. Dermal irritation caused by methacrylates is documented in guinea pigs and rabbits. In guinea pigs, HEMA, Isopropylidenediphenyl Bisglycidyl Methacrylate, Lauryl Methacrylate, and Trimethylolpropane Trimethacrylate are strong sensitizers; Butyl Methacrylate, Cyclohexyl Methacrylate, Hexyl Methacrylate, and Urethane Methacrylate are moderate sensitizers; Hydroxypropyl Methacrylate is a weak sensitizer; and PEG-4 Dimethacrylate and

  1. The lower alkyl methacrylates: Genotoxic profile of non-carcinogenic compounds.

    PubMed

    Albertini, Richard J

    2017-03-01

    All of the lower alkyl methacrylates are high production chemicals with potential for human exposure. The genotoxicity of seven mono-functional alkyl esters of methacrylic acid, i.e. methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, n-, i- and t-butyl methacrylate and 2 ethyl hexyl methacrylate, as well as methacrylic acid itself, the acyl component common to all, is reviewed and compared with the lack of carcinogenicity of methyl methacrylate, the representative member of the series so evaluated. Also reviewed are the similarity of structure, chemical and biological reactivity, metabolism and common metabolic products of this group of compounds which allows a category approach for assessing genotoxicity. As a class, the lower alkyl methacrylates are universally negative for gene mutations in prokaryotes but do exhibit high dose clastogenicity in mammalian cells in vitro. There is no convincing evidence that these compounds induce genotoxic effects in vivo in either sub-mammalian or mammalian species. This dichotomy of effects can be explained by the potential genotoxic intermediates generated in vitro. This genotoxic profile of the lower alkyl methacrylates is consistent with the lack of carcinogenicity of methyl methacrylate.

  2. 21 CFR 73.3127 - Vinyl alcohol/methyl methacrylate-dye reaction products.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Vinyl alcohol/methyl methacrylate-dye reaction... Vinyl alcohol/methyl methacrylate-dye reaction products. (a) Identity. The color additives are formed by reacting the dyes, either alone or in combination, with a vinyl alcohol/methyl methacrylate copolymer,...

  3. 21 CFR 73.3127 - Vinyl alcohol/methyl methacrylate-dye reaction products.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Vinyl alcohol/methyl methacrylate-dye reaction... Vinyl alcohol/methyl methacrylate-dye reaction products. (a) Identity. The color additives are formed by reacting the dyes, either alone or in combination, with a vinyl alcohol/methyl methacrylate copolymer,...

  4. 21 CFR 73.3127 - Vinyl alcohol/methyl methacrylate-dye reaction products.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Vinyl alcohol/methyl methacrylate-dye reaction... Vinyl alcohol/methyl methacrylate-dye reaction products. (a) Identity. The color additives are formed by reacting the dyes, either alone or in combination, with a vinyl alcohol/methyl methacrylate copolymer,...

  5. 21 CFR 73.3127 - Vinyl alcohol/methyl methacrylate-dye reaction products.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Vinyl alcohol/methyl methacrylate-dye reaction... Vinyl alcohol/methyl methacrylate-dye reaction products. (a) Identity. The color additives are formed by... methacrylate-dye reaction product listed under this section into commerce shall submit to the Food and...

  6. 21 CFR 73.3127 - Vinyl alcohol/methyl methacrylate-dye reaction products.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Vinyl alcohol/methyl methacrylate-dye reaction... Vinyl alcohol/methyl methacrylate-dye reaction products. (a) Identity. The color additives are formed by... methacrylate-dye reaction product listed under this section into commerce shall submit to the Food and...

  7. 21 CFR 177.2000 - Vinylidene chloride/methyl acrylate/methyl methacrylate polymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... methacrylate polymers. 177.2000 Section 177.2000 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic.../methyl methacrylate polymers. The vinylidene chloride/methyl acrylate/methyl methacrylate polymers...

  8. Mössbauer studies of solid state decomposition of methyl methacrylate-ethyl methacrylate copolymers containing ferric chloride

    NASA Astrophysics Data System (ADS)

    Kapur, G. S.; Brar, A. S.

    1990-07-01

    Methyl methacrylate (MMA)-ethyl methacrylate (EMA) copolymers of different monomer concentrations containing anhydrous ferric chloride were prepared by bulk polymerization at 70°C. TGA studies showed that inclusion of iron salt increases the thermal stability of copolymers by 50°C. Mössbauer spectra of copolymers heated at different temperatures showed the presence of Fe3+ species only, in different environments. The mechanism of thermal stabilization of copolymer has been proposed on the basis of IR, TGA and Mössbauer spectroscopy studies.

  9. Solid-state dye lasers based on copolymers of 2-hydroxyethyl methacrylate and methyl methacrylate doped with rhodamine 6G

    NASA Astrophysics Data System (ADS)

    Costela, A.; Florido, F.; Garcia-Moreno, I.; Duchowicz, R.; Amat-Guerri, F.; Figuera, J. M.; Sastre, R.

    1995-04-01

    Rhodamine 6G has been dissolved in copolymers of 2-HydroxyEthyl MethAcrylate (HEMA) and Methyl MethAcrylate (MMA) and the resulting solid-state solutions have been pumped at 337 nm and 532 nm. Lasing efficiencies similar to those found in ethanol solution have been obtained with a 1:1 vol/vol HEMA: MMA copolymer matrix, and lifetimes of ca. 10 000 (337 nm pumping) and ca. 75 000 (532 nm pumping) pulses at repetition rates up to 15 Hz and 10 Hz, respectively, have been demonstrated.

  10. Reordering transitions during annealing of block copolymer cylinder phases

    SciTech Connect

    Majewski, Pawel W.; Yager, Kevin G.

    2015-10-06

    While equilibrium block-copolymer morphologies are dictated by energy-minimization effects, the semi-ordered states observed experimentally often depend on the details of ordering pathways and kinetics. In this study, we explore reordering transitions in thin films of block-copolymer cylinder-forming polystyrene-block-poly(methyl methacrylate). We observe several transient states as films order towards horizontally-aligned cylinders. In particular, there is an early-stage reorganization from randomly-packed cylinders into hexagonally-packed vertically-aligned cylinders; followed by a reorientation transition from vertical to horizontal cylinder states. These transitions are thermally activated. The growth of horizontal grains within an otherwise vertical morphology proceeds anisotropically, resulting in anisotropic grains in the final horizontal state. The size, shape, and anisotropy of grains are influenced by ordering history; for instance, faster heating rates reduce grain anisotropy. These results help elucidate aspects of pathway-dependent ordering in block-copolymer thin films.

  11. Crosslinked superhydrophobic films fabricated by simply casting poly(methyl methacrylate-butyl acrylate-hydroxyethyl methacrylate)-b-poly(perfluorohexylethyl methacrylate) solution

    NASA Astrophysics Data System (ADS)

    Wen, Xiufang; Ye, Chao; Cai, Zhiqi; Xu, Shouping; Pi, Pihui; Cheng, Jiang; Zhang, Lijuan; Qian, Yu

    2015-06-01

    This study focuses on the preparation of superhydrophobic films by crosslinkable polymer material-Poly(methyl methacrylate-butyl acrylate-hydroxyethyl methacrylate)-b-Poly(perfluorohexylethyl methacrylate) (P (MMA-BA-HEMA)-b-PFMA) with a simple one-step casting process. Nanoscale micelle particles with core-shell structure was obtained by dissolving the polymer and curing agent in the mixture of acetone and 1H, 1H, 5H octafluoropentyl-1,1,2,2 tetrafluoroethyl ether (FHT). Superhydrophobic films were fabricated by casting the micelle solution on the glass slides. By controlling the polymer concentration and acetone/FHT volume ratio, superhydrophobic polymer film with water contact angle of 153.2 ± 2.1° and sliding angle of 4° was obtained. By introducing a curing agent into the micelle solution, mechanical properties of the films can be improved. The adhension grade and hardness of the crosslinked superhydrophobic films reached 2 grade and 3H, respectively. The hydrophobicity is attributed to the synergistic effect of micro-submicro-nano-meter scale roughness by nanoscale micelle particles and low surface energy of fluoropolymer. This procedure makes it possible for widespread applications of superhydrophobic film due to its simplicity and practicability.

  12. 21 CFR 177.1830 - Styrene-methyl methacrylate copolymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... methacrylate copolymers identified in this section may be safely used as components of plastic articles... weight percent of polymer units derived from styrene. (b) The finished plastic food-contact article, when... not to exceed an absorbance of 0.15. (3) Ultraviolet-absorbing distilled water and 8 and 50...

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

    SciTech Connect

    Spivey, J.J.; Gogate, M.R.; Jang, B.W.L.

    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.

  14. Synthesis and Characterization of Carboxymethylcellulose-Methacrylate Hydrogel Cell Scaffolds

    PubMed Central

    Reeves, Robert; Ribeiro, Andreia; Lombardo, Leonard; Boyer, Richard; Leach, Jennie B.

    2012-01-01

    Many carbohydrates pose advantages for tissue engineering applications due to their hydrophilicity, degradability, and availability of chemical groups for modification. For example, carboxymethylcellulose (CMC) is a water-soluble cellulose derivative that is degradable by cellulase. Though this enzyme is not synthesized by mammalian cells, cellulase and the fragments derived from CMC degradation are biocompatible. With this in mind, we created biocompatible, selectively degradable CMC-based hydrogels that are stable in routine culture, but degrade when exposed to exogenous cellulase. Solutions of CMC-methacrylate and polyethylene glycol dimethacrylate (PEG-DM) were co-crosslinked to form stable hydrogels; we found that greater CMC-methacrylate content resulted in increased gel swelling, protein diffusion and rates of degradation by cellulase, as well as decreased gel shear modulus. CMC-methacrylate/PEG-DM gels modified with the adhesive peptide RGD supported fibroblast adhesion and viability. We conclude that hydrogels based on CMC-methacrylate are suitable for bioengineering applications where selective degradability may be favorable, such as cell scaffolds or controlled release devices. PMID:22708058

  15. Occupational asthma due to methyl methacrylate and cyanoacrylates.

    PubMed Central

    Lozewicz, S; Davison, A G; Hopkirk, A; Burge, P S; Boldy, D A; Riordan, J F; McGivern, D V; Platts, B W; Davies, D; Newman Taylor, A J

    1985-01-01

    Five patients had asthma provoked by cyanoacrylates and one by methyl methacrylate, possibly because of the development of a specific hypersensitivity response. Acrylates have wide domestic as well as industrial uses, and inhalation of vapour emitted during their use can cause asthma. PMID:4071461

  16. Reactive compatibilization of PBT/ABS blends by methyl methacrylate, glycidyl methacrylate, ethyl acrylate terpolymers

    NASA Astrophysics Data System (ADS)

    Hale, Wesley Raymond

    The impact resistance of poly(butylene terephthalate), PBT, has been improved by blending with acrylonitrile-butadiene-styrene terpolymers, ABS, as a minor dispersed phase; however, extensive coarsening of the dispersed phase in the blends occurs under certain heat fabrication conditions. The incorporation of certain reactive polymers (compatibilizers) that are miscible with the styrene/acrylonitrile (SAN) matrix of ABS should result in more stable morphologies. Terpolymers of methyl methacrylate, glycidyl methacrylate (GMA), ethyl acrylate, MGE, are effective as reactive compatibilizers for blends of PBT with SAN and ABS materials. The epoxide groups of MGE react with the carboxyl endgroups of PBT to form a MGE-g-PBT graft copolymer at the PBT/SAN interface to provide improved SAN or ABS dispersion, morphological stability, and a broadening of the melt processing window. Additionally, compatibilization produces large improvements in the low temperature fracture toughness of PBT/ABS blends; however, the toughness depends on the order of mixing blend components due to crosslinking reactions involving the epoxide groups of MGE catalyzed by residual acids present in some emulsion-made ABS materials. The PBT, ABS, and MGE type, content, and composition have been examined to evaluate their effects on the mechanical and morphological properties of PBT/ABS blends. Additionally, the effects of different processing conditions have been examined. High PBT melt viscosity is desirable for improving ABS dispersion and low temperature toughness of the blends. Generally, ABS materials with a high rubber content and low melt viscosity are desirable for toughening PBT. Moderate amounts of GMA in the blend were found to significantly improve blend properties. Melt blending can be performed using a variety of equipment; however, a co-rotating intermeshing twin screw extruder is the most effective for producing blends with excellent properties. The fracture properties of PBT

  17. Release of Water Soluble Drugs from Dynamically Swelling POLY(2-HYDROXYETHYL Methacrylate - CO - Methacrylic Acid) Hydrogels.

    NASA Astrophysics Data System (ADS)

    Kou, Jim Hwai-Cher

    In this study, ionizable copolymers of HEMA and methacrylic acid (MA) are investigated for their potential use in developing pH dependent oral delivery systems. Because of the MA units, these gels swell extensively at high pH. Since solute diffusion in the hydrophilic polymers depends highly on the water content of the matrix, it is anticipated that the release rate will be modulated by this pH induced swelling. From a practical point of view, the advantage of the present system is that one can minimize drug loss in the stomach and achieve a programmed release in intestine. This approach is expected to improve delivery of acid labile drugs or drugs that cause severe gastrointestinal side effects. This work mainly focuses on the basic understanding of the mechanism involved in drug release from the poly(HEMA -co- MA) gels, especially under dynamic swelling conditions. Equilibrium swelling is first characterized since water content is the major determinant of transport properties in these gels. Phenylpropanolamine (PPA) is chosen as the model drug for the release study and its diffusion characteristics in the gel matrix determined. The data obtained show that the PPA diffusivity follows the free volume theory of Yasuda, which explains the accelerating effect of swelling on drug release. A mathematical model based on a diffusion mechanism has been developed to describe PPA release from the swelling gels. Based on this model, several significant conclusions can be drawn. First, the release rate can be modulated by the aspect ratio of the cylindrical geometry, and this has a practical implication in dosage form design. Second, the release rate can be lowered quite considerably if the dimensional increase due to swelling is significant. Consequently, it is the balance between the drug diffusivity increase and the gel dimensional growth that determines the release rate from the swelling matrix. Third, quasi-steady release kinetics, which are characteristic of swelling

  18. A single-component photo-responsive fluid based on a gemini surfactant with an azobenzene spacer.

    PubMed

    Song, Binglei; Hu, Yufang; Zhao, Jianxi

    2009-05-15

    A new gemini surfactant with an azobenzene group incorporated in the spacer has been synthesized. In water, this new compound forms a photo-responsive fluid, and the properties have been characterized by rheology and freeze-fracture electron microscopy (FF-TEM). UV/Vis irradiation causes a reversible change in zero shear viscosity of about 5 orders of magnitude. The different rheological properties correspond to different aggregation states in solution. A densely entangled network and small discrete micelles are respectively responsible for the high viscosity and the low viscosity state, as revealed by FF-TEM. The simplicity and high photo-efficiency of this single-component system act as a foundation for designing novel stimuli-responsive materials.

  19. Azobenzene liquid crystalline materials for efficient optical switching with pulsed and/or continuous wave laser beams.

    PubMed

    Hrozhyk, Uladzimir A; Serak, Svetlana V; Tabiryan, Nelson V; Hoke, Landa; Steeves, Diane M; Kimball, Brian R

    2010-04-12

    This study compares optical switching capabilities of liquid crystal (LC) materials based on different classes of azobenzene dyes. LCs based on molecules containing benzene rings with nearly symmetrical pi-pi conjugation respond more efficiently to a cw beam than to a nanosecond laser pulse and maintain the changes induced by the beam for tens of hours. Using azo dye molecules containing two benzene rings with push-pull pi-pi conjugation we demonstrate high photosensitivity to both a cw beam as well as nanosecond laser pulse with only 1 s relaxation of light-induced changes in material properties. Even faster, 1 ms restoration time is obtained for azo dye molecules containing hetaryl (benzothiazole) ring with enhanced push-pull pi-pi conjugation. These materials respond most efficiently to pulsed excitation while discriminating cw radiation.

  20. Optical properties of azobenzene-functionalized self-assembled monolayers: Intermolecular coupling and many-body interactions

    NASA Astrophysics Data System (ADS)

    Cocchi, Caterina; Moldt, Thomas; Gahl, Cornelius; Weinelt, Martin; Draxl, Claudia

    2016-12-01

    In a joint theoretical and experimental work, the optical properties of azobenzene-functionalized self-assembled monolayers (SAMs) are studied at different molecular packing densities. Our results, based on density-functional and many-body perturbation theory, as well as on differential reflectance (DR) spectroscopy, shed light on the microscopic mechanisms ruling photo-absorption in these systems. While the optical excitations are intrinsically excitonic in nature, regardless of the molecular concentration, in densely packed SAMs intermolecular coupling and local-field effects are responsible for a sizable weakening of the exciton binding strength. Through a detailed analysis of the character of the electron-hole pairs, we show that distinct excitations involved in the photo-isomerization at low molecular concentrations are dramatically broadened by intermolecular interactions. Spectral shifts in the calculated DR spectra are in good agreement with the experimental results. Our findings represent an important step forward to rationalize the excited-state properties of these complex materials.

  1. Poly(methacrylic acid-co-methyl methacrylate) beads promote vascularization and wound repair in diabetic mice.

    PubMed

    Martin, Daniel C; Semple, John L; Sefton, Michael V

    2010-05-01

    Topical application of beads made from poly(methacrylic acid-co-methyl methacrylate) (45 mol % methacrylic acid, MAA) increased the number of blood vessels and improved 1.5 x 1.5 cm full thickness wound closure in a diabetic mouse (db/db) model. Three groups were compared: MAA beads, control poly(methyl methacrylate) beads (PMMA), and no bead blanks. MAA bead treatment significantly increased percent wound closure at all timepoints (7, 14, and 21 days) with MAA bead-treated wounds almost closed at day 21 (91 +/- 5.4% MAA vs. 79 +/- 3.2% PMMA or 76 +/- 4.8% no beads; p < 0.05). This was consistent with the expected significant increase in vascularity in the MAA group at days 7 and 14. For example at day 14, MAA bead-treated wounds had a vascular density of 22.7 +/- 2.6 vessels/hpf compared with 17.0 +/- 2.0 vessels/hpf in the PMMA bead group (p < 0.05). Epithelial gap and migration measurements suggested that the increased vascularity leads to enhanced epithelial cell migration as a principal means of wound closure. Although studies are underway to elucidate the mechanism of this angiogenic response, the results presented here support the notion that such materials, perhaps in other forms, may be useful in wound care or in other situations where vascularity is to be enhanced without the use of exogenous growth factors.

  2. Organic Thin-films for Block Copolymer Lithography

    NASA Astrophysics Data System (ADS)

    Han, Eungnak

    We have developed surface modification methods for controlling the orientation of poly(styrene-block-methyl methacrylate) (P(S-b-MMA)) microdomains in thin films. First, negative-tone photoresist chemistry was exploited to generate photo-patternable ultra-thin neutral surfaces. The composition ranges of substrate-modifying random copolymers that induce the perpendicular orientation of domains in block copolymer (BCP) thin films (defined as the perpendicular window), was studied for both symmetric and asymmetric P(S-b-MMA). The substrate-modifying layers consisted of random copolymers of styrene (S) and methyl methacrylate (MMA), and contained either a terminal hydroxyl group, a third polar comonomer such as hydroxyethyl methacrylate (HEMA), or glycidyl methacrylate (GMA). Lamellae- and cylinder-forming P(S-b-MMA) (both PS and PMMA cylinders) were assembled on the modified surfaces. In all cases, a vertical orientation of domains was observed for a range of random copolymer composition, but the perpendicular window was different for each combination of surface layer and block copolymer. The detailed understanding of the perpendicular window gained from this study allowed rational selection of neutral layer composition for directed assembly of BCP and inducing perpendicular orientation of domains in thicker films of BCP. Second, we have developed a direct electron beam patternable buffer layer to spatially control the orientation of the microdomains in an overlaying P(S-b-MMA). The buffer layer consists of a surface anchored low molecular weight P(S-b-MMA), with the PMMA segment anchored to the surface and a short PS block at the buffer layer/BCP interface. The block architecture of the buffer layer combines the essential features of "bottom up" and "top down" approaches as it functions as a nonpreferential layer to dictate perpendicular orientation of BCP domains from the substrate interface and as an e-beam resist to allow a top-down lithographic process to

  3. Reversible Photoinduced Switching of Permeability in a Cast Non-Porous Film Comprising Azobenzene Liquid Crystalline Polymer.

    PubMed

    Liu, Jian; Wang, Mingle; Dong, Mingling; Gao, Liude; Tian, Jingjing

    2011-10-04

    Permeation characteristics of an azobenzene-containing liquid crystalline (LC) non-porous film are investigated using a metallic corrosion method. Thin films (300 nm) are fabricated by the solution casting of an azobenzene side-chain LC polymer on freshly polished carbon steel coupons. Coated coupons are treated under the following conditions: a) gradual annealing at a cooling rate lower than 1 °C · min(-1) from 150 °C (above its Tg ) to room temperature, and b) irradiation at 465 nm (20 mW · cm(-2) ) with either circularly polarized light (CPL) or non-polarized light (NPL). The morphology of these films is characterized using X-ray diffraction, polarized optical microscopy, and transmission measurements. The results suggest that the annealing treatment resulted in the formation of a polydomain structure consisting of locally ordered small smectic domains that lack mutual orientation. Ordered micro domains are surrounded by disordered phases. CPL and NPL irradiation generates a monodomain orientated structure and an isotropic liquid crystal glass, respectively. The permeability of these non-porous films treated by CPL, NPL, and annealing are found to be 6.14 × 10(-4) , 1.92 × 10(-2) , and 1.56 × 10(-3) cm(3)  · m(-2)  · d(-1) . An orientation-dependent structure model is constructed to explain the permeation phenomenon, considering the ordered phase is impermeable, only the disordered phase is accessible to penetrating molecules. Fast switching of gas permeation is demonstrated by alternative irradiation of the film with CPL and NPL, which results in an approximately 30-fold difference in the permeability of the non-porous film.

  4. Poly(sulfobetaine methacrylate)s as electrode modifiers for inverted organic electronics.

    PubMed

    Lee, Hyunbok; Puodziukynaite, Egle; Zhang, Yue; Stephenson, John C; Richter, Lee J; Fischer, Daniel A; DeLongchamp, Dean M; Emrick, Todd; Briseno, Alejandro L

    2015-01-14

    We demonstrate the use of poly(sulfobetaine methacrylate) (PSBMA), and its pyrene-containing copolymer, as solution-processable work function reducers for inverted organic electronic devices. A notable feature of PSBMA is its orthogonal solubility relative to solvents typically employed in the processing of organic semiconductors. A strong permanent dipole moment on the sulfobetaine moiety was calculated by density functional theory. PSBMA interlayers reduced the work function of metals, graphene, and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) by over 1 eV, and an ultrathin interlayer of PSBMA reduced the electron injection barrier between indium tin oxide (ITO) and C70 by 0.67 eV. As a result, the performance of organic photovoltaic devices with PSBMA interlayers is significantly improved, and enhanced electron injection is demonstrated in electron-only devices with ITO, PEDOT:PSS, and graphene electrodes. This work makes available a new class of dipole-rich, counterion-free, pH insensitive polymer interlayers with demonstrated effectiveness in inverted devices.

  5. Are block copolymer worms more effective Pickering emulsifiers than block copolymer spheres?

    PubMed

    Thompson, K L; Mable, C J; Cockram, A; Warren, N J; Cunningham, V J; Jones, E R; Verber, R; Armes, S P

    2014-11-21

    RAFT-mediated polymerisation-induced self-assembly (PISA) is used to prepare six types of amphiphilic block copolymer nanoparticles which were subsequently evaluated as putative Pickering emulsifiers for the stabilisation of n-dodecane-in-water emulsions. It was found that linear poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) (PGMA-PHPMA) diblock copolymer spheres and worms do not survive the high shear homogenisation conditions used for emulsification. Stable emulsions are obtained, but the copolymer acts as a polymeric surfactant; individual chains rather than particles are adsorbed at the oil-water interface. Particle dissociation during emulsification is attributed to the weakly hydrophobic character of the PHPMA block. Covalent stabilisation of these copolymer spheres or worms can be readily achieved by addition of ethylene glycol dimethacrylate (EGDMA) during the PISA synthesis. TEM studies confirm that the resulting cross-linked spherical or worm-like nanoparticles survive emulsification and produce genuine Pickering emulsions. Alternatively, stabilisation can be achieved by either replacing or supplementing the PHPMA block with the more hydrophobic poly(benzyl methacrylate) (PBzMA). The resulting linear spheres or worms also survive emulsification and produce stable n-dodecane-in-water Pickering emulsions. The intrinsic advantages of anisotropic worms over isotropic spheres for the preparation of Pickering emulsions are highlighted. The former particles are more strongly adsorbed at similar efficiencies compared to spheres and also enable smaller oil droplets to be produced for a given copolymer concentration. The scalable nature of PISA formulations augurs well for potential applications of anisotropic block copolymer nanoparticles as Pickering emulsifiers.

  6. Synthesis of molecularly imprinted organic-inorganic hybrid azobenzene materials by sol-gel for radiation induced selective recognition of 2,4-dichlorophenoxyacetic acid

    NASA Astrophysics Data System (ADS)

    Shuai Jiang, Guang; An Zhong, Shi; Chen, Lan; Blakey, Idriss; Whitaker, Andrew

    2011-02-01

    A novel photoresponsive functional monomer bearing a siloxane polymerisable group and azobenzene moieties was synthesized. This monomer was then used to prepare photoresponsive molecularly imprinted polymers (MIP), which have specific binding sites for 2,4-dichlorophenoxyacetic acid (2,4-D) through hydrogen bonding moieties. The binding affinity of the imprinted recognition sites was switchable by alternate irradiations with ultraviolet and visible light, suggesting that azobenzene groups located inside the binding sites could be used as chemical sensors and the trans-cis isomerization could regulate the affinity for the 2,4-D. In addition, the concentration of the 2,4-D was able to be quantified by monitoring the trans-to-cis photoisomerization rate constant.

  7. Pd/Cu cooperative catalysis: an efficient synthesis of (3-isoindazolyl)allenes via cross-coupling of 2-alkynyl azobenzenes and terminal alkynes.

    PubMed

    Zhu, Chuan; Feng, Chao; Yamane, Motoki

    2017-02-23

    An efficient synthesis of (3-isoindazolyl)allenes from 2-alkynyl azobenzenes and terminal alkynes via cooperative Pd(PPh3)2Cl2/CuI-catalyzed cross-coupling has been developed. By making use of this approach, (3-isoindazolyl)allenes with various substituents can be synthesized in good to excellent yields. A rapid synthesis of biologically active indazolo[2,3-a]quinoline was also achieved using this method as the key step.

  8. Synthesis of Functionalized Hydrazines: Facile Homogeneous (N‐Heterocyclic Carbene)‐Palladium(0)‐Catalyzed Diboration and Silaboration of Azobenzenes

    PubMed Central

    Ansell, Melvyn B.; Kostakis, George E.

    2016-01-01

    Abstract The bis(N‐heterocyclic carbene)(diphenylacetylene)palladium complex [Pd(ITMe)2(PhC≡CPh)] (ITMe=1,3,4,5‐tetramethylimidazol‐2‐ylidene) acts as a highly active pre‐catalyst in the diboration and silaboration of azobenzenes to synthesize a series of novel functionalized hydrazines. The reactions proceed using commercially available diboranes and silaboranes under mild reaction conditions. PMID:28111537

  9. Poly(2-hydroxyethyl methacrylate)-b-poly(L-Lysine) cationic hybrid materials for non-viral gene delivery in NIH 3T3 mouse embryonic fibroblasts.

    PubMed

    Johnson, Renjith P; Uthaman, Saji; John, Johnson V; Heo, Min Seon; Park, In Kyu; Suh, Hongsuk; Kim, Il

    2014-09-01

    In order to develop efficient and nontoxic gene delivery vectors, a series of biocompatible block copolymers, poly[(2-hydroxyethyl methacrylate)40 -block-(L-lysine)n ] (n = 40, 80, 120, 150), are prepared by combining an atom transfer radical polymerization of 2-hydroxyethyl methacrylate with a ring-opening polymerization of N(ϵ) -(carbobenzoxy)-L-lysine N-carboxyanhydride. The block copolymers are successfully condensed with plasmid DNA (pDNA) into nanosized (<200 nm) polyplexes. As a representative sample, p(HEMA)40 -b-p(lys)150 is utilized to confirm the effective cellular and nuclear uptake of pDNA. The polymer/pDNA polyplexes exhibit very low cytotoxicity and enhanced transfection activity by being easily taken up into mouse embryonic fibroblast cell line (NIH 3T3). Thus, the chimeric block copolymers provide a means for developing versatile nonviral gene vectors harboring the ideal requirements of low cytotoxicity, good stability, and high transfection efficiency for gene therapy.

  10. Solid coatings deposited from liquid methyl methacrylate via Plasma Polymerization

    NASA Astrophysics Data System (ADS)

    Wurlitzer, Lisa; Maus-Friedrichs, Wolfgang; Dahle, Sebastian

    2016-09-01

    The polymerization of methyl methacrylate via plasma discharges is well known today. Usually, plasma-enhanced chemical vapor deposition (PECVD) is used to deposit polymer coatings. Solid coatings are formed out of the liquid phase from methyl methacrylate via dielectric barrier discharge. The formation of the coating proceeds in the gas and the liquid phase. To learn more about the reactions in the two phases, the coatings from MMA monomer will be compared to those from MMA resin. Finally, attenuated total reflection infrared spectroscopy, confocal laser scanning microscopy and X-ray photoelectron spectroscopy are employed to characterize the solid coatings. In conclusion, the plasma enhanced chemical solution deposition is compared to the classical thermal polymerization of MMA.

  11. Azulene methacrylate polymers: synthesis, electronic properties, and solar cell fabrication.

    PubMed

    Puodziukynaite, Egle; Wang, Hsin-Wei; Lawrence, Jimmy; Wise, Adam J; Russell, Thomas P; Barnes, Michael D; Emrick, Todd

    2014-08-06

    We report the synthesis of novel azulene-substituted methacrylate polymers by free radical polymerization, in which the azulene moieties represent hydrophobic dipoles strung pendant to the polymer backbone and impart unique electronic properties to the polymers. Tunable optoelectronic properties were realized by adjusting the azulene density, ranging from homopolymers (having one azulene group per repeat unit) to copolymers in which the azulene density was diluted with other pendant groups. Treating these polymers with organic acids revealed optical and excitonic behavior that depended critically on the azulene density along the polymer chain. Copolymers of azulene with zwitterionic methacrylates proved useful as cathode modification layers in bulk-heterojunction solar cells, where the relative azulene content affected the device metrics and the power conversion efficiency reached 7.9%.

  12. Physical properties of agave cellulose graft polymethyl methacrylate

    SciTech Connect

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

    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.

  13. [Chest granuloma secondary to methyl methacrylate. Case report].

    PubMed

    Martínez-Bistrain, Ricardo; Robles García, Verónica; Cornejo-Morales, Ivonne

    2010-01-01

    We present the case of a patient with a history of a massive left hemithorax crushing injury in 1985; the exact management of the lesion is unknown. Twenty years later he had a thoracic fistula with a culture that was reported as positive for Enteroccocus faecalis and Staphyloccocus epidermidis. The patient was referred by the chest surgery service with the diagnosis of rib osteomyelitis once complementary imaging tests were performed (plain X-rays, CAT scan and MRI). The patient underwent surgery at our service; a granulomatous reaction secondary to a foreign body (methyl methacrylate and Ethibon) was reported. Chest reconstruction for massive lesions is possible with methyl methacrylate. Imaging studies involve the well-known difficulty to identify this material, given that it may produce signals and densities that are difficult to interpret by specialized physicians.

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

    PubMed

    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.

  15. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect

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

    1999-04-21

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

  16. Positron annihilation investigations on poly(methyl methacrylate)

    NASA Astrophysics Data System (ADS)

    Mohamed, Hamdy F. M.; Abd-Elsadek, Gomaa G.

    2000-06-01

    Positron lifetime and Doppler broadened annihilation radiation were measured for seven different samples of poly(methyl methacrylate) at room temperature in vacuum. The polymerisation of methyl methacrylate was carried out as a bulk polymerisation in the presence of benzoyl peroxide as an initiator. The effect of the amount of the initiator on the viscosity-average molecular weight was studied. It was found that the viscosity-average molecular weight decreased with increasing amount of the initiator. The average lifetime and intensity of ortho-positronium ( o-Ps) increased with increasing viscosity-average molecular weight up to 6.85 × 10 4 and remained constant after that. The S-parameter showed a similar behaviour as that of the o-Ps intensity.

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

    NASA Technical Reports Server (NTRS)

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

    1976-01-01

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

  18. Physical properties of agave cellulose graft polymethyl methacrylate

    NASA Astrophysics Data System (ADS)

    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.

  19. SYNTHESIS OF METHACRYLATES FROM COAL-DERIVED SYNGAS

    SciTech Connect

    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.

  20. Pediatric poisonings from household products: hydrofluoric acid and methacrylic acid.

    PubMed

    Perry, H E

    2001-04-01

    Household products continue to be a cause of poisoning morbibidity and mortality. Young children frequently are exposed to cleaning products and cosmetics in the course of exploring their environment. Most of these exposures are insignificant, but some result in death or permanent disability. This review discusses two products that have been responsible for serious injury and death in children: hydrofluoric acid and methacrylic acid. It also discusses federal initiatives designed to protect children from these and other household hazards.

  1. Gelatin methacrylate microspheres for controlled growth factor release.

    PubMed

    Nguyen, Anh H; McKinney, Jay; Miller, Tobias; Bongiorno, Tom; McDevitt, Todd C

    2015-02-01

    Gelatin has been commonly used as a delivery vehicle for various biomolecules for tissue engineering and regenerative medicine applications due to its simple fabrication methods, inherent electrostatic binding properties, and proteolytic degradability. Compared to traditional chemical cross-linking methods, such as the use of glutaraldehyde (GA), methacrylate modification of gelatin offers an alternative method to better control the extent of hydrogel cross-linking. Here we examined the physical properties and growth factor delivery of gelatin methacrylate (GMA) microparticles (MPs) formulated with a wide range of different cross-linking densities (15-90%). Less methacrylated MPs had decreased elastic moduli and larger mesh sizes compared to GA MPs, with increasing methacrylation correlating to greater moduli and smaller mesh sizes. As expected, an inverse correlation between microparticle cross-linking density and degradation was observed, with the lowest cross-linked GMA MPs degrading at the fastest rate, comparable to GA MPs. Interestingly, GMA MPs at lower cross-linking densities could be loaded with up to a 10-fold higher relative amount of growth factor than conventional GA cross-linked MPs, despite the GA MPs having an order of magnitude greater gelatin content. Moreover, a reduced GMA cross-linking density resulted in more complete release of bone morphogenic protein 4 and basic fibroblast growth factor and accelerated release rate with collagenase treatment. These studies demonstrate that GMA MPs provide a more flexible platform for growth factor delivery by enhancing the relative binding capacity and permitting proteolytic degradation tunability, thereby offering a more potent controlled release system for growth factor delivery.

  2. Gelatin Methacrylate Microspheres for Growth Factor Controlled Release

    PubMed Central

    Nguyen, Anh H.; McKinney, Jay; Miller, Tobias; Bongiorno, Tom; McDevitt, Todd C.

    2014-01-01

    Gelatin has been commonly used as a delivery vehicle for various biomolecules for tissue engineering and regenerative medicine applications due to its simple fabrication methods, inherent electrostatic binding properties, and proteolytic degradability. Compared to traditional chemical cross-linking methods, such as the use of glutaraldehyde (GA), methacrylate modification of gelatin offers an alternative method to better control the extent of hydrogel cross-linking. Here we examined the physical properties and growth factor delivery of gelatin methacrylate (GMA) microparticles formulated with a wide range of different cross-linking densities (15–90%). Less methacrylated MPs had decreased elastic moduli and larger mesh sizes compared to GA MPs, with increasing methacrylation correlating to greater moduli and smaller mesh sizes. As expected, an inverse correlation between microparticle cross-linking density and degradation was observed, with the lowest cross-linked GMA MPs degrading at the fastest rate, comparable to GA MPs. Interestingly, GMA MPs at lower cross-linking densities could be loaded with up to a 10-fold higher relative amount of growth factor over conventional GA cross-linked MPs, despite an order of magnitude greater gelatin content of GA MPs. Moreover, a reduced GMA cross-linking density resulted in more complete release of bone morphogenic protein 4 (BMP4) and basic fibroblast growth factor (bFGF) and accelerated release rate with collagenase treatment. These studies demonstrate that GMA MPs provide a more flexible platform for growth factor delivery by enhancing the relative binding capacity and permitting proteolytic degradation tunability, thereby offering a more potent controlled release system for growth factor delivery. PMID:25463489

  3. Multifunctional methacrylate-based coatings for glass and metal surfaces

    NASA Astrophysics Data System (ADS)

    Pospiech, Doris; Jehnichen, Dieter; Starke, Sandra; Müller, Felix; Bünker, Tobias; Wollenberg, Anne; Häußler, Liane; Simon, Frank; Grundke, Karina; Oertel, Ulrich; Opitz, Michael; Kruspe, Rainer

    2017-03-01

    In order to prevent freshwater biofouling glass and metal surfaces were coated with novel transparent methacrylate-based copolymers. The multifunctionality of the copolymers, such as adhesion to the substrate, surface polarity, mechanical long-term stability in water, and ability to form metal complexes was inserted by the choice of suitable comonomers. The monomer 2-acetoacetoxy ethyl methacrylate (AAMA) was used as complexing unit to produce copper(II) complexes in the coating's upper surface layer. The semifluorinated monomer 1H,1H,2H,2H-perfluorodecyl methacrylate was employed to adjust the surface polarity and wettability. Comprehensive surface characterization techniques, such as X-ray photoelectron spectroscopy (XPS) and contact angle measurements showed that surface compositions and properties can be easily adjusted by varying the concentrations of the comonomers. The formation of copper(II) complexes along the copolymer chains and their stability against washing out with plenty of water was proven by XPS. Copolymers containing semifluorinated comonomers significantly inhibited the growth of Achnanthidium species. Copolymers with copper-loaded AAMA-sequences were able to reduce both the growth of Achnanthidium spec. and Staphylococcus aureus.

  4. Methacrylate based gel polymer electrolyte for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Isken, P.; Winter, M.; Passerini, S.; Lex-Balducci, A.

    2013-03-01

    A methacrylate based gel polymer electrolyte (GPE) was prepared and electrochemically investigated. The polymer was synthesized as a statistical co-polymer of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) and benzyl methacrylate (BnMA) by free radical polymerization. The ethylene glycol side chain of OEGMA should be able to interact with the liquid electrolyte, thus keeping it inside the GPE, whereas BnMA was used to enhance the mechanical stability of the GPE. Such a polymer was able to retain liquid electrolyte up to 400% of its own weight, while the mechanical stability of the GPE was still high enough to be used as separator in lithium-ion batteries. The GPE displayed a conductivity of 1.8 mS cm-1 at 25 °C and an electrochemical stability window comparable to that of a standard liquid electrolyte. When used in lithium-ion batteries, such a GPE allowed a performance comparable to that obtained using conventional liquid electrolytes. Therefore the reported electrolyte was identified as a promising candidate as electrolyte for lithium-ion batteries.

  5. Evaluation of alternate routes for the synthesis of methyl methacrylate

    SciTech Connect

    Spivey, J.J.; Gogate, M.R.; Zoeller, J.R.; Colberg, R.D.; Choi, G.N.

    1998-12-31

    The use of coal-derived syngas to produce high value chemicals is an important means of upgrading this resource. One example of a chemical that can be produced from coal-derived syngas is methyl methacrylate (MMA). Poly-methyl methacrylate is widely used in coatings and in various industrial molded products. The most widely practiced commercial technology for the synthesis of MMA is the acetone cyanohydrin (ACH) process. This process requires handling of large quantities of toxic hydrogen cyanide and generates one mole of ammonium bisulfate waste per mole of MMA. This bisulfate must either be regenerated or discarded, either of which substantially increases the cost. The ACH technology is thus environmentally and economically untenable for any new MMA plant expansions that would be needed to meet increasing demand. The RTI-Eastman-Bechtel research team is developing an alternative, environmentally benign route to MMA consisting of three steps; (step 1) synthesis of a propionate from ethylene, carbon monoxide, and steam, (step 2) condensation of this propionate with formaldehyde, and (step 3) esterification of resulting methacrylic acid with methanol to form MMA. This paper describes the preliminary economics of the overall process compared to other emerging processes, and focuses on step 2, including long term testing of catalysts for the condensation of propionic acid with formaldehyde to form MAA.

  6. Reactive block copolymer vesicles with an epoxy wall.

    PubMed

    Zhu, Hui; Liu, Qingchun; Chen, Yongming

    2007-01-16

    Recently, block copolymer vesicles have attracted considerable attention because of their properties in encapsulation and release. To explore their applications in biorelated fields, functionalization of the polymer vesicle is necessary. Herein, a reactive unilamellar vesicle is reported by self-assembly of poly(ethylene oxide)-block-poly(glycidyl methacrylate) copolymer (PEO-b-PGMA) in solution. When water was added into the PEO-b-PGMA solution in THF, unilamellar vesicles were produced. If hydrophobic primary amine additives, such as hexamethylenediamine (HDA) and dodecylamine (DA), were introduced during block copolymer assembling, the vesicular morphology remained unchanged; instead, the amines reacted with the epoxys and the vesicles were fixed by cross-linking. Furthermore, when 3-aminopropyl trimethoxysilane (APS) was applied, the organic/inorganic hybrid vesicles were obtained, which were stable against the solvent change. Therefore, this research not only supplies a new way to fix the vesicular morphology but also a reactive vesicle scaffold for introducing functional species.

  7. Nanostructured photovoltaic materials using block polymer assemblies

    NASA Astrophysics Data System (ADS)

    Mastroianni, Sarah Elizabeth

    Despite its potential as an abundant, sustainable alternative to non-renewable energy sources, solar energy currently is underutilized. Photovoltaics, which convert energy from sunlight into electricity, commonly are made from inorganic semiconductor materials that require expensive manufacturing and processing techniques. Alternatively, organic materials can be used to produce flexible and lightweight organic photovoltaic (OPV) devices, which can be prepared using solution-based processing techniques. However, OPV devices are limited by low efficiencies and short lifetimes compared to their inorganic counterparts. In OPV systems, charge carriers are generated in the active layer via the separation of excitons (electron-hole pairs) at interfaces between donor and acceptor materials. Because excitons have a limited diffusion length (˜10 nm), they may recombine before reaching a donor-acceptor interface if domain sizes are large. This exciton recombination can limit device efficiency; thus, the design parameters for improved active layer morphologies include large interfacial areas, small size scales, and continuous conducting pathways. Currently, most OPV devices are prepared by blending donor and acceptor materials in bulk heterojunction (BHJ) devices, often resulting in non-ideal, process-dependent morphologies. Alternatively, the self-assembly of block polymers (BP)s offers a reproducible means to generate nanostructured active layers. The work presented in this dissertation examines the synthetic approaches to preparing BPs containing different electroactive materials: non-conjugated, amorphous poly(vinyl-m-triphenylamine) [PVmTPA] and conjugated poly(3-alkythiophene) [P3AT] p-type materials as well as fullerene-based n-type materials. The synthesis and self-assembly of a model poly(methyl methacrylate)- b-PVmTPA system is presented. This work was extended to synthesize PVmTPA BPs with complementary poly(methyl methacrylate- co-hydroxyethyl methacrylate) [P

  8. Synthesis and characterization of injectable, water-soluble copolymers of tertiary amine methacrylates and poly(ethylene glycol) containing methacrylates.

    PubMed

    Anderson, Brian C; Mallapragada, Surya K

    2002-11-01

    Several homopolymers and copolymers of 2-(diethylamino)ethyl methacrylate (DEAEM) and poly(ethylene glycol) methyl ether methacrylate (PEGMEM) were synthesized using anionic polymerization initiated by potassium t-butoxide. The polymers were characterized by average molecular weight, polydispersity and monomeric unit composition. A very narrow molecular weight distribution was achieved with a well-controlled composition. The glass transition temperatures and compositions of the copolymers followed a Gordon-Taylor relationship. The water solubility and biocompatibility of the copolymers was compared to their parent homopolymers to determine if the addition of a poly(ethylene glycol) group was sufficient to solubilize the polymers in aqueous buffer solutions and to increase the biocompatibility of the polymers. These water-soluble, injectable cationic copolymers have potential applications in gene delivery as well as other biomaterial applications.

  9. Motion of integrated CdS nanoparticles by phase separation of block copolymer brushes.

    PubMed

    Yu, Kai; Wang, Hanfu; Han, Yanchun

    2007-08-14

    A new method of reversibly moving CdS nanoparticles in the perpendicular direction was developed on the basis of the phase separation of block copolymer brushes. Polystyrene-b-(poly(methyl methacrylate)-co-poly(cadmium dimethacrylate)) (PS-b-(PMMA-co-PCdMA)) brushes were grafted from the silicon wafer by surface-initiated atom transfer radical polymerization (ATRP). By exposing the polymer brushes to H2S gas, PS-b-(PMMA-co-PCdMA) brushes were converted to polystyrene-b-(poly(methyl methacrylate)-co-poly(methacrylic acid)(CdS)) (PS-b-(PMMA-co-PMAA(CdS))) brushes, in which CdS nanoparticles were chemically bonded by the carboxylic groups of PMAA segment. Alternating treatment of the PS-b-(PMMA-co-PMAA(CdS)) brushes by selective solvents for the outer block (a mixed solvent of acetone and ethanol) and the inner PS block (toluene) induced perpendicular phase separation of polymer brushes, which resulted in the reversible lifting and lowering of CdS nanoparticles in the perpendicular direction. The extent of movement can be adjusted by the relative thickness of two blocks of the polymer brushes.

  10. Preparation of hydroxyapatite/poly(methyl methacrylate) and calcium silicate/poly(methyl methacrylate) interpenetrating hybrid composites.

    PubMed

    Monvisade, Pathavuth; Siriphannon, Punnama; Jermsungnern, Rapee; Rattanabodee, Sirirat

    2007-10-01

    Hydroxyapatite/poly(methyl methacrylate) (HAp/PMMA) and calcium silicate/poly(methyl methacrylate) (CS/PMMA) composites were prepared by interpenetrating bulk polymerization of methyl methacrylate (MMA) monomer in porous structures of HAp and CS. The porous HAp and CS templates were prepared by mixing their calcined powders with poly(vinyl alcohol) (PVA) solution, shaping by uniaxial pressing and then firing at 1,100 degrees C for HAp and 900 degrees C for CS. The templates were soaked in the solution mixture of MMA monomer and 0.1 mol% of benzoyl peroxide (BPO) for 24 h. The pre-composites were then bulk polymerized at 85 degrees C for 24 h under nitrogen atmosphere. The microstructures of the composites showed the interpenetrating of PMMA into the porous HAp and CS structures. Thermogravimetric analysis indicated that the PMMA content in the HAp/PMMA and CS/PMMA composites were 13 and 26 wt%, respectively. Weight average molecular weights (M(w)) of PMMA were about 491,000 for HAp/PMMA composites and about 348,000 for CS/PMMA composites. Compressive strengths of these composites were about 90-131 MPa in which they were significantly higher than their starting porous templates.

  11. Affinity chromatography of proteins on non-porous copolymerized particles of styrene, methyl methacrylate and glycidyl methacrylate.

    PubMed

    Chen, C H; Lee, W C

    2001-06-29

    Non-porous particles having an average diameter of 2.1 microm were prepared by co-polymerization of styrene, methyl methacrylate and glycidyl methacrylate, which was abbreviated as P(S-MMA-GMA). The particles were mechanically stable due to the presence of benzene rings in the backbone of polymer chains, and could withstand high pressures when a column packed with these particles was operated in the HPLC mode. The polymer particles were advantaged by immobilization of ligands via the epoxy groups on the particle surface that were introduced by one of the monomers, glycidyl methacrylate. As a model system, Cibacron Blue 3G-A was covalently immobilized onto the non-porous copolymer beads. The dye-immobilized P(S-MMA-GMA) particles were slurry packed into a 1.0 cm x 0.46 cm I.D. column. This affinity column was effective for the separation of turkey egg white lysozyme from a protein mixture. The bound lysozyme could be eluted to yield a sharp peak by using a phosphate buffer containing 1 M NaCl. For a sample containing up to 8 microg of lysozyme, the retained portion of proteins could be completely eluted without any slit peak. Due to the use of a shorter column, the analysis time was shorter in comparison with other affinity systems reported in the literature. The retention time could be reduced significantly by increasing the flow-rate, while the capacity factor remained at the same level.

  12. Molecular Dynamics Simulations of Hugoniot Relations for Poly[methyl methacrylate

    DTIC Science & Technology

    2011-11-01

    Molecular Dynamics Simulations of Hugoniot Relations for Poly[ methyl methacrylate ] by Tanya L. Chantawansri, Edward F. C. Byrd, Betsy M. Rice...Ground, MD 21005-5066 ARL-TR-5819 November 2011 Molecular Dynamics Simulations of Hugoniot Relations for Poly[ methyl methacrylate ...4. TITLE AND SUBTITLE Molecular Dynamics Simulations of Hugoniot Relations for Poly[ methyl methacrylate ] 5a. CONTRACT NUMBER 5b. GRANT NUMBER

  13. Modification of the adhesive properties of silicone-based coatings by block copolymers.

    PubMed

    Ngo, T Chinh; Kalinova, Radostina; Cossement, Damien; Hennebert, Elise; Mincheva, Rosica; Snyders, Rony; Flammang, Patrick; Dubois, Philippe; Lazzaroni, Roberto; Leclère, Philippe

    2014-01-14

    The improvement of the (bio)adhesive properties of elastomeric polydimethylsiloxane (PDMS) coatings is reported. This is achieved by a surface modification consisting of the incorporation of block copolymers containing a PDMS block and a poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) block in a PDMS matrix, followed by matrix cross-linking and immersion of the obtained materials in water. Contact angle measurements (CA), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) showed the presence of the PDMAEMA block at the surface, drastic morphology changes, and improved adhesion properties after immersion in water. Finally, underwater bioadhesion tests show that mussels adhere only to block copolymer-filled coatings and after immersion in water, i.e., when the PDMAEMA blocks have been brought to the coating surface. These observations highlight the significant role of hydrophilic groups in the surface modification of silicone coatings.

  14. Testing block subdivision algorithms on block designs

    NASA Astrophysics Data System (ADS)

    Wiseman, Natalie; Patterson, Zachary

    2016-01-01

    Integrated land use-transportation models predict future transportation demand taking into account how households and firms arrange themselves partly as a function of the transportation system. Recent integrated models require parcels as inputs and produce household and employment predictions at the parcel scale. Block subdivision algorithms automatically generate parcel patterns within blocks. Evaluating block subdivision algorithms is done by way of generating parcels and comparing them to those in a parcel database. Three block subdivision algorithms are evaluated on how closely they reproduce parcels of different block types found in a parcel database from Montreal, Canada. While the authors who developed each of the algorithms have evaluated them, they have used their own metrics and block types to evaluate their own algorithms. This makes it difficult to compare their strengths and weaknesses. The contribution of this paper is in resolving this difficulty with the aim of finding a better algorithm suited to subdividing each block type. The proposed hypothesis is that given the different approaches that block subdivision algorithms take, it's likely that different algorithms are better adapted to subdividing different block types. To test this, a standardized block type classification is used that consists of mutually exclusive and comprehensive categories. A statistical method is used for finding a better algorithm and the probability it will perform well for a given block type. Results suggest the oriented bounding box algorithm performs better for warped non-uniform sites, as well as gridiron and fragmented uniform sites. It also produces more similar parcel areas and widths. The Generalized Parcel Divider 1 algorithm performs better for gridiron non-uniform sites. The Straight Skeleton algorithm performs better for loop and lollipop networks as well as fragmented non-uniform and warped uniform sites. It also produces more similar parcel shapes and patterns.

  15. Preparation of Pickering Double Emulsions Using Block Copolymer Worms

    PubMed Central

    2015-01-01

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

  16. Preparation and evaluation of poly(alkyl methacrylate-co-methacrylic acid-co-ethylene dimethacrylate) monolithic columns for separating polar small molecules by capillary liquid chromatography.

    PubMed

    Lin, Shu-Ling; Wu, Yu-Ru; Lin, Tzuen-Yeuan; Fuh, Ming-Ren

    2015-04-29

    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.

  17. Directive Evidence for the Creation of Micropores in UV-Irradiated Poly(Methyl Methacrylate)

    DTIC Science & Technology

    1990-05-31

    behavior of photochromic labels allows the study of processes such as physical aging. plasticization. and volume dilation caused by glassy deformation... photochromic labels [15. 16]. In this work. azobenzene was used as a molecular label to study the formation of micropores in irradiated PMMA film. Trans...the polymer matrix could be probed by the use of photochromic labels [13-161. Analysis of the photoisomerization behavior of photochromic labels

  18. Drug-loading of poly(ethylene glycol methyl ether methacrylate) (PEGMEMA)-based micelles and mechanisms of uptake in colon carcinoma cells.

    PubMed

    Chang, Teddy; Gosain, Pallavi; Stenzel, Martina H; Lord, Megan S

    2016-08-01

    In this study polymeric micelles formed from poly(poly(ethylene glycol) methyl ether methacrylate)-block-poly(methyl methacrylate) (P(PEGMEMA75)-b-PMMA80) block copolymer of approximately 25nm in diameter were used to encapsulate the model drug, Nile Red, with a loading efficiency of 0.08wt% and a chemotherapeutic drug, doxorubicin (DOX), with an efficiency of 2.75wt%. The release of DOX from the micelles was sufficient to be cytotoxic to human colon carcinoma cells, WiDr, while Nile Red and the unloaded micelles were found not to be cytotoxic when exposed to the cells at polymer concentrations up to 200μg/mL. Nile Red loaded micelles were used to analyze uptake of the micelles into the cells which were rapidly internalized within minutes of exposure. The three major endocytotic pathways were involved in the internalization of micelles; however other passive mechanisms were also at play as the addition of inhibitors to all three pathways did not completely inhibit the uptake of these nanoparticles. These data demonstrate the potential of the P(PEGMEMA)75-b-PMMA80 block copolymer micelles to be rapidly internalized by carcinoma cells and deliver low doses of drugs intracellularly for controlled drug release.

  19. Photochromic Composite for Random Lasing Based on Porous Polypropylene Infiltrated with Azobenzene-Containing Liquid Crystalline Mixture.

    PubMed

    Lisinetskii, Victor; Ryabchun, Alexander; Bobrovsky, Alexey; Schrader, Sigurd

    2015-12-09

    We report on a new low-cost and easily fabricated type of liquid crystalline polymer composites demonstrating low threshold random lasing, which can be used as a cheap and simple mirror-less laser source. The composite is based on mass-producible commercially available porous polypropylene (Celgard 2500) infiltrated with low-molar-mass liquid crystal material doped with Rhodamine 800 laser dye. Excitation with red nanosecond laser (630 nm) induces random lasing with the emission peak in NIR spectral range (804 nm) with noticeable degree of linear polarization. The possibility to control the lasing threshold and polarization of the output light with UV radiation through photoswitching of liquid crystal phase from nematic to isotropic is demonstrated. The photocontrollable phase switching is achieved by reversible E/Z isomerization of the azobenzene dopant introduced to the nematic host matrix. It is revealed that the isotropic state of liquid crystal provides more efficient random lasing with lower threshold due to significant scattering of the ordinary wave.

  20. Supra-dendron Gelator Based on Azobenzene-Cyclodextrin Host-Guest Interactions: Photoswitched Optical and Chiroptical Reversibility.

    PubMed

    Xie, Fan; Ouyang, Guanghui; Qin, Long; Liu, Minghua

    2016-12-12

    A novel amphiphilic dendron (AZOC8 GAc) with three l-glutamic acid units and an azobenzene moiety covalently linked by an alkyl spacer has been designed. The compound formed hydrogels with water at very low concentration and self-assembled into chiral-twist structures. The gel showed a reversible macroscopic volume phase transition in response to pH variations and photo-irradiation. During the photo-triggered changes, although the gel showed complete reversibility in its optical absorptions, only an incomplete chiroptical property change was achieved. On the other hand, the dendron could form a 1:1 inclusion complex through a host-guest interaction with α-cyclodextrin (α-CD), designated as supra-dendron gelator AZOC8 GAc/α-CD. The supra-dendron showed similar gelation behavior to that of AZOC8 GAc, but with enhanced photoisomerization-transition efficiency and chiroptical switching capacity, which was completely reversible in terms of both optical and chiroptical performances. The self-assembly of the supra-dendron is a hierarchical or multi-supramolecular self-assembling process. This work has clearly illustrated that the hierarchical and multi-supramolecular self-assembling system endows the supramolecular nanostructures or materials with superior reversible optical and chiroptical switching.

  1. Effect of photoisomerization of azobenzene dopants on the flexoelectric properties of short-pitch cholesteric liquid crystals

    PubMed

    Komitov; Ruslim; Ichimura

    2000-05-01

    The flexoelectric properties of short-pitch cholesteric mixtures doped with three different azobenzenes, 4,4'-dihexyloxyazobenzene (4,4'-azo), 3,3'-dihexyloxy-2,2'-dimethylazobenzene (3,3'-azol), and 3,3'-dihexanoyloxy-2,2'-dimethylazobenzene (3,3'-azo2), respectively, were studied upon illumination with uv light. Their effective flexoelectric coefficients were derived from the flexoelectro-optic response of the mixtures aligned in uniform lying helix texture. Considering the fact that the pitch of the mixtures became shorter upon uv illumination, an increase of their effective flexoelectric coefficients was found to take place due to the photoisomerization of the dyes. The largest change was found for the coefficient of the guest-host mixture containing 4,4'-azo dye, most probably due to the bent shape of the dye cis-isomer. This observation is in good agreement with our previous studies on the influence of the molecular shape on the liquid-crystal flexoelectric properties and it suggests a possible way for enhancement of the amplitude of flexoelectro-optic response in cholesterics by using liquid-crystal materials with pronounced molecular shape dissymmetry.

  2. Room temperature optical image storage devices based on novel photo-responsive chiral azobenzene liquid crystal dopants

    NASA Astrophysics Data System (ADS)

    Chen, Si; Chen, Yining; Tong, Xiaoqian; Wu, Bozhen; Ma, Meng; Shi, Yanqin; Wang, Xu

    2016-11-01

    A room temperature optical image storage device based on a novel kind of chiral azobenzene liquid crystal compound (Azo-CC) dopant was reported in this paper, which could realize room temperature photocatalytic phase transition when doping in host liquid crystal E7. With a comparation of the referential achiral compound (Azo-ACC), the chemical structure, liquid crystalline and photoresponsive properties of the compounds were characterized by 1H-NMR, POM and UV-vis, respectively. The result showed that the compound with chiral group (Azo-CC) exhibited better photoresponsive properties than the referential achiral compound (Azo-ACC), indicating the introduction of chiral group is the key factor to provide E7 host room temperature photosensitive properties, which could not only made the liquid crystal molecular reoriented but also could change the whole nematic host liquid crystal to helical-twisted matrix. In addition, to understand the optical-switching behavior into detail, the photoisomerization dynamics of the systems o was also analyzed.

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

    PubMed

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

    2013-11-19

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

  4. Femtosecond fluorescence dynamics of rotation-restricted azobenzenophanes: new evidence on the mechanism of trans --> cis photoisomerization of azobenzene.

    PubMed

    Lu, Ying-Chih; Diau, Eric Wei-Guang; Rau, Hermann

    2005-03-17

    The ultrafast relaxation dynamics of two rotation-restricted (azobenzeno-2S-phane and azobenzeno-4S-phane) and one rotation-free (4,4'-dimethylazobenzene) azobenzene derivatives were investigated using femtosecond fluorescence up-conversion on both S(1)(n,pi) and S(2)(pi,pi) excitations. On S(2) excitation, pulse-limited kinetics with a decay coefficient of approximately 100 fs corresponding to ultrafast S(2) --> S(1) relaxation is found to be common for all molecules under investigation regardless of the molecular structure. This indicates that a direct rotational relaxation on the S(2) surface is unfavorable. On S(1) excitation, we observed biphasic fluorescence decay with a femtosecond component attributed to the decay of the Franck-Condon state prepared by excitation and a picosecond component attributed to the deactivation of the relaxed molecule on the S(1) surface. This picosecond component is slowed by at least a factor of 2 for the rotation-restricted 2S-bridged molecule compared to that of the rotation-free molecule; for the even stronger rotation-restricted azobenzeno-4S-phane, the decrease is by a factor of 10. These differences in deactivation suggest that the relaxed states and probably the trajectories for rotation-free and rotation-restricted molecules are different on the S(1) surface, which should be important for the quantum yield of photoisomerization.

  5. DFT study of linear and nonlinear optical properties of donor-acceptor substituted stilbenes, azobenzenes and benzilideneanilines.

    PubMed

    Krawczyk, Przemysław

    2010-04-01

    A theoretical analysis of the linear and nonlinear optical properties of six push-pull pi-conjugated molecules with stilbene, azobenzene and benzilideneaniline as a backbone is presented. The photophysical properties of the investigated systems were determined by using response functions combined with density functional theory (DFT). Several different exchange-correlation potentials were applied in order to determine parameters describing the one- and two-photon spectra of the studied molecules. In particular, the recently proposed Coulomb-attenuated model (CAM-B3LYP) was used to describe charge-transfer (CT) excited states. In order to compare theoretical predictions with available experimental data, calculations with inclusion of solvent effects were performed. The BLYP and the CAM-B3LYP functionals were found to yield values of two-photon absorption (TPA) probabilities closer to experimental values than the B3LYP functional or the HF wavefunction. Moreover, molecular static hyperpolarisabilities were determined using both DFT and second-order Møller-Plesset perturbation (MP2) theory. Likewise, the CAM-B3LYP functional was found to outperform other applied exchange-correlation potentials in determining first hyperpolarisability (beta). Moreover, it was confirmed on a purely theoretical basis that the presence of a -C=C- bridge between the phenyl rings leads to a much larger nonlinear optical response in comparison with a -N=N- bridge.

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed

    Toy, Mehmet; Tanak, Hasan

    2016-01-05

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

  8. Monolayer alignment on azobenzene surfaces during UV light irradiation: Analysis of optical polarized absorption measurement results and theoretical treatment

    SciTech Connect

    Zakharov, A.V.; Taguchi, Dai; Manaka, Takaaki; Iwamoto, Mitsumasa

    2006-01-14

    The influence of the charge separation during the trans-cis conformational change on the surface of azobenzene 6Az10PVA monolayer on the polar liquid-crystal monolayer film, such as 4-n-pentyl-4{sup '}-cyanobiphenyl(5CB), is investigated. The effective anchoring energy (in the Rapini-Papolar form) is phenomenologically described in the framework of the molecular model, which takes into account the interaction between the surface polarization and surface electric field, for number of conformational states of the boundary surface. It is shown, using the experimental data for the voltage across the 6Az10PVA+5CB film, provided by the surface-potential technique, that the charge separation during the conformational changing, caused by the UV irradiation, may lead to changing of the surface alignment of liquid-crystalline molecules. The influence of the photoisomerization process on the orientational order parameter S{sub 2}(t) using the optical polarized absorption measurement is also investigated.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  10. Hardness of irradiated poly(methyl methacrylate) at elevated temperatures

    SciTech Connect

    Lu, K.-P.; Lee, Sanboh; Cheng, Cheu Pyeng

    2001-08-15

    The decrease in hardness induced by gamma irradiation in poly(methyl methacrylate) (PMMA) has been investigated. The hardness is assumed to decrease linearly with the concentration of radiation-induced defects. Annealing at high temperatures induces defect annihilation as tracked by an increase in hardness. The annihilation follows first-order kinetics during isothermal annealing. The dependence of hardness on the reciprocal of the time constant satisfies the Arrhenius equation, and the corresponding activation energy of the kinetic process decreases with increasing dose. The hardness of postannealed PMMA decreases linearly with increasing dose. {copyright} 2001 American Institute of Physics.

  11. Characterization and degradation of functionalized chitosan with glycidyl methacrylate.

    PubMed

    Flores-Ramírez, Nelly; Elizalde-Peña, Eduardo A; Vásquez-García, Salomón R; González-Hernández, Jesús; Martinez-Ruvalcaba, Agustín; Sanchez, Isaac C; Luna-Bárcenas, Gabriel; Gupta, Ram B

    2005-01-01

    The synthesis, characterization and degradation of a hybrid chitosan (CTS)/glycidyl methacrylate (GMA) material are reported. These versatile materials (natural-synthetic materials) are potential candidates for dental restoratives. All materials were characterized by infrared spectroscopy (FT-IR), X-ray diffraction and thermal (DSC) analysis. Particular attention was paid to the thermal stability and chemical resistance of the hybrid CTS materials. From dynamical rheological tests, it was concluded that CTS-GMA solutions behave as physical hydrogels. These pH-sensitive gels are an example of stimuli-responsive polymers, also known as 'smart polymers'.

  12. Methyl methacrylate permeability of dental and industrial gloves.

    PubMed

    Thomas, Sebastian; Padmanabhan, T V

    2009-01-01

    Our study was undertaken to measure the amount and time it took for methyl methacrylate monomer (MMA) to permeate latex, vinyl and industrial neoprene gloves and to compare the results to obtain a rating of the permeability of each of the gloves studied to MMA. The monomer, permeated under static conditions, was measured using a spectrophotometer. Latex and vinyl clinical gloves became permeable to MMA in a very short amount of time. Neoprene industrial gloves remained impervious for 25 minutes. Dentists and dental technicians should be aware of the toxic effects of MMA and understand that clinical gloves do not afford protection from MMA.

  13. Influence of Ionic Complexes on Phase Behavior of Polystyrene-b-poly(methyl methacrylate) Copolymers

    SciTech Connect

    Wang,J.; Chen, W.; Roy, C.; Sievert, J.; Russell, T.

    2008-01-01

    The influence of ionic complexes on phase behavior of PS-b-PMMA copolymers over a wide range of molecular weights and PS volume fractions was investigated by small-angle X-ray scattering (SAXS), grazing incidence small-angle X-ray scattering (GISAXS), transmission electron microscopy (TEM), and neutron reflectivity (NR). The disorder-to-order transition (DOT) in both symmetric and asymmetric copolymers indicates that the overall Flory-Huggins segmental interaction parameter, eff, between polystyrene (PS) and poly(methyl methacrylate) (PMMA) blocks with lithium-PMMA complexes is increased compared to that of the neat copolymers. This enhanced eff further results in an order-to-order transition (OOT), from spheres to cylinders, and an increase in the ordering and spacing of microdomains. Moreover, transitional metal ionic complexes, such as copper-PMMA complexes, are found to have the similar influence on phase behavior of PS-b-PMMA copolymers. The formation of ionic complexes in the copolymers not only offers a parameter to tune the degree of microphase separation of PS-b-PMMA copolymers but also provides a way to fabricate multifunctional materials.

  14. Block That Pain!

    MedlinePlus

    ... 314. This combination produces a unique effect, blocking pain-sensing neurons without impairing signals from other cells. In contrast, most pain relievers used for surgical procedures block activity in ...

  15. Preparation of novel poly(hydroxyethyl methacrylate-co-glycidyl methacrylate)-grafted core-shell magnetic chitosan microspheres and immobilization of lactase.

    PubMed

    Zhao, Wei; Yang, Rui-Jin; Qian, Ting-Ting; Hua, Xiao; Zhang, Wen-Bin; Katiyo, Wendy

    2013-06-06

    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.

  16. Synthesis of branched poly(methyl methacrylate)s via controlled/living polymerisations exploiting ethylene glycol dimethacrylate as branching agent.

    PubMed

    Isaure, Francoise; Cormack, Peter A G; Graham, Susan; Sherrington, David C; Armes, Steven P; Bütun, Vural

    2004-05-07

    With appropriate choice of reaction composition and conditions, copolymerisation of methyl methacrylate and ethylene glycol dimethacrylate using Cu-based ATRP or GTP methodologies yields soluble branched polymers in facile one-pot reactions.

  17. Cell toxicity of methacrylate monomers-the role of glutathione adduct formation.

    PubMed

    Ansteinsson, V; Kopperud, H B; Morisbak, E; Samuelsen, J T

    2013-12-01

    Polymer-based dental restorative materials are designed to polymerize in situ. However, the conversion of methacrylate monomer to polymer is never complete, and leakage of the monomer occurs. It has been shown that these monomers are toxic in vitro; hence concerns regarding exposure of patients and dental personnel have been raised. Different monomer methacrylates are thought to cause toxicity through similar mechanisms, and the sequestration of cellular glutathione (GSH) may be a key event. In this study we examined the commonly used monomer methacrylates, 2-hydroxyethylmethacrylate (HEMA), triethylenglycol-dimethacrylate (TEGDMA), bisphenol-A-glycidyl-dimethacrylate (BisGMA), glycerol-dimethacrylate (GDMA) and methyl-methacrylate (MMA). The study aimed to establish monomers' ability to complex with GSH, and relate this to cellular toxicity endpoints. Except for BisGMA, all the monomer methacrylates decreased the GSH levels both in cells and in a cell-free system. The spontaneous formation of methacrylate-GSH adducts were observed for all methacrylate monomers except BisGMA. However, we were not able to correlate GSH depletion and toxic response measured as SDH activity and changes in cell growth pattern. Together, the current study indicates mechanisms other than GSH-binding to be involved in the toxicity of methacrylate monomers.

  18. 40 CFR 721.6920 - Butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Butyl acrylate, polymer with... acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane. (a... butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

  19. 40 CFR 721.6920 - Butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Butyl acrylate, polymer with... acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane. (a... butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

  20. 40 CFR 721.6920 - Butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Butyl acrylate, polymer with... acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane. (a... butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

  1. 40 CFR 721.6920 - Butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Butyl acrylate, polymer with... acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane. (a... butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

  2. 21 CFR 177.2000 - Vinylidene chloride/methyl acrylate/methyl methacrylate polymers.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 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...

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

    Code of Federal Regulations, 2011 CFR

    2011-04-01

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

  4. 21 CFR 177.2000 - Vinylidene chloride/methyl acrylate/methyl methacrylate polymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 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...

  5. 21 CFR 177.2000 - Vinylidene chloride/methyl acrylate/methyl methacrylate polymers.

    Code of Federal Regulations, 2010 CFR

    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...

  6. 40 CFR 721.6920 - Butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Butyl acrylate, polymer with... acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane. (a... butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

  7. Allergic contact gingivostomatitis from a temporary crown made of methacrylates and epoxy diacrylates.

    PubMed

    Kanerva, L; Alanko, K; Estlander, T

    1999-12-01

    Occupational allergic contact dermatitis caused by (meth)acrylates is common in dental personnel, whereas dental acrylic fillings and crowns have rarely been reported to cause problems in dental patients. Here we report on a 48-year-old woman who developed gingivitis, stomatitis, and perioral dermatitis after a temporary crown made of restorative, two-component material had been inserted. The manufacturer stated that the temporary crown base paste and catalyst contained three (meth)acrylates, namely, a proacrylate, which is a modification of 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (BIS-GMA); a tricyclate, which is a saturated, aliphatic, tricyclic methacrylate; and urethane methacrylate. The manufacturer refused to give more exact information on the (meth)acrylates. Patch testing revealed that the patient was highly allergic to BIS-GMA, other epoxy diacrylates, and (meth)acrylates, as well as to the base paste and catalyst of the temporary crown. Accordingly, it was concluded that the allergic reaction was caused by BIS-GMA, or a cross-reacting (meth)acrylate, or other (meth)acrylates in the temporary crown.

  8. Water absorption of poly(methyl methacrylate) measured by vertical interference microscopy.

    PubMed

    N'Diaye, Mambaye; Pascaretti-Grizon, Florence; Massin, Philippe; Baslé, Michel Felix; Chappard, Daniel

    2012-08-07

    PMMA (poly(methyl methacrylate)) is widely used to prepare orthopedic cements. They are in direct contact with cells and body fluids. PMMA, despite its hydrophobic nature, can absorb ~2% w/w water. We have evaluated by vertical interference microscopy if water absorption can produce a significant swelling in different types of PMMA blocks: pure, with a plasticizer, with a cross-linker, and in two types of commercial bone cements. Graphite rods which do not swell in water were used as internal standard. Hardness, indentation modulus, plastic, and elastic works were determined by nanoindentation under a 25mN fixed force. Vertical interference microscopy was used to image the polymer in the dry state and hydrated states (after 24 h in distilled water). On the surface of the polished polymers (before and after hydration), we measured roughness by the fractal dimension, the swelling in the vertical and the lateral directions. For each polymer block, four images were obtained and values were averaged. Comparison and standardization of the images in the dry and hydrated states were done with Matlab software. The average value measured on the graphite rod between the two images (dried and hydrated) was used for standardization of the images which were visualized in 3D. After grinding, a small retraction was noticeable between the surface of the rod and the polymers. A retraction ring was also visible around the graphite rod. After hydration, only the pure PMMA and bone cements had a significant swelling in the vertical direction. The presence of polymer beads in the cements limited the swelling in the lateral direction. Swelling parameters correlated with the nanoindentation data. PMMA can swell by absorbing a small amount of water and this induces a swelling that varies with the polymer composition and particle inclusions.

  9. Blocked Tear Duct

    MedlinePlus

    Blocked tear duct Overview By Mayo Clinic Staff When you have a blocked tear duct, your tears can't drain normally, leaving you ... in the tear drainage system. A blocked tear duct is common in newborns. The condition usually gets ...

  10. Interface-enforced complexation between copolymer blocks.

    PubMed

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

    2015-05-14

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

  11. Electrical induction and optical erasure of birefringence in the isotropic liquid phase of a dichiral azobenzene liquid-crystalline compound (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Yamamoto, Takahiro; Nishiyama, Isa

    2015-10-01

    Liquid crystal is a representative soft matter, which has physical properties between those of conventional liquid and those of crystal in a temperature range above a melting point. A liquid-crystal display (LCD) employs the response of the liquid-crystal alignment to the electric field and is a key device of an information display. For common LCDs, the precise control of the initial alignment of LC molecules is needed so that a good dark state, thus a high contrast ratio, can be obtained. If the birefringence can be induced in the liquid phase by the application of electric field, it is of great use as a material for the LCD application. In this study, we will report a unique property of dichiral azobenzene liquid crystals: an electric induction of birefringence in a liquid phase of an antiferroelectric dichiral azobenzene liquid crystal. The optically isotropic texture changes into the homogenous birefringent texture by the application of the in-plane electric field above the clearing temperature of the liquid crystal. We find that one of the possible reasons of the induction of the birefringence in the isotropic phase is the electrically-induced increase of the phase transition temperature between the antiferroelectric liquid-crystalline and "liquid" phases, i.e., increase in the clearing temperature. The resulting birefringence can be disappeared by the irradiation of UV light, due to the photoinduced isomerization of the azobenzene compound, thus dual control of the birefringent structure, by the irradiation of light and/or by the application of the electric field, is achieved.

  12. Antibacterial Adhesion of Polymethyl Methacrylate Modified by Borneol Acrylate.

    PubMed

    Sun, Xueli; Qian, Zhiyong; Luo, Lingqiong; Yuan, Qipeng; Guo, Ximin; Tao, Lei; Wei, Yen; Wang, Xing

    2016-10-07

    Polymethyl methacrylate (PMMA) is a widely used biomaterial. But there is still a challenge facing its unwanted bacterial adhesion, because the subsequent biofilm formation usually leads to failure of related implants. Herein, we present a borneol-modified PMMA based on a facile and effective stereochemical strategy, generating antibacterial copolymer named as P(MMA-co-BA). It was synthesized by free radical polymerization and studied with different ratio between methyl methacrylate (MMA) and borneol acrylate (BA) monomers. NMR, GPC and EA etc. were used to confirm their chemical features. Their films were challenged with Escherichia coli (Gram-negative) and Bacillus subtilis (Gram-positive), showing a BA content-dependent antibacterial performance. The minimum effective dose should be 10%. Then in vivo subcutaneous implantations in mice demonstrated their biocompatibilities through routine histotomy and HE staining. Therefore, P(MMA-co-BA)s not only exhibited their unique antibacterial character, but also suggested a potential for the safe usage of borneol-modified PMMA frame and devices for further implantation.

  13. Modified acrylic bone cement with high amounts of ethoxytriethyleneglycol methacrylate.

    PubMed

    Pascual, B; Gurruchaga, M; Ginebra, M P; Gil, F J; Planell, J A; Vázquez, B; San Román, J; Goñi, I

    1999-03-01

    One cause of arthroplasty failure is the brittle mechanical behavior of bone cements. However, the improvement of cement formulations must also be accompanied by the maintenance of a wide variety of characteristics. New bone cements were obtained by the substitution of high percentages, up to 60% (v/v), of methyl methacrylate (MMA) by a higher molecular weight and more hydrophilic monomer, ethoxytriethyleneglycol methacrylate (TEG). The essential advantages of these materials were the decrease of maximum temperature together with a decrease in the residual monomer content with respect to conventional cement formulations. The water absorption process obeyed diffusion laws and the equilibrium water content increased by the introduction of higher percentages of the hydrophilic component. This characteristic had an appreciable effect on the viscoelastic behavior analyzed by DMTA. These modified bone cements had reduced polymerization shrinkage and similar levels of porosity. Tensile test revealed that the introduction of TEGMA gave rise to an important modification of the mechanical behavior, with a noticeable increase in the fracture strain. This fact was also confirmed by means of the analysis of the fracture surfaces by SEM.

  14. Synthesis of Methyl Methacrylate from Coal-Derived Syngas

    SciTech Connect

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

    1998-04-17

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

  15. CEC separation of heterocyclic amines using methacrylate monolithic columns.

    PubMed

    Barceló-Barrachina, Elena; Moyano, Encarnación; Puignou, Lluís; Galceran, Maria Teresa

    2007-06-01

    Two methacrylate-based monolithic columns, one with a negatively charged group (sulfonic group) and another with a new monomer N,N-dimethylamino ethyl acrylate (DMAEA), were prepared and tested for the separation of basic compounds by CEC. This new monolithic stationary phase was prepared by the in situ polymerization of DMAEA with butyl methacrylate and ethylene dimethacrylate, using a ternary porogenic solvent consisting of water, 1-propanol and 1,4-butanediol. The performance of this column was evaluated by means of the analysis of a family of heterocyclic amines. Separation conditions such as pH, amount of organic modifier, ionic strength and elution mode (normal or counterdirectional flow) were studied. At the optimal running electrolyte composition, and using the counterdirectional mode, symmetrical electrochromatographic peaks were obtained, with the number of theoretical plates up to 30,000 and a good resolution between closely related peaks. The 2-acrylamido-2-methyl-1-propane-sulfonic acid column was used for CEC-MS, taking advantage of the compatibility of its elution mode (normal flow) with the MS coupling.

  16. Degradation of poly(methyl methacrylate) in solution

    SciTech Connect

    Madras, G.; Smith, J.M.; McCoy, B.J.

    1996-06-01

    The rate of degradation of poly(methyl methacrylate) (PMMA) to methyl methacrylate (MMA) was investigated in the liquid phase with toluene as the solvent. The degradation experiments were carried out in a tubular flow reactor at 1,000 psig (6.8 MPa) and at four different temperatures (200, 225, 275, and 300 C). The polymer concentration was varied by 1 to 4 g/L. A discrete model for the first-order rate of polymer degradation was derived and compared to the continuous kinetics approach. Both models lead to the same expression for monomer concentration increasing linearly with time. Rate constants were evaluated using the moments of the molecular weight distributions of the reacted and unreacted polymer. The rate was first order in polymer concentration, and the activation energy was 8.4 kcal/mol (34 kJ/mol). This activation energy suggests that the rate controlling step for the thermal degradation of PMMA is the depropagation process.

  17. The biological properties of a novel ethyl methacrylate resin.

    PubMed

    Suzuki, T; Jinno, S; Hattori, N; Okeya, H; Ishikawa, A; Deguchi, M; Ohno, Y; Kawai, T; Noguchi, T

    2006-01-01

    A novel ethyl methacrylate (EMA) resin was developed to overcome the tissue, organ and systemic damage associated with the residual monomer of conventional methyl methacrylate (MMA) resin bone cement. EMA resin is a chemical/ photopolymerizable material and is easy to handle during clinical procedures. The biocompatibility of EMA was evaluated in accordance with ISO10993-6. No inflammatory response was observed 1 and 9 weeks after implantation in the dorsal subcutaneous tissue of ddY mice. EMA resin also demonstrated better biocompatibility when compared with conventional bone cements. Poly-L-lactic acid (PLLA) was used as a carrier for bone morphogenetic protein (BMP) and added to the EMA slurry. The EMA-PLLA composite membrane was sticky and BMP readily adhered to its surface. The EMA-PLLA-BMP composite membrane induced new bone formation, the new bone growing in the shape of the EMA in the thigh muscle pouch of ddY mice. This novel EMA resin has many potential clinical applications.

  18. Superhydrophobic terpolymer nanofibers containing perfluoroethyl alkyl methacrylate by electrospinning

    NASA Astrophysics Data System (ADS)

    Cengiz, Ugur; Avci, Merih Z.; Erbil, H. Yildirim; Sarac, A. Sezai

    2012-05-01

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

  19. Novel syngas-based process for methyl methacrylate

    SciTech Connect

    Gogate, M.R.; Spivey, J.J.; Zoeller, J.R.; Choi, G.N.; Tam, S.S.; Tischer, R.E.; Srivastava, R.D.

    1996-12-31

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel are developing a novel process for synthesis of methyl methacrylate (MMA) from coal-derived syngas, under a contract from the U.S. Department of Energy, Pittsburgh Energy Technology Center. This three-step process consists of synthesis of a propionate, its condensation with formaldehyde, and esterification of resulting methacrylic acid (MAA) with methanol to produce MMA. Eastman has focused on the research on propionate synthesis step. The resultant Mo catalysts work efficiently at much less severe conditions (170{degrees}C and 30 atm) than the conventional Ni catalysts (270{degrees}C and 180 atm). Bechtel has performed an extensive cost analysis, which shows that Eastman`s propionate synthesis process is competitive with other technologies to produce the anhydride. In the second step, RTI and Eastman have developed active and stable V-SI-P and Ta metal oxide catalysts for condensation reactions of propionates with formaldehyde. RTI has demonstrated a novel correlation among the catalyst acid-base properties, condensation reaction yield, and long-term catalyst activity. Current research focuses on enhancing the condensation reaction yields, acid-base properties, in situ condensation in a high- temperature, high-pressure (HTHP) slurry reactor, and alternate formaldehyde feedstocks. Based on Eastman and RTI laboratory reactor operating data, a cost estimate is also being developed for the integrated process.

  20. The acute aquatic toxicity of a series of acrylate and methacrylate esters

    SciTech Connect

    Staples, C.A.; McLaughlin, J.E.; Hamilton, J.D.

    1994-12-31

    Acute aquatic toxicity data for several acrylate and methacrylate esters were reviewed. Acrylates included acrylic acid, ethyl-, and butyl-acrylate. Methacrylates included methacrylic acid, methyl-, and butyl-methacrylate. Tests were 48 hr or 96 hr standard flow through (invertebrates and fish) assays (measured exposure concentrations). These data are currently used in a risk assessment of acrylate/methacrylate environmental safety. Algal growth (Selanastrum capricomutum) 96 hr EC{sub 50}s were 0.17 mg/L (NOEC < 0.13 mg/L) for acrylic acid, 11.0 mg/L (NOEC < 6.5 mg/L) for ethyl acrylate, and 5.2 mg/L (NOEC < 3.8 mg/L) for butyl acrylate. Invertebrate (Daphnia magna) 48 hr LC{sub 50}s were 95.0 mg/L (NOEC 23.0 mg/L) for acrylic acid, 7.9 mg/L (NOEC 3.4 mg/L) for ethyl acrylate, and 8.2 mg/L (NOEC 2.4 mg/L) for butyl acrylate. Rainbow trout (Oncorhynchus mykiss) 96 hr LC{sub 50}s were 27.0 mg/L (NOEC 6.3 mg/L) for acrylic acid, 4.6 mg/L (NOEC 0.78 mg/L) for ethyl acrylate, and 5.2 mg/L (NOEC 3.8 mg/L) for butyl acrylate. Algae 96 hr EC{sub 50}s were 0.59 mg/L (NOEC 0.38 mg/L) for methacrylic acid, 170.0 mg/L (NOEC 100.0 mg/L) for methyl methacrylate, and 130.0 mg/L for butyl methacrylate. Daphnia magna 48 hr LC{sub 50}s were > 130.0 mg/L (NOEC 130.0 mg/L) for methacrylic acid, 69.0 mg/L (NOEC 48.0 mg/L) for methyl methacrylate, and 32.0 mg/L (NOEC 23.0 mg/L) for butyl methacrylate. Trout 96 hr LC{sub 50}s were 85.0 mg/L (NOEC 12.0 mg/L) for methacrylic acid and > 79.0 mg/L (NOEC 40.0 mg/L) for methyl methacrylate. The fathead minnow (Pimephales promelas) 96 hr LC{sub 50} was 11.0 mg/L for butyl methacrylate.

  1. Total Spinal Block after Thoracic Paravertebral Block

    PubMed Central

    Beyaz, Serbülent Gökhan; Özocak, Hande; Ergönenç, Tolga; Erdem, Ali Fuat; Palabıyık, Onur

    2014-01-01

    Thoracic paravertebral block (TPVB) can be performed with or without general anaesthesia for various surgical procedures. TPVB is a popular anaesthetic technique due to its low side effect profile and high analgesic potency. We used 20 mL of 0.5% levobupivacaine for a single injection of unilateral TPVB at the T7 level with neurostimulator in a 63 year old patient with co-morbid disease who underwent cholecystectomy. Following the application patient lost consciousness, and was intubated. Haemodynamic instability was normalised with rapid volume replacement and vasopressors. Anaesthetic drugs were stopped at the end of the surgery and muscle relaxant was antagonised. Return of mucle strenght was shown with neuromuscular block monitoring. Approximately three hours after TPVB, spontaneous breathing started and consciousness returned. A total spinal block is a rare and life-threatening complication. A total spinal block is a complication of spinal anaesthesia, and it can also occur after peripheral blocks. Clinical presentation is characterised by hypotension, bradicardia, apnea, and cardiac arrest. An early diagnosis and appropriate treatment is life saving. In this case report, we want to present total spinal block after TPVB. PMID:27366387

  2. The Space Block

    NASA Technical Reports Server (NTRS)

    1984-01-01

    Ciba-Geigy Corporation's "Space Block," technically known as TDT-177-51 Ren Shape epoxy model block, is a two-foot by two-foot by five- inch plastic block from which master models of the Space Shuttle protective tiles are cut by NC machines. Space Block is made of epoxy resin with low viscosity and slow curing time, enabling the large block to cure uniformly without cracking. Rockwell International uses master models of Shuttle tiles to check accuracy of NC machines accurately by comparing model dimensions with specifications. New epoxy resins are attracting broad interest as a replacement for traditional materials used in modeling auto, aerospace or other parts.

  3. Congenital complete heart block.

    PubMed Central

    Agarwala, B.; Sheikh, Z.; Cibils, L. A.

    1996-01-01

    Congenital complete heart block in utero has become diagnosed more frequently with the clinical use of fetal echocardiography. The fetus with complete heart block may remain asymptomatic or may develop congestive heart failure. Congenital complete heart block is more frequently seen in infants of mothers with systemic lupus erythematosus, both clinically manifested and subclinical systemic lupus erythematosus with positive antibodies (SS-A and SS-B antibodies). At birth, the neonate with complete heart block may remain asymptomatic and may not require a pacemaker to increase the heart rate. The indications for a pacemaker in neonates with complete heart block have been discussed. Both in-utero and neonatal management of congenital complete heart block are discussed to manage congestive heart failure in a fetus. Four patients with congenital complete heart block are presented covering a broad spectrum of clinical presentation, diagnosis, and management both in the fetal and neonatal period. Images Figure 1 PMID:8961692

  4. The effect of RAFT-derived cationic block copolymer structure on gene silencing efficiency.

    PubMed

    Hinton, Tracey M; Guerrero-Sanchez, Carlos; Graham, Janease E; Le, Tam; Muir, Benjamin W; Shi, Shuning; Tizard, Mark L V; Gunatillake, Pathiraja A; McLean, Keith M; Thang, San H

    2012-10-01

    In this work a series of ABA tri-block copolymers was prepared from oligo(ethylene glycol) methyl ether methacrylate (OEGMA(475)) and N,N-dimethylaminoethyl methacrylate (DMAEMA) to investigate the effect of polymer composition on cell viability, siRNA uptake, serum stability and gene silencing. Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization was used as the method of polymer synthesis as this technique allows the preparation of well-defined block copolymers with low polydispersity. Eight block copolymers were prepared by systematically varying the central cationic block (DMAEMA) length from 38 to 192 monomer units and the outer hydrophilic block (OEGMA(475)) from 7 to 69 units. The polymers were characterized using size exclusion chromatography and (1)H NMR. Chinese Hamster Ovary-GFP and Human Embryonic Kidney 293 cells were used to assay cell viability while the efficiency of block copolymers to complex with siRNA was evaluated by agarose gel electrophoresis. The ability of the polymer-siRNA complexes to enter into cells and to silence the targeted reporter gene enhanced green fluorescent protein (EGFP) was measured by using a CHO-GFP silencing assay. The length of the central cationic block appears to be the key structural parameter that has a significant effect on cell viability and gene silencing efficiency with block lengths of 110-120 monomer units being the optimum. The ABA block copolymer architecture is also critical with the outer hydrophilic blocks contributing to serum stability and overall efficiency of the polymer as a delivery system.

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

    PubMed

    Giordanengo, Rémi; Viel, Stéphane; Hidalgo, Manuel; Allard-Breton, Béatrice; Thévand, André; Charles, Laurence

    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. 1H and 13C 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.

  6. Analytical strategy for the molecular weight determination of random copolymers of poly(methyl methacrylate) and poly(methacrylic acid).

    PubMed

    Giordanengo, Rémi; Viel, Stéphane; Hidalgo, Manuel; Allard-Breton, Béatrice; Thévand, André; Charles, Laurence

    2010-06-01

    Molecular weight characterization of random amphiphilic copolymers currently represents an analytical challenge. In particular, molecules composed of methacrylic acid (MAA) and methyl methacrylate (MMA) as the repeat units raise issues in commonly used techniques. The present study shows that when random copolymers cannot be properly ionized by MALDI, and hence detected and measured in MS, one possible analytical strategy is to transform them into homopolymers, which are more amenable to this ionization technique. Then, by combining the molecular weight of the so-obtained homopolymers, as measured by MS, with the relative molar proportion of the MMA and MMA units, as given by (1)H NMR spectrum, one can straightforwardly estimate the molecular weight of the initial copolymer. A methylation reaction was performed to transform MAA-MMA copolymer samples into PMMA homopolymers, using trimethylsilyldiazomethane as a derivatization agent. Weight average molecular weight (M(w)) parameters of the MAA-MMA copolymers could then be derived from M(w) values obtained for the methylated MAA-MMA molecules by MALDI, which were also validated by pulsed gradient spin echo (PGSE) NMR. An alkene function in one of the studied copolymer end-groups was also shown to react with the methylation agent, giving rise to MMA-like polymeric by-products characterized by tandem mass spectrometry and which could be avoided by adjusting the amount of the trimethylsilyldiazomethane in the reaction medium.

  7. Poly(2-hydroxyethyl methacrylate-co-dodecyl methacrylate-co-acrylic acid): synthesis, physico-chemical characterisation and nafcillin carrier.

    PubMed

    Zecheru, Teodora; Rotariu, Traian; Rusen, Edina; Mărculescu, Bogdan; Miculescu, Florin; Alexandrescu, Laura; Antoniac, Iulian; Stancu, Izabela-Cristina

    2010-10-01

    In the present study polymeric microbeads of poly(2-hydroxyethyl methacrylate-co-dodecyl methacrylate-co-acrylic acid) or p(HEMA-co-dDMA-co-AA) were synthesised and characterized through FT-IR and scanning electron microscopy (SEM); their swelling behavior against saline solution was explored and their in vitro cytotoxicity was evaluated. Further, in order to elucidate kinetic aspects regarding the ternary system p(HEMA-co-dDMA-co-AA), a mathematical model of the reactivity ratios of the comonomers in the terpolymer has been conceived and analyzed. An intensified tendency of AA units accumulation in the copolymer has been noticed, in spite of HEMA units, while dDMA conserves in the copolymer the fraction from the feed. Three compositions have been selected for nafcillin-loading and their in vitro release capacity was evaluated. The compositions of 80:10:10 and 75:10:15 M ratios appear suitable for further in vivo testing, in order to be used as drug delivery systems in the treatment of different osseous diseases.

  8. Feedback-regulated paclitaxel delivery based on poly(N,N-dimethylaminoethyl methacrylate-co-2-hydroxyethyl methacrylate) nanoparticles.

    PubMed

    You, Jin-Oh; Auguste, Debra T

    2008-04-01

    pH-Sensitive poly(N,N-dimethylaminoethyl methacrylate (DMAEMA)/2-hydroxyethyl methacrylate (HEMA)) nanoparticles were prepared for the triggered release of paclitaxel within a tumor microenvironment. Tumors exhibit a lower extracellular pH than normal tissues. We show that paclitaxel release from DMAEMA/HEMA particles can be actively triggered by small, physiological changes in pH (within 0.2-0.6 pH units). Monodispersed nanoparticles were synthesized by forming an O/W emulsion followed by photopolymerization. Particles were characterized by transmission electron microscopy, dynamic light scattering, electrophoresis, and cytotoxicity. High release rates and swelling ratios are achieved at low pH, low crosslinking density, and high content of DMAEMA. Paclitaxel release is limited to 9% of the payload at pH 7.4 after a 2-h incubation at 37 degrees C. After adjusting to pH 6.8, 25% of the payload is released within 2h. Cell viability studies indicate that pH-sensitive DMAEMA/HEMA nanoparticles are not cytotoxic and may be used as an efficient, feedback-regulated drug delivery carrier.

  9. Radiation-grafted polymers for biomaterial applications. I. 2-hydroxyethyl methacrylate: ethyl methacrylate grafting onto low density polyethylene films

    SciTech Connect

    Cohn, D.; Hoffman, A.S.; Ratner, B.D.

    1984-08-01

    Studies were conducted on the radiation grafting of 2-hydroxyethyl methacrylate (HEMA) and ethyl methacrylate (EMA) by the mutual irradation technique onto low density polyethylene. Four different solution concentrations were used, and radiation doses ranged from 0.03 to 0.50 Mrad. Four copolymer compositions having different HEMA:EMA ratios were also studied using two total monomer concentrations. The kinetics of the grafting process demonstrated by the two monomers were basically different. While EMA showed a typical diffusion-controlled kinetic pattern, HEMA exhibited a more complex behavior, the main features of which were an induction period, a slight autoacceleration and a significant drop in graft level after a maximum is reached. The difference in behavior was interpreted in terms of partitioning of monomers into the polyethlene substrate. The surface topography of the grafted films was studied by means of scanning electron microscopy. A mechanism based on osmotic cell formation was suggested for the HEMA graft system. The copolymer systems investigated showed that the graft reaction is faster in the initial stages for higher percentages of EMA in the monomer mixtures; as grafting proceeds the trend is reversed. 24 references, 16 figures, 2 tables.

  10. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect

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

    1999-01-20

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

  11. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect

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

    1999-01-20

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

  12. Block copolymer/ferroelectric nanoparticle nanocomposites

    NASA Astrophysics Data System (ADS)

    Pang, Xinchang; He, Yanjie; Jiang, Beibei; Iocozzia, James; Zhao, Lei; Guo, Hanzheng; Liu, Jin; Akinc, Mufit; Bowler, Nicola; Tan, Xiaoli; Lin, Zhiqun

    2013-08-01

    Nanocomposites composed of diblock copolymer/ferroelectric nanoparticles were formed by selectively constraining ferroelectric nanoparticles (NPs) within diblock copolymer nanodomains via judicious surface modification of ferroelectric NPs. Ferroelectric barium titanate (BaTiO3) NPs with different sizes that are permanently capped with polystyrene chains (i.e., PS-functionalized BaTiO3NPs) were first synthesized by exploiting amphiphilic unimolecular star-like poly(acrylic acid)-block-polystyrene (PAA-b-PS) diblock copolymers as nanoreactors. Subsequently, PS-functionalized BaTiO3 NPs were preferentially sequestered within PS nanocylinders in the linear cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer upon mixing the BaTiO3 NPs with PS-b-PMMA. The use of PS-b-PMMA diblock copolymers, rather than traditional homopolymers, offers the opportunity for controlling the spatial organization of PS-functionalized BaTiO3 NPs in the PS-b-PMMA/BaTiO3 NP nanocomposites. Selective solvent vapor annealing was utilized to control the nanodomain orientation in the nanocomposites. Vertically oriented PS nanocylinders containing PS-functionalized BaTiO3 NPs were yielded after exposing the PS-b-PMMA/BaTiO3 NP nanocomposite thin film to acetone vapor, which is a selective solvent for PMMA block. The dielectric properties of nanocomposites in the microwave frequency range were investigated. The molecular weight of PS-b-PMMA and the size of BaTiO3 NPs were found to exert an apparent influence on the dielectric properties of the resulting nanocomposites.Nanocomposites composed of diblock copolymer/ferroelectric nanoparticles were formed by selectively constraining ferroelectric nanoparticles (NPs) within diblock copolymer nanodomains via judicious surface modification of ferroelectric NPs. Ferroelectric barium titanate (BaTiO3) NPs with different sizes that are permanently capped with polystyrene chains (i.e., PS-functionalized BaTiO3NPs) were

  13. Block copolymer/ferroelectric nanoparticle nanocomposites.

    PubMed

    Pang, Xinchang; He, Yanjie; Jiang, Beibei; Iocozzia, James; Zhao, Lei; Guo, Hanzheng; Liu, Jin; Akinc, Mufit; Bowler, Nicola; Tan, Xiaoli; Lin, Zhiqun

    2013-09-21

    Nanocomposites composed of diblock copolymer/ferroelectric nanoparticles were formed by selectively constraining ferroelectric nanoparticles (NPs) within diblock copolymer nanodomains via judicious surface modification of ferroelectric NPs. Ferroelectric barium titanate (BaTiO3) NPs with different sizes that are permanently capped with polystyrene chains (i.e., PS-functionalized BaTiO3NPs) were first synthesized by exploiting amphiphilic unimolecular star-like poly(acrylic acid)-block-polystyrene (PAA-b-PS) diblock copolymers as nanoreactors. Subsequently, PS-functionalized BaTiO3 NPs were preferentially sequestered within PS nanocylinders in the linear cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer upon mixing the BaTiO3 NPs with PS-b-PMMA. The use of PS-b-PMMA diblock copolymers, rather than traditional homopolymers, offers the opportunity for controlling the spatial organization of PS-functionalized BaTiO3 NPs in the PS-b-PMMA/BaTiO3 NP nanocomposites. Selective solvent vapor annealing was utilized to control the nanodomain orientation in the nanocomposites. Vertically oriented PS nanocylinders containing PS-functionalized BaTiO3 NPs were yielded after exposing the PS-b-PMMA/BaTiO3 NP nanocomposite thin film to acetone vapor, which is a selective solvent for PMMA block. The dielectric properties of nanocomposites in the microwave frequency range were investigated. The molecular weight of PS-b-PMMA and the size of BaTiO3 NPs were found to exert an apparent influence on the dielectric properties of the resulting nanocomposites.

  14. Poly(divinylbenzene-alkyl methacrylate) monolithic stationary phases in capillary electrochromatography.

    PubMed

    Huang, Hsi-Ya; Cheng, Yi-Jie; Liu, Wan-Ling; Hsu, Yi-Fen; Lee, Szetsen

    2010-09-10

    In this study, a series of poly(divinylbenzene-alkyl methacrylate) monolithic stationary phases, which were prepared by single step in situ polymerization of divinylbenzene and various alkyl methacrylates (butyl-, octyl-, or lauryl-methacrylate), were developed as separation columns of benzophenone compounds for capillary electrochromatography (CEC). In addition to the presence of plenty of benzene moieties, the stationary phases contained long and flexible alkyl groups on the surface. With an increase in the molecular length of alkyl methacrylate, the polymeric monolith, which had higher hydrophobicity, effectively reduced the peak tailing of benzophenones, but a weaker retention was observed. The unusual phenomenon was likely due to the pi-pi interaction between the aromatic compound and the polymeric material. The usage of longer alkyl methacrylate as reaction monomer limited the retention of aromatic compounds on the stationary phase surface, thus the pi-pi interaction between them was possibly reduced. Consequently, the retention time of aromatic compounds was markedly decreased with an increase in carbon length of alkyl methacrylate that was carried on the polymeric monolith. Compared to previous reports on polystyrene-based columns in which the peak-tailing problem was reduced by decreasing the benzene moieties on the stationary phase, this study demonstrated that the undesirable retention (peak-tailing) could also be improved by the inclusion of long alkyl methacrylate to the polystyrene-based columns.

  15. Cytotoxic effects of acrylates and methacrylates: relationships of monomer structures and cytotoxicity.

    PubMed

    Yoshii, E

    1997-12-15

    Thirty-nine acrylates and methacrylates that had been used in dental resin materials were evaluated by a cytotoxicity test, and the relationships between their structures and cytotoxicity were studied to predict cytotoxic levels of dental resin materials in order to develop new low-toxic resin materials. All the acrylates evaluated were more toxic than corresponding methacrylates. In both the acrylates and methacrylates, a hydroxyl group seemed to enhance cytotoxicity. Dimethacrylates with 14 or fewer oxyethylene chains showed similar cytotoxicity while dimethacrylates with 23 oxyethylene chains showed lower cytotoxicity. The cytotoxicity ranking of monomers widely used in dental resin materials was bisphenol A bis 2-hydroxypropyl methacrylate (bisGMA) > urethane dimethacrylate (UDMA) > triethyleneglycol dimethacrylate (3G) > 2-hydroxyethyl methacrylate (HEMA) > methyl methacrylate (MMA). In acrylates, methacrylates, and ethylmethacrylates with either substituents, the lipophilicity of substituents affected their cytotoxicity, and an inverse correlation between IC50 and logP was observed. These results will be useful in developing new resin materials with low toxic monomer compositions.

  16. Synthesis and fluorescence properties of divalent europium-poly(methacrylate containing crown ether structure) complexes

    SciTech Connect

    Higashiyama, N.; Nakamura, H.; Mishima, T.; Shiokawa, J.; Adachi, G. )

    1991-02-01

    This paper reports on divalent europium complexes with poly(methacrylate containing crown ether structure)s, poly(crown ether)s, prepared and their fluorescence properties studied. The polymers used were poly(15-crown-5-methyl methacrylate) (PMA15C5), copoly(15- crown-5-methyl methacrylate-X) (copoly(MA15C5-X)); (X = MMA, EMA, BMA, 2-methoxyethyl methacrylate (MAGI) 3,6,9,12,15- pentaoxahexadecyl methacrylate (MAG5)), poly(18-crown-6- methyl methacrylate) (PMA18C6), and copoly(18-crown-6-methyl methacrylate-MMA) (copoly(MA18C6-MMA)), which were obtained by bulk polymerization. The fluorescence properties of Eu{sup 2+} polymers activated by complexing Eu{sup 2+} ions with crown ether groups were measured in powder form. The Eu{sup 2+}-poly (crown ether)s irradiated by UV light generally gave blue bright emission in the region of 420-465 nm. It was Eu{sup 2+}-copoly(Ma15C5-X); (X = MMA, EMA, and MAG1) that showed the largest emission intensity among the Eu{sup 2+} polymers, and its emission intensity was ca. 20% of that for CaWO{sub 4}:Pb (NBS1026) whose quantum efficiency is about 76%. The intensities of emission for the Eu{sup 2+} polymers containing 15-crown-5 were much larger than that for the ones containing 18-crown-6.

  17. Dye attached poly(hydroxyethyl methacrylate) cryogel for albumin depletion from human serum.

    PubMed

    Andac, Muge; Galaev, Igor; Denizli, Adil

    2012-05-01

    Cibacron Blue F3GA was immobilized on poly(hydroxyethyl methacrylate) cryogel and it was used for selective and efficient depletion of albumin from human serum. The poly(hydroxyethyl methacrylate) was selected as the basic component because of its inertness, mechanical strength, chemical and biological stability, and biocompatibility. Cibacron Blue F3GA was covalently attached to the poly(hydroxyethyl methacrylate) cryogel to produce poly(hydroxyethyl methacrylate)-Cibacron Blue F3GA cryogel affinity column. The poly(hydroxyethyl methacrylate)-Cibacron Blue F3GA cryogel was characterized with respect to gelation yield, swelling degree, total volume of macropores, Fourier Transform Infrared spectroscopy, and scanning electron microscopy. It was found that the maximum amount of adsorption (343 mg/g of dry cryogel) obtained from experimental results is very close to the calculated Langmuir adsorption capacity (345 mg/g of dry cryogel). The maximum adsorption capacity for poly(hydroxyethyl methacrylate)-Cibacron Blue F3GA cryogel column was obtained as 950 mg/g of dry cryogel for nondiluted serum. The adsorption capacity decreased with increasing dilution ratios while the depletion ratio of albumin remained as 77% in serum sample. Finally, the poly(hydroxyethyl methacrylate)-Cibacron Blue F3GA cryogel was optimized for using in the fast protein liquid chromatography system for rapid removal of the high abundant proteins from the human serum.

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

    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.

  19. A review of methods used to reinforce polymethyl methacrylate resin.

    PubMed

    Vallittu, P K

    1995-09-01

    Various methods to reinforce acrylic denture base material have been used to repair fractures in complete dentures. Metal wires and plates have been tested as reinforcement of polymethyl methacrylate (PMMA) resin. The contributions of the studies conducted on this biphase composite system are discussed in this review article. The literature has reported that even thin metal wires incorporated into the PMMA matrix increased the transverse strength of the PMMA construction. Metal mesh inserted into PMMA resin had negligible effects on the transverse strength of the restoration. macroscopic retention of the metal strengtheners to the PMMA had only a minor effect on the strength in contrast to microscopic retention, which showed a more marked effect. Chemical bonding between the PMMA and metal reinforcer enhanced the strength of the prosthesis with some exceptions.

  20. Methyl Methacrylate Polymerization in Nanoporous Matrix: Reactivity and Molecular Weight

    NASA Astrophysics Data System (ADS)

    Zhao, Haoyu; Simon, Sindee

    2011-03-01

    The influence of nanoconfinement on the free radical polymerization of methyl methacrylate is investigated. Nanoporous controlled pore glass (CPG) is used as a nanoconfining matrix for the polymerization. The reaction is followed by measuring heat flow as a function of reaction time during isothermal polymerization using differential scanning calorimetry (DSC). Preliminary results indicate several interesting effects for polymerization in 110 nm diameter pores: the induction time increases under nanoconfinement, the effective reaction rate constant increases, the effective activation energy is unchanged, and the gel effect or autoaccleration occurs at earlier times after induction. The latter result concerning the gel effect is presumably due to the decrease in diffusivity under nanoconfinement which results in a decrease in the termination rate of free radicals. The cause of the longer induction times and accelerated reaction rates just after induction are under investigation. The influence of nanoconfinement on molecular weight will also be examined.

  1. Interaction between N-vinylpyrrolidone and methyl methacrylate

    NASA Astrophysics Data System (ADS)

    Zaitseva, V. V.; Shtonda, A. V.; Tyurina, T. G.; Bagdasarova, A. R.; Zaitsev, S. Yu.

    2014-04-01

    It is established that the interaction of the isomers of N-vinylpyrrolidone (NVP) and methyl methacrylate (MMA) leads to the formation of molecular π-H- and H-complexes with energies within the limits of 10.2-13.6 (AM1) or 18.2-24.0 (B3LYP/6-311++G( d)) kJ/mol. The structures of complex-bound molecules are examined with respect to changes in the charges on terminal -C1=C2- groups, the distance between them and atoms in an H-bond, and the presence of combined overlapping molecular orbitals (MOs). The presence of an averaged complex that includes presumably all possible structures and allows us to perform the copolymerization of specified monomers in the absence of an initiator is confirmed by means of UV and NMR spectroscopy.

  2. Porous conductive polyblends of polyaniline in poly(methyl methacrylate)

    NASA Astrophysics Data System (ADS)

    Price, Aaron D.; Naguib, Hani E.

    2008-03-01

    The conductive polymer polyaniline is typically blended with conventional industrial thermoplastics in order to obtain an electrically conductive polymer blend with adequate mechanical properties. Processing these polyblends into foams yields a porous conductive material that exhibits immense application potential such as dynamic separation media and low-density electrostatic discharge protection. In the current study, the morphology of a thermally-processable blend consisting of an electrically conductive polyaniline-dodecylbenzene sulfonic acid complex and poly(methyl methacrylate) is explored using a two-phase batch foaming setup. The effect of blend composition and processing parameters on the resulting cellular morphology is investigated. Finally, the impact of the underlying microstructure on the frequency dependent electrical conductivity is elucidated.

  3. Radiation synthesis of nanosilver nanohydrogels of poly(methacrylic acid)

    NASA Astrophysics Data System (ADS)

    Gupta, Bhuvanesh; Gautam, Deepti; Anjum, Sadiya; Saxena, Shalini; Kapil, Arti

    2013-11-01

    Nanosilver nanohydrogels (nSnH) of poly(methacrylic acid) were synthesized and stabilized using gamma irradiation. The main objective of this study was to develop silver nanoparticles and to evaluate the antimicrobial activity. Radiation helps in the polymerization, crosslinking and reduction of silver nitrate as well. Highly stable and uniformly distributed silver nanoparticles have been obtained within hydrogel network by water in oil nanoemulsion polymerization and were evaluated by dynamic light scattering (DLS) and transmission electron microscopy (TEM) respectively. TEM showed almost spherical and uniform distribution of silver nanoparticles through the hydrogel network. The mean size of silver nanoparticles ranging is 10-50 nm. The nanohydrogels showed good swelling in water. Antibacterial studies of nSnH suggest that it can be a good candidate as coating material in biomedical applications.

  4. Chest wall reconstruction with methacrylate prosthesis in Poland syndrome.

    PubMed

    Arango Tomás, Elisabet; Baamonde Laborda, Carlos; Algar Algar, Javier; Salvatierra Velázquez, Angel

    2013-10-01

    Poland syndrome is a rare congenital malformation. This syndrome was described in 1841 by Alfred Poland at Guy's Hospital in London. It is characterized by hypoplasia of the breast and nipple, subcutaneous tissue shortages, lack of the costosternal portion of the pectoralis major muscle and associated alterations of the fingers on the same side. Corrective treatment of the chest and soft tissue abnormalities in Poland syndrome varies according to different authors. We report the case of a 17-year-old adolescent who underwent chest wall reconstruction with a methyl methacrylate prosthesis. This surgical procedure is recommended for large anterior chest wall defects, and it prevents paradoxical movement. Moreover it provides for individual remodeling of the defect depending on the shape of the patient's chest.

  5. Effect of trans-cis photoisomerization on phase equilibria and phase transition of liquid-crystalline azobenzene chromophore and its blends with reactive mesogenic diacrylate

    NASA Astrophysics Data System (ADS)

    Kim, Namil; Li, Quan; Kyu, Thein

    2011-03-01

    Photoisomerization-induced phase transition of neat liquid-crystalline azobenzene chromophore (LCAC) and its effect on phase diagrams of its mixtures with reactive mesogenic diacrylate monomer (RM257) have been investigated experimentally and theoretically. Upon irradiation with ultraviolet light, the nematic phase of LCAC transformed to isotropic, while the crystal phase showed corrugated textures on the surface (i.e., ripples). The phase-transition temperatures and corresponding morphologies of the blends have been investigated by means of differential scanning calorimetry and optical microscopy. A theoretical phase diagram of a binary nematic and crystalline system was constructed by self-consistently solving the combined free energies of Flory-Huggins, Maier-Saupe, and phase-field theory. The calculation revealed various coexistence regions such as nematic + liquid (N1 + L2), crystal + liquid (Cr1 + L2), crystal + nematic (Cr1 + N2), and crystal + crystal (Cr1 + Cr2) over a broad range of compositions including the single-phase nematic (N1, N2) of the corresponding constituents. The calculated liquidus lines were in good accord with the depressed mesophase-isotropic transition points. The present paper demonstrates the effect of trans-cis photoisomerization on the mesophase transitions of neat LCAC and the phase diagram of LCAC-RM257 as well as on the ripple formation (i.e., periodic undulation) on the azobenzene crystals.

  6. Effect of trans-cis photoisomerization on phase equilibria and phase transition of liquid-crystalline azobenzene chromophore and its blends with reactive mesogenic diacrylate.

    PubMed

    Kim, Namil; Li, Quan; Kyu, Thein

    2011-03-01

    Photoisomerization-induced phase transition of neat liquid-crystalline azobenzene chromophore (LCAC) and its effect on phase diagrams of its mixtures with reactive mesogenic diacrylate monomer (RM257) have been investigated experimentally and theoretically. Upon irradiation with ultraviolet light, the nematic phase of LCAC transformed to isotropic, while the crystal phase showed corrugated textures on the surface (i.e., ripples). The phase-transition temperatures and corresponding morphologies of the blends have been investigated by means of differential scanning calorimetry and optical microscopy. A theoretical phase diagram of a binary nematic and crystalline system was constructed by self-consistently solving the combined free energies of Flory-Huggins, Maier-Saupe, and phase-field theory. The calculation revealed various coexistence regions such as nematic + liquid (N₁ + L₂), crystal + liquid (Cr₁ + L₂), crystal + nematic (Cr₁ + N₂), and crystal + crystal (Cr₁ + Cr₂) over a broad range of compositions including the single-phase nematic (N₁, N₂) of the corresponding constituents. The calculated liquidus lines were in good accord with the depressed mesophase-isotropic transition points. The present paper demonstrates the effect of trans-cis photoisomerization on the mesophase transitions of neat LCAC and the phase diagram of LCAC-RM257 as well as on the ripple formation (i.e., periodic undulation) on the azobenzene crystals.

  7. Photoinduced dichroism and optical anisotropy in a liquid-crystalline azobenzene side chain polymer caused by anisotropic angular distribution of trans and cis isomers

    NASA Astrophysics Data System (ADS)

    Blinov, Lev M.; Kozlovsky, Mikhail V.; Ozaki, Masanori; Skarp, Kent; Yoshino, Katsumi

    1998-10-01

    Photochromism has been studied for two comb-like liquid-crystalline copolymers (I) and (II) containing azobenzene chromophores in their side chains. In a smectic glass phase of both copolymers, upon short-time irradiation by UV light, long-living cis isomers are observed. Both copolymers manifest the photoinduced anisotropy, the physical mechanisms of which seem to be quite different. In spin-coated films of polymer (II), the origin of the anisotropy is a strong stable dichroism, which is due to an enrichment and depletion of the chosen angular direction, correspondingly, with trans and cis isomers of the azobenzene chromophores. Polymer (I) manifests no dichroism at all, and its induced optical anisotropy may be accounted for by a rather slow chromophore reorientation. In copolymer (II) a considerable reorientation of the mesogenic groups also occurs as a secondary phenomenon at the stage of the cis isomer formation only. This observation shed more light on the general process of the light-induced molecular reorientation in polymers, liquid crystals, and Langmuir-Blodgett films, which is of great importance for holographic information recording.

  8. Synthesis of Methyl Methacrylate From Coal-Derived Syngas

    SciTech Connect

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

    1998-07-27

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

  9. Reactivity of Monovinyl (Meth)Acrylates Containing Cyclic Carbonates.

    PubMed

    Berchtold, Kathryn A; Nie, Jun; Stansbury, Jeffrey W; Bowman, Christopher N

    2008-12-09

    The tremendous diversity of materials properties available with polymers is due in large part to the ability to design structures from the monomeric state. The ease of use of comonomer mixtures only expands this versatility. While final polymer properties are obviously important in the selection or development of a material for a given purpose, for a number of applications, such as optical fiber coatings, photolithography and microelectronics, the additional requirement of a very rapid polymerization process may be equally critical. A class of unusually reactive mono-(meth)acrylate monomers bearing secondary functionality that includes carbonates, carbamates and oxazolidones, has been demonstrated but not fully explained. Here, the influence of an integral cyclic carbonate functional group on (meth)acrylate photopolymerization kinetics is examined in detail with respect to monomers with a wide variety of alternative secondary functionality structure as well as in comparison to conventional mono- and di-(meth)acrylates. The kinetic results from full cure studies of several cyclic carbonate-containing monomers clearly highlight specific structural variations that effectively promote monomer reactivity. Copolymerizations with tetrahydrofurfuryl methacrylate reflect similar dramatic kinetic effects associated with the novel monomers while partial cure homopolymerization studies reveal exceptional dark cure behavior linked to observations of uncommonly low ratios of termination to propagation rates throughout the conversion profile. Temperature effects on reaction kinetics, including both reaction rate and the individual kinetic parameters, as well as the temperature dependence of hydrogen bonding interactions specifically involving the secondary functional groups are probed as a means to understand better the fundamentally interesting and practically important behavior of these monomers.

  10. Vascular responsiveness to dimethylaminoethyl methacrylate and its degradation products.

    PubMed

    Abebe, Worku; Maddux, William F; Schuster, George S; Lewis, Jill B

    2003-07-01

    The increasing use of acrylate-based resins in dentistry has raised questions about the biocompatibility of these substances with oral tissues. The focus of the present investigation was to assess the responsiveness of blood vessels to the resin polymerization accelerating agent dimethylaminoethyl methacrylate (DMAEMA) and its degradation products dimethylethanolamine (DME) and methacrylic acid (MAA), using the rat aortic ring preparation as a tissue model. DMAEMA induced concentration-dependent relaxation of norepinephrine (NE)-contracted aortic rings with and without endothelium. N-nitro-L-arginine methyl ester (L-NAME) selectively inhibited the endothelium-dependent relaxation induced by DMAEMA, suggesting the release of nitric oxide from the endothelium by DMAEMA. Both indomethacin and glybenclamide attenuated the vasorelaxation elicited by DMAEMA in the presence as well as in the absence of endothelium, providing evidence for the role of vasorelaxant prostanoid(s) and K(ATP) channel activation in the responses observed. On the other hand, while MAA was without any apparent effect on the rat aorta, DMAEMA at high and DME at relatively low concentrations caused contraction of the tissues with and without endothelium in the absence of NE. The DME-induced contraction was inhibited by indomethacin, suggesting the involvement of contractile arachidonic acid metabolite(s) in the action of DME. This observation was supported by the findings of increased thromboxane A(2) (TXA(2)) production in aortic rings incubated with DME. Taken together, the data suggest that both DMAEMA and its degradation product, DME, are vasoactive, inducing vasorelaxation and contraction by various mechanisms that may involve the release of nitric oxide from the endothelium, the activation of smooth muscle K(ATP) channels, and the generation of vasorelaxant prostanoid(s) and TXA(2). These effects may play a role in tissue homeostasis and certain adverse conditions associated with the use of

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

    SciTech Connect

    1997-05-12

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

  12. Protein based Block Copolymers

    PubMed Central

    Rabotyagova, Olena S.; Cebe, Peggy; Kaplan, David L.

    2011-01-01

    Advances in genetic engineering have led to the synthesis of protein-based block copolymers with control of chemistry and molecular weight, resulting in unique physical and biological properties. The benefits from incorporating peptide blocks into copolymer designs arise from the fundamental properties of proteins to adopt ordered conformations and to undergo self-assembly, providing control over structure formation at various length scales when compared to conventional block copolymers. This review covers the synthesis, structure, assembly, properties, and applications of protein-based block copolymers. PMID:21235251

  13. Manufacture of poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) hydrogel tubes for use as nerve guidance channels.

    PubMed

    Dalton, Paul D; Flynn, Lauren; Shoichet, Molly S

    2002-09-01

    Hydrogel tubes of poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) (p(HEMA-co-MMA)) made by liquid-liquid centrifugal casting are being investigated as potential nerve guidance channels in the central nervous system. An important criterion for the nerve guidance channel is that its mechanical properties are similar to those of the spinal cord, where it will be implanted. The formulated p(HEMA-co-MMA) tubes are soft and flexible, consisting of a gel-like outer layer, and an interconnected macroporous, inner layer. The relative thickness of the gel phase to macroporous phase is controlled by the formulation chemistry, and specifically by the ratio of co-monomers, HEMA and MMA. By varying the surface chemistry of the mold within which the tubes are synthesized, tubes were prepared with either a "cracked" or a smooth outer morphology. Tubes with the cracked outer morphology had periodic channels that traversed the wall of the tube, which resulted in a lower modulus than smooth outer morphology tubes, yet likely greater diffusive permeability. For tubes (and not rods) to be formed, phase separation must precede gelation as is detailed in a formulation phase diagram for HEMA, MMA and water. The tensile elastic modulus of p(HEMA-co-MMA) tubes reflected the formulation chemistry, with greater moduli (up to 400 kPa) recorded for tubes having 10 wt% MMA. The p(HEMA-co-MMA) tubes therefore had similar mechanical properties to those of the spinal cord, which has a reported elastic modulus range between 200 and 600 kPa.

  14. Monitoring of acid-base status of workers at a methyl methacrylate and polymethyl methacrylate production plant in Bulgaria.

    PubMed

    Prakova, Gospodinka R

    2003-01-01

    This study was carried out on 104 workers at three work operations and a control (nonproduction) area, within a methyl methacrylate (MMA)/polymethyl methacrylate (PMMA) production facility in Bulgaria. Airborne monitoring was conducted over a 10-year period for MMA and the reactant chemicals methanol and acetone cyanhydrine at the MMA operation, and MMA was monitored at the PMMA operation. Acid-base status of the workers was evaluated using traditional criteria (pH, pCO(2), pO(2), and HCO(3) in plasma). Data from retrospective monitoring of air levels of the chemicals were compared with the acid-base status of workers at the plant. In some cases air concentrations exceeded the threshold limit value, with the highest percentage of overexposure occurring with airborne MMA in the PMMA production operation. Acid-base disruption indicated by reductions in plasma pH and HCO(3) was found for all groups except the control population. The highest percentage reduction was associated with PMMA production workers. Additionally, respiratory acidosis, indicated by increased pCO(2), was noted in the MMA production and maintenance groups, implying that the response to MMA exposure may involve both the metabolic and respiratory acidosis component. This study was unique in that the combined exposure to MMA and the precursor chemical (methanol) were shown to produce the same effects in workers. It is suggested that when combined exposure occurs, disruption of acid-base status may occur. Enforcement of PPM requirements for coveralls and gloves should prevent skin contamination. Additionally, improvement of equipment in MMA and PMMA production areas is recommended: (1) automation of some manual operations; (2) use of respiratory protection during equipment cleaning; and (3) installation of local ventilation when applicable.

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

    PubMed Central

    ISAAC, Stephano Zerlottini; BERGAMIN, Ana Claudia Pietrobom; TURSSI, Cecília Pedroso; do AMARAL, Flávia Lucisano Botelho; BASTING, Roberta Tarkany; FRANÇA, Fabiana Mantovani Gomes

    2013-01-01

    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 (p<0.05). No statistical difference between restorative systems was shown for Class I cavity model (p>0.05), 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. PMID:24212992

  16. Thermally actuated wedge block

    DOEpatents

    Queen, Jr., Charles C.

    1980-01-01

    This invention relates to an automatically-operating wedge block for maintaining intimate structural contact over wide temperature ranges, including cryogenic use. The wedging action depends on the relative thermal expansion of two materials having very different coefficients of thermal expansion. The wedge block expands in thickness when cooled to cryogenic temperatures and contracts in thickness when returned to room temperature.

  17. Poly(2-hydroxyethyl methacrylate) for enzyme immobilization: impact on activity and stability of horseradish peroxidase.

    PubMed

    Lane, Sarah M; Kuang, Zhifeng; Yom, Jeannie; Arifuzzaman, Shafi; Genzer, Jan; Farmer, Barry; Naik, Rajesh; Vaia, Richard A

    2011-05-09

    On the basis of their versatile structure and chemistry as well as tunable mechanical properties, polymer brushes are well-suited as supports for enzyme immobilization. However, a robust surface design is hindered by an inadequate understanding of the impact on activity from the coupling motif and enzyme distribution within the brush. Herein, horseradish peroxidase C (HRP C, 44 kDa), chosen as a model enzyme, was immobilized covalently through its lysine residues on a N-hydroxysuccinimidyl carbonate-activated poly(2-hydroxyethyl methacrylate) (PHEMA) brush grafted chemically onto a flat impenetrable surface. Up to a monolayer coverage of HRP C is achieved, where most of the HRP C resides at or near the brush-air interface. Molecular modeling shows that lysines 232 and 241 are the most probable binding sites, leading to an orientation of the immobilized HRP C that does not block the active pocket of the enzyme. Michaelis-Menten kinetics of the immobilized HRP C indicated little change in the K(m) (Michaelis constant) but a large decrease in the V(max) (maximum substrate conversion rate) and a correspondingly large decrease in the k(cat) (overall catalytic rate). This indicates a loss in the percentage of active enzymes. Given the relatively ideal geometry of the HRPC-PHEMA brush, the loss of activity is most likely due to structural changes in the enzyme arising from either secondary constraints imposed by the connectivity of the N-hydroxysuccinimidyl carbonate linking moiety or nonspecific interactions between HRP C and DSC-PHEMA. Therefore, a general enzyme-brush coupling motif must optimize reactive group density to balance binding with neutrality of surroundings.

  18. Incorporation of polymerizable surfactants in hydroxyethyl methacrylate lenses for improving wettability and lubricity.

    PubMed

    Bengani, Lokendrakumar C; Scheiffele, Gary W; Chauhan, Anuj

    2015-05-01

    Dryness and discomfort are the main reasons for dropouts in contact lens wearers. Incorporating surfactants in lens formulations could improve wettability and lubricity, which can improve comfort. We have focused on incorporating polymerizable surfactants in hydroxyethyl methacrylate lenses to improve comfort, while minimizing the potential for surfactant release into the tears. The surfactants were added to the polymerization mixture, followed by UV curing and extraction of leachables in hot water. Wettability and lubricity were characterized by measuring the contact angle and coefficient of friction. Lenses were also characterized by measuring transmittance, loss and storage moduli and ion permeability. Incorporation of surfactants significantly reduced contact angle from 90° for p-HEMA gels to about 10° for 2.43% (w/w) surfactant loading in hydrated gel. The coefficient of friction also decreased from about 0.16 for HEMA gels to 0.05 for the gels with 2.43% surfactant loading. There was a good correlation between the contact angle and coefficient of friction suggesting that both effects can be related to the stretching of the surfactant tails near the surface into the aqueous phase. The water content was also correlated with the surfactant loading but the contact angle was more sensitive suggesting that the observed improvements in wettability and lubricity arise from the protrusion of the surfactant tails in into the liquid, and not purely from the increase in the water content. The gels were clear and certain compositions also have the capability to block UVC and UVB radiation. The results suggest that incorporation of polymerizable surfactants could be useful in improving surface properties without significantly impacting any bulk property.

  19. Radical Polymerization of Vinyl Acetate and Methyl Methacrylate Using Organochromium Initiators Complexed with Macrocyclic Polyamines

    DTIC Science & Technology

    1994-06-30

    METHYL METHACRYLATE USING ORGANOCHROMIUM REA NTS COMPLEXED WITH MACROCYCLIC A• by Daniela Mardare, Scott Gaynor, Krzysztof Matyjaszewski DTIC Published... Daniela Mardare, Scott Gaynor, Krzysztof Matyjaszewski 7. PERFORMING ORGANIZATION NAME(S) AND ADORESS(ES) a. PERFORMING ORGANIZATION Carnegie Mellon

  20. Amphiphilic copolymers of sucrose methacrylate and acrylic monomers: bio-based materials from renewable resource.

    PubMed

    de Oliveira, Heitor F N; Felisberti, Maria Isabel

    2013-04-15

    Regioselective sucrose 1'-O-methacrylate obtained by transesterification catalyzed by Proteinase-N was copolymerized with hydrophilic N-isopropylacrylamide and hydrophobic methyl methacrylate in different molar ratios by free radical polymerization. The copolymers were characterized by (13)C nuclear magnetic resonance spectroscopy, gel permeation chromatography, differential scanning calorimetry and thermogravimetry. Solubility and phase behavior of aqueous solutions were also investigated. The glass transition of the copolymers presents a positive deviation from the values of the homopolymers due to the high density of inter and intramolecular hydrogen bonding. Their solubility is strongly dependent on the composition. Copolymers poor in methyl methacrylate are water soluble, while copolymers richer in methyl methacrylate behaves as hydrogel. These hydrogels are not chemically crosslinked and their form can be design prior swelling by the conventional processing methods, such as solvent casting and extrusion for instance. Copolymers of N-isopropylacrylamide are water soluble and their aqueous solutions present a lower critical solution temperature behavior forming thermoreversible hydrogels.

  1. Biomimetic potential of some methacrylate-based copolymers: a comparative study.

    PubMed

    Zecheru, Teodora; Filmon, Robert; Rusen, Edina; Mărculescu, Bogdan; Zerroukhi, Amar; Cincu, Corneliu; Chappard, Daniel

    2009-11-01

    Preparation of new biocompatible materials for bone recovery has consistently gained interest in the last few decades. Special attention was given to polymers that contain negatively charged groups, such as phosphate, carboxyl, and sulfonic groups toward calcification. This present paper work demonstrates that other functional groups present also potential application in bone pathology. New copolymers of 2-hydroxyethyl methacrylate with diallyldimethylammonium chloride (DADMAC), glycidyl methacrylate (GlyMA), methacrylic acid (MAA), 2-methacryloyloxymethyl acetoacetate (MOEAA), 2-methacryloyloxyethyltriethylammonium chloride (MOETAC), and tetrahydrofurfuryl methacrylate (THFMA) were obtained. The copolymers were characterized by FTIR, swelling potential, and they were submitted to in vitro tests for calcification and cytotoxicity evaluation. GlyMA and MOETAC-containing copolymers show promising results for further in vivo mineralization tests, as a potential alternative to the classical bone grafts, in bone tissue engineering.

  2. Estimation of monomer content in polymethyl methacrylate contact lens materials by Raman spectroscopy.

    PubMed

    Kantarci, Z; Aksoy, S; Hasirci, N

    1997-07-01

    Polymethyl methacrylate is the most commonly used contact lens material due to its excellent optical properties. However the presence of residual monomer in the structure alters its transparency as well as its biocompatibility, thus, there is a need to detect any remaining methyl methacrylate. Raman spectroscopy is a rapid, sensitive, and non destructive method as compared to other spectroscopic, chromatographic or polarographic methods. In this study, the spectra of some lens materials (prepared from methyl methacrylate, 2-hydroxy ethyl methacrylate, Hexamethyl disiloxane and polypropylene glycol with or without the addition of crosslinker ethylene glycol dimethylacrylate) were obtained by Raman spectroscopy. It was observed that an amount of crosslinker present in the structure proves effective for the unpolymerized monomer content. None of the samples, except those containing nexamethyl disiloxane, demonstrated any monomer residue.

  3. 40 CFR 721.10517 - Alkyl methacrylates, polymer with substituted carbomonocycle, hydroxymethyl acrylamide and...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... substituted carbomonocycle, hydroxymethyl acrylamide and fluorinatedalkyl acrylate (generic). 721.10517... Substances § 721.10517 Alkyl methacrylates, polymer with substituted carbomonocycle, hydroxymethyl acrylamide... substituted carbomonocycle, hydroxymethyl acrylamide and fluorinatedalkyl acrylate (PMN P-10-485) is...

  4. 40 CFR 721.10517 - Alkyl methacrylates, polymer with substituted carbomonocycle, hydroxymethyl acrylamide and...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... substituted carbomonocycle, hydroxymethyl acrylamide and fluorinatedalkyl acrylate (generic). 721.10517... Substances § 721.10517 Alkyl methacrylates, polymer with substituted carbomonocycle, hydroxymethyl acrylamide... substituted carbomonocycle, hydroxymethyl acrylamide and fluorinatedalkyl acrylate (PMN P-10-485) is...

  5. Nitroxide-mediated radical ring-opening copolymerization: chain-end investigation and block copolymer synthesis.

    PubMed

    Delplace, Vianney; Harrisson, Simon; Tardy, Antoine; Gigmes, Didier; Guillaneuf, Yohann; Nicolas, Julien

    2014-02-01

    Well-defined, degradable copolymers are successfully prepared by nitroxide-mediated radical ring opening polymerization (NMrROP) of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) or methyl methacrylate (MMA), a small amount of acrylonitrile (AN) and cyclic ketene acetals (CKAs) of different structures. Phosphorous nuclear magnetic resonance allows in-depth chain-end characterization and gives crucial insights into the nature of the copoly-mer terminal sequences and the living chain fractions. By using a small library of P(OEGMA-co-AN-co-CKA) and P(MMA-co-AN-co-CKA) as macroinitiators, chain extensions with styrene are performed to furnish (amphiphilic) block copolymers comprising a degradable segment.

  6. Preparation of Optically Transparent Films of Poly(methyl methacrylate) (PMMA) and Montmorillonite

    DTIC Science & Technology

    2001-11-01

    methacrylate] [PMMA] and Montmorillonite DISTRIBUTION: Approved for public release, distribution unlimited This paper is part of the following report...Society V6.4 Preparation of Optically Transparent Films of Poly(methyl methacrylate) (PMMA) and Montmorillonite Elena Vasiliul, Chyi-Shan Wang"’ 2...exchanged with 1.40 meq/g of dimethyl dehydrogenated tallow ammonium from a sodium montmorillonite , Cloisite Na+ (CNa). Since the cation-exchange

  7. Reordering transitions during annealing of block copolymer cylinder phases

    DOE PAGES

    Majewski, Pawel W.; Yager, Kevin G.

    2015-10-06

    While equilibrium block-copolymer morphologies are dictated by energy-minimization effects, the semi-ordered states observed experimentally often depend on the details of ordering pathways and kinetics. In this study, we explore reordering transitions in thin films of block-copolymer cylinder-forming polystyrene-block-poly(methyl methacrylate). We observe several transient states as films order towards horizontally-aligned cylinders. In particular, there is an early-stage reorganization from randomly-packed cylinders into hexagonally-packed vertically-aligned cylinders; followed by a reorientation transition from vertical to horizontal cylinder states. These transitions are thermally activated. The growth of horizontal grains within an otherwise vertical morphology proceeds anisotropically, resulting in anisotropic grains in the final horizontalmore » state. The size, shape, and anisotropy of grains are influenced by ordering history; for instance, faster heating rates reduce grain anisotropy. These results help elucidate aspects of pathway-dependent ordering in block-copolymer thin films.« less

  8. Synthesis of Acrylates and Methacrylates from Coal-Derived Syngas.

    SciTech Connect

    Gogate, M.R.; Spivey, J.J.; Zoeller, J.R.; Colberg, R.D.; Choi, G.N.; Tam, S.S.

    1997-10-17

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas, under a contract from the U.S. Department of Energy/Federal Energy Technology Center (DOE/FETC). This three-step process consists of synthesis of a propionate, its condensation with formaldehyde, and esterification of resulting methacrylic acid (MAA) with methanol to produce MMA. Over the last quarter, RTI carried out activity tests on a pure (99 percent) Nb{sub 2}O{sub 5} catalyst, received from Alfa Aesar, under the following experimental conditions: T=300 C; P=4 atm, 72:38:16:4:220 mmol/h, PA:H{sub 2}0:HCHO:CH{sub 3}0H:N{sub 2}; 5-g catalyst charge. For the pure material, the MAA yields (based on HCHO and PA) were at 8.8 and 1.5 percent, clearly inferior compared to those for a 10-percent Nb{sub 2}O{sub 5}/Si0{sub 2} catalyst (20.1 and 4.5 percent). The X-ray diffraction (XRD) patterns of pure Nb{sub 2}O{sub 5} and 20-percent Nb{sub 2}O{sub 5}/Si0{sub 2} that while pure Nb{sub 2}O{sub 5} is very highly crystalline, Si0{sub 2} support for an amorphous nature of the 20 percent Nb{sub 2}O{sub 5}/Si0{sub 2} catalyst the last quarter, RTI also began research on the use of dimethyl ether (DME), product of methanol dehydrocondensation, as an alternate feedstock in MMA synthesis. As a result, formaldehyde is generated either externally or in situ, from DME, in the process envisaged in the contract extension. The initial work on the DME extension of the contract focuses on a tradeoff analysis that will include a preliminary economic analysis of the DME and formaldehyde routes and catalyst synthesis and testing for DME partial oxidation and condensation reactions. Literature guides exist for DME partial oxidation catalysts; however, there are no precedent studies on catalyst development for DME-methyl propionate (MP) condensation reactions, thereby making DME-MP reaction studies a

  9. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect

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

    1999-07-19

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. The research team has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, we are currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. During the April-June quarter(04-06/99) the first in-situ formaldehyde generation from DME and condensation with methyl propionate is demonstrated and the results are summarized. The supported niobium catalyst shows better condensation activity, but supported tungsten catalyst has higher formaldehyde selectivity. The project team has also completed a 200-hour long term test of PA-HCHO condensation over 30% Nb{sub 2}O{sub 5}/SiO{sub 2}. Three activity cycles and two regeneration cycles were carried out. 30% Nb{sub 2}O{sub 5}/SiO{sub 2} showed similar MAA yields as 10% Nb{sub 2}O{sub 5}/SiO{sub 2} at 300 C. However, the deactivation appears to be slower with 30% Nb{sub 2}O{sub 5}/SiO{sub 2} than 10% Nb{sub 2}O{sub 5}/SiO{sub 2}. An detailed economic analysis of PA-HCHO condensation process for a 250 million lb/yr MMA plant is currently studied by Bechtel. Using the Amoco data-based azeotropic distillation model as the basis, an ASPEN flow sheet model was constructed to simulate the formaldehyde and propionic acid condensation processing section based on RTI's design data. The RTI MAA effluent azeotropic distillation column was found to be much more difficult to converge. The presence of non-condensible gases along with the byproduct DEK (both of which were not presented in

  10. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect

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

    1998-10-20

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. RTI has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, RTI is currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last quarter (July-September, 1998), the project team has completed the continuous condensation of formaldehyde with propionic acid over 10% Nb{sub 2}O{sub 5}/SiO{sub 2} at 300 C. Six activity and five regeneration cycles have been completed. The results show that 10% Nb{sub 2}O{sub 5}/SiO{sub 2} deactivates slowly with time but can be regenerated to its original activity with 2% O{sub 2} in nitrogen over night at 400 C. We have investigated the effects of regeneration, propionic acid/formaldehyde ratio (PA/HCHO = 4.5/1 to 1.5/1) and reaction temperature(280-300 C) on reaction activity and product selectivity over 20% Nb{sub 2}O{sub 5}/SiO{sub 2} catalysts. The regeneration effect on 20% Nb{sub 2}O{sub 5}/SiO{sub 2} is similar to the effect on 10% Nb{sub 2}O{sub 5}/SiO{sub 2}. The regeneration can bring the deactivated catalyst to its original activity. However, the selectivity to MAA decreases with regeneration while the selectivity to DEK and CO{sub 2} increases. When PA/HCHO ratio is decreased from 4.5/1 to 2.25/1 then to 1.5/1 at 300 C the MAA yield decreases but the MAA selectivity first increases then decreases. Decreasing the reaction temperature from 300 C to 280 C decreases the MAA yield from 39.5% to 30.7% but increases the MAA selectivity from 73.7% to 82.2%. The

  11. Novel catalysts for the environmentally friendly synthesis of methyl methacrylate

    SciTech Connect

    Spivey, J.J.; Gogate, M.R.; Zoeller, J.R.; Colberg, R.D.

    1997-11-01

    The development of a process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas can alleviate the environmental hazards associated with the current commercial MMA technology, the acetone cyanohydrin (ACH) process. A three-step syngas-based process consisted of synthesis of a propionic acid, its condensation with formaldehyde, and esterification of resulting methacrylic acid (MAA) to form MMA. The first two steps, propionic acid synthesis and condensation, are discussed here. The low-temperature, low-pressure process for single-step hydrocarbonylation of ethylene to propionic acid is carried out using a homogeneous iodine-promoted Mo(CO){sub 6} catalyst at pressures (30--70 atm) and temperatures (150--200 C) lower than those reported for other catalysts. Mechanistic investigations suggest that catalysis is initiated by a rate-limiting CO dissociation from Mo(CO){sub 6}. This dissociation appears to be followed by an inner electron-transfer process of an I atom from EtI to the coordinately unsaturated Mo(CO){sub 5}. This homogeneous catalyst for propionate synthesis represents the first case of an efficient carbonylation process based on Cr group metals. The condensation of formaldehyde with propionic acid is carried out by acid-base bifunctional catalysts. As a result of screening over 80 catalytic materials, group V metals supported on an amorphous silica are found to be most effective. A 20% Nb/SiO{sub 2} catalyst appears to be the most active and stable catalyst thus far. Preliminary relations among the reaction yield and catalyst properties indicate that a high surface area and a low overall surface acidity (<50 = mol of NH{sub 3}/g), with a high proportion of the acidity being weak (<350 C desorption of NH{sub 3}), are desirable. Long-term deactivation of V-Si-P, Nb-Si, and Ta-Si catalysts suggests that carbon deposition is the primary cause for activity decay, and the catalyst activity is partially restorable by oxidative regeneration.

  12. Cholesterol-modified superporous poly(2-hydroxyethyl methacrylate) scaffolds for tissue engineering.

    PubMed

    Kubinová, Sárka; Horák, Daniel; Syková, Eva

    2009-09-01

    Modifications of poly(2-hydroxyethyl methacrylate) (PHEMA) with cholesterol and laminin have been developed to design scaffolds that promote cell-surface interaction. Cholesterol-modified superporous PHEMA scaffolds have been prepared by the bulk radical copolymerization of 2-hydroxyethyl methacrylate (HEMA), cholesterol methacrylate (CHLMA) and the cross-linking agent ethylene dimethacrylate (EDMA) in the presence of ammonium oxalate crystals to introduce interconnected superpores in the matrix. With the aim of immobilizing laminin (LN), carboxyl groups were also introduced to the scaffold by the copolymerization of the above monomers with 2-[(methoxycarbonyl)methoxy]ethyl methacrylate (MCMEMA). Subsequently, the MCMEMA moiety in the resulting hydrogel was hydrolyzed to [2-(methacryloyloxy)ethoxy]acetic acid (MOEAA), and laminin was immobilized via carbodiimide and N-hydroxysulfosuccinimide chemistry. The attachment, viability and morphology of mesenchymal stem cells (MSCs) were evaluated on both nonporous and superporous laminin-modified as well as laminin-unmodified PHEMA and poly(2-hydroxyethyl methacrylate-co-cholesterol methacrylate) P(HEMA-CHLMA) hydrogels. Neat PHEMA and laminin-modified PHEMA (LN-PHEMA) scaffolds facilitated MSC attachment, but did not support cell spreading and proliferation; the viability of the attached cells decreased with time of cultivation. In contrast, MSCs spread and proliferated on P(HEMA-CHLMA) and LN-P(HEMA-CHLMA) hydrogels.

  13. Control of Protein Affinity of Bioactive Nanocellulose and Passivation Using Engineered Block and Random Copolymers.

    PubMed

    Vuoriluoto, Maija; Orelma, Hannes; Zhu, Baolei; Johansson, Leena-Sisko; Rojas, Orlando J

    2016-03-02

    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.

  14. Preparation and icephobic properties of polymethyltrifluoropropylsiloxane-polyacrylate block copolymers

    NASA Astrophysics Data System (ADS)

    Li, Xiaohui; Zhao, Yunhui; Li, Hui; Yuan, Xiaoyan

    2014-10-01

    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.

  15. Types of Heart Block

    MedlinePlus

    ... is less serious than Mobitz type II. The animation below shows how your heart's electrical system works. ... block. Click the "start" button to play the animation. Written and spoken explanations are provided with each ...

  16. Superalloy Lattice Block Structures

    NASA Technical Reports Server (NTRS)

    Nathal, M. V.; Whittenberger, J. D.; Hebsur, M. G.; Kantzos, P. T.; Krause, D. L.

    2004-01-01

    Initial investigations of investment cast superalloy lattice block suggest that this technology will yield a low cost approach to utilize the high temperature strength and environmental resistance of superalloys in lightweight, damage tolerant structural configurations. Work to date has demonstrated that relatively large superalloy lattice block panels can be successfully investment cast from both IN-718 and Mar-M247. These castings exhibited mechanical properties consistent with the strength of the same superalloys measured from more conventional castings. The lattice block structure also accommodates significant deformation without failure, and is defect tolerant in fatigue. The potential of lattice block structures opens new opportunities for the use of superalloys in future generations of aircraft applications that demand strength and environmental resistance at elevated temperatures along with low weight.

  17. What Causes Heart Block?

    MedlinePlus

    ... of congenital heart block occurs in babies whose mothers have autoimmune diseases, such as lupus. People who have these diseases make proteins called antibodies that attack and damage the body's tissues or ...

  18. Blocked tear duct

    MedlinePlus

    ... your baby may have an eye infection called conjunctivitis . ... increase the chance of other infections, such as conjunctivitis. ... be prevented. Proper treatment of nasal infections and conjunctivitis may reduce the risk of having a blocked ...

  19. Resolving writer's block.

    PubMed Central

    Huston, P.

    1998-01-01

    PROBLEM BEING ADDRESSED: Writer's block, or a distinctly uncomfortable inability to write, can interfere with professional productivity. OBJECTIVE OF PROGRAM: To identify writer's block and to outline suggestions for its early diagnosis, treatment, and prevention. MAIN COMPONENTS OF PROGRAM: Once the diagnosis has been established, a stepwise approach to care is recommended. Mild blockage can be resolved by evaluating and revising expectations, conducting a task analysis, and giving oneself positive feedback. Moderate blockage can be addressed by creative exercises, such as brainstorming and role-playing. Recalcitrant blockage can be resolved with therapy. Writer's block can be prevented by taking opportunities to write at the beginning of projects, working with a supportive group of people, and cultivating an ongoing interest in writing. CONCLUSIONS: Writer's block is a highly treatable condition. A systematic approach can help to alleviate anxiety, build confidence, and give people the information they need to work productively. PMID:9481467

  20. Mid-Career Block.

    ERIC Educational Resources Information Center

    Payne, Richard A.

    1984-01-01

    Considers typical reactions of midcareer employees to blocked opportunity; reasons for correcting these attitudes; ways of motivating these employees; methods of rekindling midcareer employees' interest in their jobs; encouraging competition; job switching; self-development programs; and supervisory attitudes. (CT)

  1. Block copolymer battery separator

    SciTech Connect

    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.

  2. View of cell block eight (left), cell block seven, and ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    View of cell block eight (left), cell block seven, and southwest guard tower, looking from cell block eight roof - Eastern State Penitentiary, 2125 Fairmount Avenue, Philadelphia, Philadelphia County, PA

  3. Cell block eleven (left) and cell block fifteen, looking from ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Cell block eleven (left) and cell block fifteen, looking from cell block two into the "Death Row" exercise yard - Eastern State Penitentiary, 2125 Fairmount Avenue, Philadelphia, Philadelphia County, PA

  4. Synthesis and properties of methacrylic-functionalized tween monomer networks.

    PubMed

    Muzzalupo, Rita; Tavano, Lorena; Rossi, Cesare Oliviero; Cassano, Roberta; Trombino, Sonia; Picci, Nevio

    2009-02-03

    Tween surfactants possess very interesting properties such as biodegradability, biocompatibility, and low toxicity. The synthesis of acrylate monomers by means of the chemical modification of polysorbate surfactants Tween 20, 40, and 60 with unsaturated groups is described. Monomers were obtained as a result of the reaction of methacrylic anhydride with different grades of Tween surfactants. Further polymerization was carried out in tetrahydrofuran, dimethylformamide, and a mixture of water-tetrahydrofuran. Physicochemistry properties of the polymer networks were investigated, and the obtained results reveal that they strongly depend on the type of solvent used during the polymerization, as well as on the concentration of the casting solution. In particular, our study demonstrated that, depending on the solvent boiling point, i.e., the facility to remove the solvent from the polymer matrix, it is possible to predict properties of the network morphology. Moreover, in vitro studies on controlled release were accomplished to demonstrate the possibility of utilizing these new materials as drug delivery systems. All resulting networks represent a novel class of cross-linked polymeric materials useful both in pharmaceutical and chemical applications.

  5. Methyl methacrylate and respiratory sensitization: A Critical review

    PubMed Central

    Borak, Jonathan; Fields, Cheryl; Andrews, Larry S; Pemberton, Mark A

    2011-01-01

    Methyl methacrylate (MMA) is a respiratory irritant and dermal sensitizer that has been associated with occupational asthma in a small number of case reports. Those reports have raised concern that it might be a respiratory sensitizer. To better understand that possibility, we reviewed the in silico, in chemico, in vitro, and in vivo toxicology literature, and also epidemiologic and occupational medicine reports related to the respiratory effects of MMA. Numerous in silico and in chemico studies indicate that MMA is unlikely to be a respiratory sensitizer. The few in vitro studies suggest that MMA has generally weak effects. In vivo studies have documented contact skin sensitization, nonspecific cytotoxicity, and weakly positive responses on local lymph node assay; guinea pig and mouse inhalation sensitization tests have not been performed. Cohort and cross-sectional worker studies reported irritation of eyes, nose, and upper respiratory tract associated with short-term peaks exposures, but little evidence for respiratory sensitization or asthma. Nineteen case reports described asthma, laryngitis, or hypersensitivity pneumonitis in MMA-exposed workers; however, exposures were either not well described or involved mixtures containing more reactive respiratory sensitizers and irritants.The weight of evidence, both experimental and observational, argues that MMA is not a respiratory sensitizer. PMID:21401327

  6. Methyl Methacrylate Polymerization in Nanoporous Matrix: Reactivity and Resulting Properties

    NASA Astrophysics Data System (ADS)

    Zhao, Haoyu; Begum, Fatema; Simon, Sindee

    2012-02-01

    Nanoconfinement is well known to affect the properties of polymers, including changes in the glass transition temperature (Tg). In this work, the focus is on the influence of nanoconfinement on free radical polymerization reaction kinetics and the properties of the polymer produced. Controlled pore glass (CPG) is used as a nanoconfining matrix for methyl methacrylate (MMA) polymerization with pore diameters of 13 nm, 50 nm, and 110 nm. The reaction is followed by measuring heat flow as a function of reaction time during isothermal polymerization at temperatures ranging from 60 C to 95 C using differential scanning calorimetry (DSC). After reaction, the properties of the polymer are measured, including Tg, molecular weight, and tacticity. Nanoconfiment is found to result in earlier onset of autoacceleration, presumablely due to a decrease in the rate of termination arising from decreases in chain diffusivity in the confined state. In addition, Tg and molecular weight of the resulting PMMA are found to increase. A model of the nanoconfined reaction is able to quantitatively capture these effects by accounting for changes in chain diffusivity, and in native pores, also accounting for changes in intrinsic reaction rates.

  7. Directed Endothelial Cell Morphogenesis in Micropatterned Gelatin Methacrylate Hydrogels

    PubMed Central

    Nikkhah, Mehdi; Eshak, Nouran; Zorlutuna, Pinar; Annabi, Nasim; Castello, Marco; Kim, Keekyoung; Dolatshahi-Pirouz, Alireza; Edalat, Faramarz; Bae, Hojae; Yang, Yunzhi; Khademhosseini, Ali

    2013-01-01

    Engineering of organized vasculature is a crucial step in the development of functional and clinically relevant tissue constructs. A number of previous techniques have been proposed to spatially regulate the distribution of angiogenic biomolecules and vascular cells within biomaterial matrices to promote vascularization. Most of these approaches have been limited to two-dimensional (2D) micropatterned features or have resulted in formation of random vasculature within three-dimensional (3D) microenvironments. In this study, we investigate 3D endothelial cord formation within micropatterned gelatin methacrylate (GelMA) hydrogels with varying geometrical features (50–150 µm height). We demonstrated the significance dependence of endothelial cells proliferation, alignment and cord formation on geometrical dimensions of the patterned features. The cells were able to align and organize within the micropatterned constructs and assemble to form cord structures with organized actin fibers and circular/elliptical cross-sections. The inner layer of the cord structure was filled with gel showing that the micropatterned hydrogel constructs guided the assembly of endothelial cells into cord structures. Notably, the endothelial cords were retained within the hydrogel microconstructs for all geometries after two weeks of culture; however, only the 100 µm-high constructs provided the optimal microenvironment for the formation of circular and stable cord structures. Our findings suggest that endothelial cord formation is a preceding step to tubulogenesis and the proposed system can be used to develop organized vasculature for engineered tissue constructs. PMID:23018132

  8. The toxicokinetics and distribution of 2-hydroxyethyl methacrylate in mice.

    PubMed

    Durner, J; Kreppel, H; Zaspel, J; Schweikl, H; Hickel, R; Reichl, Franz X

    2009-04-01

    The cytotoxicity of dental composites has been attributed to the release of residual monomers from polymerized resin-based composites due to the degradation processes or the incomplete polymerisation of materials. 2-Hydroxyethyl methacrylate (HEMA) is one of the major components released from dental resin-based composites. It was shown in vitro that HEMA was released into the adjacent biophase from such materials during the first days after placement. In this study uptake, distribution, and excretion of 14C-HEMA applied via gastric tube or subcutaneous administration at dose levels well above those encountered in dental care were examined in mice to test the hypothesis that HEMA can reach cytotoxic levels in mammalian tissues. 14C-HEMA was taken up rapidly from the stomach and intestines after gastric administration and was widely distributed in the body following administration by each route. Most 14C was excreted within one day as (14)CO(2). Two metabolic pathways of 14C-HEMA can be described. The peak HEMA levels in all tissues examined after 24h were lower than known toxic levels. Therefore the study did not support the hypothesis.

  9. Aggregation and transport of Brij surfactants in hydroxyethyl methacrylate hydrogels.

    PubMed

    Kapoor, Yash; Bengani, Lokendrakumar C; Tan, Grace; John, Vijay; Chauhan, Anuj

    2013-10-01

    Surfactant loaded polymeric hydrogels find applications in several technological areas including drug delivery. Drug transport can be attenuated in surfactant loaded gels through partitioning of the drug in the surfactant aggregates. The drug transport depends on the type of the aggregates and also on the surfactant transport because diffusion of the surfactant leads to dissolution of the aggregates. The drug and the surfactant transport can be characterized by the surfactant monomer diffusivity Ds. and the critical aggregation concentration C(*). Here we focus on the transport in hydroxyethyl methacrylate (HEMA) hydrogels loaded with three different types of Brij surfactants. We measure transport of a hydrophobic drug cyclosporine and the surfactant for surfactant loadings ranging from 0.1% to 8%, and utilize the data to predict the values of Ds. and C(*). We show that the predictions based on surfactant transport are significantly different from those based on modeling the drug transport. The differences are attributed to the assumption of just one type of aggregate in the gel irrespective of the total concentration. The transport data suggests existence of multiple types of aggregates and this hypothesis is validated for Brij 98 by imaging of the microstructure with free fracture SEM.

  10. 2-hydroxyethyl methacrylate as an inhibitor of matrix metalloproteinase-2.

    PubMed

    Carvalho, Rodrigo V; Ogliari, Fabrício A; de Souza, Ana P; Silva, Adriana F; Petzhold, Cesar L; Line, Sergio R P; Piva, Evandro; Etges, Adriana

    2009-02-01

    This study evaluated the effect of different concentrations of 2-hydroxyethyl methacrylate (HEMA) on the inhibition of matrix metalloproteinase-2 (MMP-2) in vitro. Mouse gingival explants were cultured overnight in Dulbecco's modified Eagle's minimal essential medium, following which the expression of secreted enzymes was analyzed by gelatin zymography and the effects of different amounts of HEMA on enzyme activity were investigated. The gelatinolytic proteinases present in the conditioned media were characterized as being matrix metalloproteinases (MMPs) by means of specific chemical inhibition. The MMPs present in the conditioned media were identified, using immunoprecipitation, as MMP-2. Three major bands were detected in the zymographic assays and were characterized, according to their respective molecular weights, into the following forms of MMP-2: zymogene (72 kDa), intermediate (66 kDa), and active (62 kDa). All forms of MMP-2 were inhibited by HEMA in a dose-dependent manner, implying that MMP-2 may be inhibited by HEMA in vivo.

  11. Carboxybetaine methacrylate oligomer modified nylon for circulating tumor cells capture.

    PubMed

    Dong, Chaoqun; Wang, Huiyu; Zhang, Zhuo; Zhang, Tao; Liu, Baorui

    2014-10-15

    Circulating tumor cells (CTC) capture is one of the most effective approaches in diagnosis and treatment of cancers in the field of personalized cancer medicine. In our study, zwitterionic carboxybetaine methacrylate (CBMA) oligomers were grafted onto nylon via atomic transfer random polymerization (ATRP) which would serve as a novel material for the development of convenient CTC capture interventional medical devices. The chemical, physical and biological properties of pristine and modified nylon surfaces were assessed by Fourier transform infrared spectra, atomic force microscope, water contact angle measurements, X-ray photoelectron spectroscopy, protein adsorption, platelet adhesion, and plasma recalcification time (PRT) determinations, etc. The results, including the significant decrease of proteins adsorption and platelets adhesion, as well as prolonged PRTs demonstrated the extraordinary biocompatibility and blood compatibility of the modified surface. Furthermore, we showed that upon immobilization of anti-epithelial cell adhesion molecular (anti-EpCAM) antibody onto the CBMA moiety, the modified nylon surface can selectively capture EpCAM positive tumor cells from blood with high efficiency, indicating the potential of the modified nylon in the manufacture of convenient interventional CTC capture medical devices.

  12. Wettability interpretation of oxygen plasma modified poly(methyl methacrylate).

    PubMed

    Chai, Jinan; Lu, Fuzhi; Li, Baoming; Kwok, Daniel Y

    2004-12-07

    Poly(methyl methacrylate) (PMMA) has been modified via a dc pulsed oxygen plasma for different treatment times. The modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS), optical profilometer, zeta potential, and advancing contact angle measurements. The measured advancing contact angles of water decreased considerably as a function of discharge. Several oxygen-based functionalities (carbonyl, carboxyl, carbonate, etc.) were detected by XPS, while zeta potential measurements confirmed an increase in negative charge for the treated PMMA surface. Evaluating the correlation between the concentration of polar chemical species and zeta potential, we found that increase in surface hydrophilicity results from the coeffect due to incorporation of oxygen functional groups and creation of charge states. The electrical double layer (EDL) effect was also considered in contact angle interpretation by introducing an additional surface tension term into Young's equation. We also found that EDL contribution to the solid-liquid interfacial tension is negligible and can be safely ignored for the systems considered here.

  13. Superalloy Lattice Block Structures

    NASA Technical Reports Server (NTRS)

    Whittenberger, J. D.; Nathal, M. V.; Hebsur, M. G.; Kraus, D. L.

    2003-01-01

    In their simplest form, lattice block panels are produced by direct casting and result in lightweight, fully triangulated truss-like configurations which provide strength and stiffness [2]. The earliest realizations of lattice block were made from A1 and steels, primarily under funding from the US Navy [3]. This work also showed that the mechanical efficiency (eg., specific stiffness) of lattice block structures approached that of honeycomb structures [2]. The lattice architectures are also less anisotropic, and the investment casting route should provide a large advantage in cost and temperature capability over honeycombs which are limited to alloys that can be processed into foils. Based on this early work, a program was initiated to determine the feasibility of extending the high temperature superalloy lattice block [3]. The objective of this effort was to provide an alternative to intermetallics and composites in achieving a lightweight high temperature structure without sacrificing the damage tolerance and moderate cost inherent in superalloys. To establish the feasibility of the superalloy lattice block concept, work was performed in conjunction with JAMCORP, Inc. Billerica, MA, to produce a number of lattice block panels from both IN71 8 and Mar-M247.

  14. All-optically controllable and highly efficient scattering mode light modulator based on azobenzene liquid crystals and poly(N-vinylcarbazole) films.

    PubMed

    Liu, Yen-Chen; Cheng, Ko-Ting; Chen, Yuan-Di; Fuh, Andy Ying-Guey

    2013-07-29

    The present study reports that isothermal phase transition induced by photoisomerization of azobenzene liquid crystals (azo-LCs) from trans- to cis-isomers results in the dissolution of poly(N-vinylcarbazole) (PVK) into azo-LCs. Transparent (scattering) states can be demonstrated using uniform (rough) morphologies of PVK generated by slow (rapid) phase separation of PVK and azo-LCs from cis- to trans-isomers. The PVK films were examined in detail using scanning electron microscopy. Scattering performance resulting from the rough PVK surface induced micron-sized LC domains, and transparent performance resulting from the reformed uniform PVK surface can be optically and reversibly switched. Finally, all-optically controllable and highly efficient (contrast ratio of 370:1) scattering mode light modulators based on azo-LCs and PVK films were demonstrated.

  15. RAFT polymerization of temperature- and salt-responsive block copolymers as reversible hydrogels

    PubMed Central

    Hemp, Sean T.; Smith, Adam E.; Bunyard, W. Clayton; Rubinstein, Michael H.; Long, Timothy E.

    2016-01-01

    Reversible-addition fragmentation chain transfer (RAFT) polymerization enabled the synthesis of novel, stimuli-responsive, AB and ABA block copolymers. The B block contained oligo(ethylene glycol) methyl ether methacrylate (OEG) and was permanently hydrophilic in the conditions examined. The A block consisted of diethylene glycol methyl ether methacrylate (DEG) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TMA). The A block displayed both salt- and temperature-response with lower critical solution temperatures (LCSTs) dependent on the molar content of TMA and the presence of salt. Higher TMA content in the AB diblock copolymers increased the critical micelle temperatures (CMT) in HPLC-grade water due to an increased hydrophilicity of the A block. Upon addition of 0.9 wt% NaCl, the CMTs of poly(OEG-b-DEG95TMA5) decreased from 50 °C to 36 °C due to screening of electrostatic repulsion between the TMA units. ABA triblock copolymers displayed excellent hydrogel properties with salt- and temperature-dependent gel points. TMA incorporation in the A block increased the gel points for all triblock copolymers, and salt-response increased with higher TMA composition in the A block. For example, poly(DEG98TMA2-b-OEG-b-DEG98TMA2) formed a hydrogel at 40 °C in HPLC-grade water and 26 °C in 0.9 wt% NaCl aqueous solution. These salt- and temperature-responsive AB diblock and ABA triblock copolymers find applications as drug delivery vehicles, adhesives, and hydrogels. PMID:27041771

  16. Remarkable pH-responsive polypropylene microfiltration membrane through surface entrapment of poly(2-(diethylamino) ethyl methacrylate)-containing macromolecules by ATRP method.

    PubMed

    Jiang, Ping; Li, Duxin; Liu, Yuejun; Zhang, Xiuju; Lai, Dengwang

    2013-03-01

    Polypropylene (PP) microfiltration membrane were functionalized with an adsorption/surface entrapment process, using block copolymers with poly(n-butyl acrylate) (PBA) as anchor block being capable to tether the pH-responsive block poly(2-(diethylamino) ethyl methacrylate) (PDEA) to the surface, Homopolymer and Block copolymer synthesis was investigated by atom transfer radical polymerization (ATRP) using PMDETA, CuBr and ethyl acetate. These polymers were characterized by 1H NMR and GPC. Copolymer of PDEA with polybutylacrylate (PBA) was selected as best suitable modifier. Models related to the underlying deswelling/entrapment process which leads to fixation of the modifier were considered. Surface properties were analyzed by ATR-FTIR spectroscopy and water contact angle measurements, which confirmed the presence of modifier and a strong improvement of surface and pore wettability. The structure of membranes was evaluated using Polarized Optical Microscopy. Furthermore the pH-sensitive properties of modified PP membranes were verified by pH-dependence of water permeability which due to protonation/deprotonation and volume phase transition of PDEA around the pH 6-6.9.

  17. 2-hydroxylethyl methacrylate (HEMA), a tooth restoration component, exerts its genotoxic effects in human gingival fibroblasts trough methacrylic acid, an immediate product of its degradation.

    PubMed

    Szczepanska, Joanna; Poplawski, Tomasz; Synowiec, Ewelina; Pawlowska, Elzbieta; Chojnacki, Cezary J; Chojnacki, Jan; Blasiak, Janusz

    2012-02-01

    HEMA (2-hydroxyethyl methacrylate), a methacrylate commonly used in dentistry, was reported to induce genotoxic effects, but their mechanism is not fully understood. HEMA may be degraded by the oral cavity esterases or through mechanical stress following the chewing process. Methacrylic acid (MAA) is the primary product of HEMA degradation. In the present work we compared cytotoxic and genotoxic effects induced by HEMA and MAA in human gingival fibroblasts (HGFs). A 6-h exposure to HEMA or MAA induced a weak decrease in the viability of HGFs. Neither HEMA nor MAA induced strand breaks in the isolated plasmid DNA, but both compounds evoked DNA damage in HGFs, as evaluated by the alkaline comet assay. Oxidative modifications to the DNA bases were monitored by the DNA repair enzymes Endo III and Fpg. DNA damage induced by HEMA and MAA was not persistent and was removed during a 120 min repair incubation. Results from the neutral comet assay indicated that both compounds induced DNA double strand breaks (DSBs) and they were confirmed by the γ-H2AX assay. Both compounds induced apoptosis and perturbed the cell cycle. Therefore, methacrylic acid, a product of HEMA degradation, may be involved in its cytotoxic and genotoxic action.

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

    PubMed

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

    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 24h. The structure and properties of the modified fiber were characterized by Fourier Transform Infrared Spectroscopy, (13)C, (29)Si Nuclear Magnetic Resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), confirming the presence of the coupling molecule and the methacrylate groups onto the silk fibroin fiber surface. Molecular weight distributions were assessed by triple detection size exclusion chromatography (TD-SEC) in order to verify the livingness of the polymerization.

  19. Poly(glycidyl methacrylate-co-2-hydroxyethyl methacrylate) Brushes as Peptide/Protein Microarray Substrate for Improving Protein Binding and Functionality.

    PubMed

    Lei, Zhen; Gao, Jiaxue; Liu, Xia; Liu, Dianjun; Wang, Zhenxin

    2016-04-27

    We developed a three-dimensional (3D) polymer-brush substrate for protein and peptide microarray fabrication, and this substrate was facilely prepared by copolymerization of glycidyl methacrylate (GMA) and 2-hydroxyethyl methacrylate (HEMA) monomers via surface-initiated atom transfer radical polymerization (SI-ATRP) on a glass slide. The performance of obtained poly(glycidyl methacrylate-co-2-hydroxyethyl methacrylate) (P(GMA-HEMA)) brush substrate was assessed by binding of human IgG with rabbit antihuman IgG antibodies on a protein microarray and by the determination of matrix metalloproteinase (MMP) activities on a peptide microarray. The P(GMA-HEMA) brush substrate exhibited higher immobilization capacities for proteins and peptides than those of a two-dimensional (2D) planar epoxy slide. Furthermore, the sensitivity of the P(GMA-HEMA) brush-based microarray on rabbit antihuman IgG antibody detection was much higher than that of its 2D counterpart. The enzyme activities of MMPs were determined specifically with a low detection limit of 6.0 pg mL(-1) for MMP-2 and 5.7 pg mL(-1) for MMP-9. By taking advantage of the biocompatibility of PHEMA, the P(GMA-HEMA) brush-based peptide microarray was also employed to evaluate the secretion of MMP-2 and MMP-9 by cells cultured off the chip or directly on the chip, and satisfactory results were obtained.

  20. Efficient Condensation of DNA into Environmentally Responsive Polyplexes Produced from Block Catiomers Carrying Amine or Diamine Groups.

    PubMed

    Albuquerque, Lindomar J C; Annes, Kelly; Milazzotto, Marcella P; Mattei, Bruno; Riske, Karin A; Jäger, Eliézer; Pánek, Jiří; Štěpánek, Petr; Kapusta, Peter; Muraro, Paulo I R; De Freitas, Augusto G O; Schmidt, Vanessa; Giacomelli, Cristiano; Bonvent, Jean-Jacques; Giacomelli, Fernando C

    2016-01-19

    The intracellular delivery of nucleic acids requires a vector system as they cannot diffuse across lipid membranes. Although polymeric transfecting agents have been extensively investigated, none of the proposed gene delivery vehicles fulfill all of the requirements needed for an effective therapy, namely, the ability to bind and compact DNA into polyplexes, stability in the serum environment, endosome-disrupting capacity, efficient intracellular DNA release, and low toxicity. The challenges are mainly attributed to conflicting properties such as stability vs efficient DNA release and toxicity vs efficient endosome-disrupting capacity. Accordingly, investigations aimed at safe and efficient therapies are still essential to achieving gene therapy clinical success. Taking into account the mentioned issues, herein we have evaluated the DNA condensation ability of poly(ethylene oxide)113-b-poly[2-(diisopropylamino)ethyl methacrylate]50 (PEO113-b-PDPA50), poly(ethylene oxide)113-b-poly[2-(diethylamino)ethyl methacrylate]50 (PEO113-b-PDEA50), poly[oligo(ethylene glycol)methyl ether methacrylate]70-b-poly[oligo(ethylene glycol)methyl ether methacrylate10-co-2-(diethylamino)ethyl methacrylate47-co-2-(diisopropylamino)ethyl methacrylate47] (POEGMA70-b-P(OEGMA10-co-DEA47-co-DPA47), and poly[oligo(ethylene glycol)methyl ether methacrylate]70-b-poly{oligo(ethylene glycol)methyl ether methacrylate10-co-2-methylacrylic acid 2-[(2-(dimethylamino)ethyl)methylamino]ethyl ester44} (POEGMA70-b-P(OEGMA10-co-DAMA44). Block copolymers PEO113-b-PDEA50 and POEGMA70-b-P(OEGMA10-co-DEA47-co-DPA47) were evidenced to properly condense DNA into particles with a desirable size for cellular uptake via endocytic pathways (R(H) ≈ 65-85 nm). The structure of the polyplexes was characterized in detail by scattering techniques and atomic force microscopy. The isothermal titration calorimetric data revealed that the polymer/DNA binding is endothermic; therefore, the process in entropically driven

  1. Synthesis and characterization of fluorinated methacrylates-based copolymers containing cross-linkable pendant groups for optical waveguides

    NASA Astrophysics Data System (ADS)

    Kim, Ho June; Kim, Kwangsok; Chin, In-Joo

    2006-02-01

    Methacrylate based copolymers containing thermal and UV cross-linkable groups were prepared, ad their optical properties were investigated. Copolymerization of octafluoropentyl methacrylate (OFPMA) with hydroxyethyl methacrylate (HEMA) was followed by reacting HEMA and methacrylic anhydride (MAAN), yielding a fluorinated copolymer with cross-linkable pendant group. The refractive indices of the copolymers before cross-linking ranged from 1.4329 to 1.4646, and those of the cross-linked copolymers varied from 1.4500 to 1.4822, depending on the fluorine content.

  2. Impression block with orientator

    NASA Astrophysics Data System (ADS)

    Brilin, V. I.; Ulyanova, O. S.

    2015-02-01

    Tool review, namely the impression block, applied to check the shape and size of the top of fish as well as to determine the appropriate tool for fishing operation was realized. For multiple application and obtaining of the impress depth of 3 cm and more, the standard volumetric impression blocks with fix rods are used. However, the registered impress of fish is not oriented in space and the rods during fishing are in the extended position. This leads to rods deformation and sinking due to accidental impacts of impression block over the borehole irregularity and finally results in faulty detection of the top end of fishing object in hole. The impression blocks with copy rods and fixed magnetic needle allow estimating the object configuration and fix the position of magnetic needle determining the position of the top end of object in hole. However, the magnetic needle fixation is realized in staged and the rods are in extended position during fishing operations as well as it is in standard design. The most efficient tool is the impression block with copy rods which directs the examined object in the borehole during readings of magnetic needles data from azimuth plate and averaging of readings. This significantly increases the accuracy of fishing toll direction. The rods during fishing are located in the body and extended only when they reach the top of fishing object.

  3. Horseradish peroxidase mediated free radical polymerization of methyl methacrylate.

    PubMed

    Kalra, B; Gross, R A

    2000-01-01

    This paper reports the free radical polymerization of methyl methacrylate (MMA) catalyzed by horseradish peroxidase (HRP). A novel method was developed whereby MMA polymerization can be carried out at ambient temperatures in the presence of low concentrations of hydrogen peroxide and 2,4-pentanedione in a mixture of water and a water-miscible solvent. Polymers of MMA formed were highly stereoregular with predominantly syndiotactic sequences (syn-dyad fractions from 0.82 to 0.87). Analyses of the chloroform-soluble fraction of syndio-PMMA products by GPC showed that they have number-average molecular weights, Mn, that range from 7500 to 75,000. By using 25% v/v of the cosolvents dioxane, tetrahydrofuran, acetone, and dimethylformamide, 85, 45, 7 and 2% product yields, respectively, resulted after 24 h. Increasing the proportion of dioxane to water from 1:3 to 1:1 and 3:1 resulted in a decrease in polymer yield from 45 to 38 and 7%, respectively. Increase in the enzyme concentration from 70 to 80 and 90 mg/mL resulted in increased reaction kinetics. By adjustment of the molar ratio of 2,4-pentanedione to hydrogen peroxide between 1.30:1.0 and 1.45:1.0, the product yields and Mn values were increased. On the basis of the catalytic properties of HRP and studies herein, we believe that the keto-enoxy radicals from 2,4-pentanedione are the first radical species generated. Then, initiation may take place through this radical or by the radical transfer to another molecule.

  4. Dual-functional electrospun poly(2-hydroxyethyl methacrylate).

    PubMed

    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.

  5. Assessment of methyl methacrylate genotoxicity by the micronucleus test.

    PubMed

    Araújo, Amarildo Mariano de; Alves, Guilherme Rodrigues; Avanço, Guilherme Trevisan; Parizi, José Luiz Santos; Nai, Gisele Alborghetti

    2013-01-01

    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.

  6. Can quaternary ammonium methacrylates inhibit matrix MMPs and cathepsins?

    PubMed Central

    Tezvergil-Mutluay, Arzu; Agee, Kelli A.; Mazzoni, Annalisa; Carvalho, Ricardo M.; Carrilho, Marcela; Tersariol, Ivarne L.; Nascimento, Fabio D.; Imazato, Satoshi; Tjäderhane, Leo; Breschi, Lorenzo; Tay, Franklin R; Pashley, David H.

    2014-01-01

    Objective Dentin matrices release ICTP and CTX fragments during collagen degradation. ICTP fragments are known to be produced by MMPs. CTX fragments are thought to come from cathepsin K activity. The purpose of this study was to determine if quaternary methacrylates (QAMs) can inhibit matrix MMPs and cathepsins. Methods Dentin beams were demineralizated, and dried to constant weight. Beams were incubated with rh-cathepsin B, K, L or S for 24 h at pH 7.4 to identify which cathepsins release CTX at neutral pH. Beams were dipped in ATA, an antimicrobial QAM to determine if it can inhibit dentin matrix proteases. Other beams were dipped in another QAM (MDPB) to determine if it produced similar inhibition of dentin proteases. Results Only beams incubated with cathepsin K lost more dry mass than the controls and released CTX. Dentin beams dipped in ATA and incubated for 1 week at pH 7.4, showed a concentration-dependent reduction in weight-loss. There was no change in ICTP release from control values, meaning that ATA did not inhibit MMPs. Media concentrations of CTX fell significantly at 15 wt% ATA indicating that ATA inhibits capthesins. Beams dipped in increasing concentrations of MDPB lost progressively less mass, showing that MDPB is a protease-inhibitor. ICTP released from controls or beams exposed to low concentrations were the same, while 5 or 10% MDPB significantly lowered ICTP production. CTX levels were strongly inhibited by 2.5–10% MDPB, indicating that MDPB is a potent inhibitor of both MMPs and cathepsin K. Significance CTX seems to be released from dentin matrix only by cathepsin K. MMPs and cathepsin K and B may all contribute to matrix degradation. PMID:25467953

  7. WATER-BORNE BLOCK COPOLYMER SYNTHESIS AND A SIMPLE AND EFFECTIVE ONE-POT SYNTHESIS OF ACRYLATE-METHACRYLATE BLOCK COPOLYMERS BY ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  8. A route to nanoscopic materials via seeded sequential infiltration synthesis on block copolymer templates.

    SciTech Connect

    Peng, Q.; Tseng, Y.-C.; Darling, S. B.; Elam, J. W.

    2011-06-01

    Sequential infiltration synthesis (SIS), combining stepwise molecular assembly reactions with self-assembled block copolymer (BCP) substrates, provides a new strategy to pattern nanoscopic materials in a controllable way. The selective reaction of a metal precursor with one of the pristine BCP domains is the key step in the SIS process. Here we present a straightforward strategy to selectively modify self-assembled polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) BCP thin films to enable the SIS of a variety of materials including SiO{sub 2}, ZnO, and W. The selective and controlled interaction of trimethyl aluminum with carbonyl groups in the PMMA polymer domains generates Al-CH{sub 3}/Al-OH sites inside the BCP scaffold which can seed the subsequent growth of a diverse range of materials without requiring complex block copolymer design and synthesis.

  9. Facile Fabrication of Gradient Surface Based on (meth)acrylate Copolymer Films

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Yang, H.; Wen, X.-F.; Cheng, J.; Xiong, J.

    2016-08-01

    This paper describes a simple and economic approach for fabrication of surface wettability gradient on poly(butyl acrylate - methyl methacrylate) [P (BA-MMA)] and poly(butyl acrylate - methyl methacrylate - 2-hydroxyethyl methacrylate) [P (BA-MMA-HEMA)] films. The (meth)acrylate copolymer [including P (BA-MMA) and P (BA-MMA-HEMA)] films are hydrolyzed in an aqueous solution of NaOH and the transformation of surface chemical composition is achieved by hydrolysis in NaOH solution. The gradient wetting properties are generated based on different functional groups on the P (BA-MMA) and P (BA-MMA-HEMA) films. The effects of both the surface chemical and surface topography on wetting of the (meth)acrylate copolymer film are discussed. Surface chemical composition along the materials length is determined by XPS, and surface topography properties of the obtained gradient surfaces are analyzed by FESEM and AFM. Water contact angle system (WCAs) results show that the P (BA-MMA-HEMA) films provide a larger slope of the gradient wetting than P (BA-MMA). Moreover, this work demonstrates that the gradient concentration of chemical composition on the poly(meth) acrylate films is owing to the hydrolysis processes of ester group, and the hydrolysis reactions that have negligible influence on the surface morphology of the poly(meth) acrylate films coated on the glass slide. The gradient wettability surfaces may find broad applications in the field of polymer coating due to the compatibility of (meth) acrylate polymer.

  10. Conversion of (Meth)acrylic acids to methane granular sludge: Initiation by specific anerobic microflora

    SciTech Connect

    Shtarkman, N.B.; Obraztova, A.Y.; Laurinavichyus, K.S.; Galushko, A.S.; Akimenko, V.K.

    1995-03-01

    The role of a specific anaerobic microflora in the initiation of degradation of (meth)acrylic acids to methane by granular sludge from a UASB reactor was investigated. Associations of anaerobic bacteria isolated from the anaerobic sludge, which was used for a long time for treatment of wastewater from (meth)acrylate production, were able to realize the initial stage of (meth)acrylic acid decomposition, i.e., a conversion of acrylic and methacrylic acids to propionic and isobutyric acids, respectively. When added to granules, these association played a role of an {open_quotes}initiator{close_quotes} of the degradation process, which was then continued by the granular sludge microflora utilizing propionate and isobutyrate. Some characteristics of the granules adapted to propionate or isobutyrate are presented. The rates of propionate and isobutyrate consumption by adapted granules is, respectively, 21 and 53 times higher than the values obtained for nonadapted granules. A combined use of {open_quotes}initiating{close_quotes} bacteria and adapted granules provided degradation of (meth)acrylic acids with a maximum methane yield. The possibility is discussed of employing the granules, which are adapted to short-chain fatty acids, and the {open_quotes}initiating{close_quotes} bacteria, which accomplish the initial steps of the organic material decomposition to lower fatty acids, for the conversion of various chemical compounds to methane. 10 refs., 3 figs., 2 tabs.

  11. Preparation and characterization of alkyl methacrylate-based monolithic columns for capillary gas chromatography applications.

    PubMed

    Yusuf, Kareem; Aqel, Ahmad; A L Othman, Zeid; Badjah-Hadj-Ahmed, Ahmed Yacine

    2013-08-02

    Gas chromatography (GC) is considered the least common application of both polymer and silica-based monolithic columns. This study describes the fabrication of alkyl methacrylate monolithic materials for use as stationary phases in capillary gas chromatography. Following the deactivation of the capillary surface with 3-(trimethoxysilyl)propyl methacrylate (TMSM), the monoliths were formed by the co-polymerization of either hexyl methacrylate (HMA) or lauryl methacrylate (LMA) with different percentage of ethylene glycol dimethacrylate (EDMA) in presence of an initiator (azobisisobutyronitrile, AIBN) and a mixture of porogens include 1-propanol, 1,4-butanediol and water. The monoliths were prepared in 500mm length capillaries possessing inner diameters of 250μm. The efficiencies of the monolithic columns for low molecular weight compounds significantly improved as the percentage of crosslinker was increased, because of the greater proportion of pores less than 50nm. The columns containing lower percentages of crosslinker were able to rapidly separate a series of 8 alkane members in 0.7min, but the separation was less efficient for the light alkanes. Columns prepared with the lauryl methacrylate monomer yielded a different morphology for the monolith-interconnected channels. The channels were more branched, which increased the separation time, and unlike the other columns, allowed for temperature programming.

  12. Flexural properties of ethyl or methyl methacrylate-UDMA blend polymers.

    PubMed

    Kanie, Takahito; Kadokawa, Akihiko; Arikawa, Hiroyuki; Fujii, Koichi; Ban, Seiji

    2010-10-01

    Light-curing polyethyl methacrylate (PEMA)-urethane dimethacrylate (UDMA) resins and polymethyl methacrylate (PMMA)-UDMA resins were prepared by two processes. For first step, PEMA or PMMA powders were fully dissolved in ethyl methacrylate (EMA) or methyl methacrylate (MMA) and then the PEMA-EMA/PMMA-MMA mixtures were mixed with UDMA. The flexural properties of cured PEMA-UDMA and PMMA-UDMA polymers were measured using two PEMA (Mw: 300,000-400,000 and 650,000-1,000,000) and three PMMA (Mw: 30,000-60,000, 350,000 and 650,000-1,000,000) powders with different molecular weight, four mixing ratios of PMMA-MMA, and three mixing ratios of PMMA-MMA mixture and UDMA oligomer. Polymers with PMMA(Mw: 350,000) MMA=25/50, and with PMMA(Mw: 350,000)-MMA/UDMA=1/2 and =1/1, showed no-fracture in a flexural test at 1 mm/min and flexural strength and flexural modulus showed no significant difference compared with those of commercially available heat- and self-curing acrylic resins (p>0.01). Within limitation of this investigation, methyl methacrylate-UDMA blend polymer of this composition is available for denture base resin.

  13. Ion Transport in Polymerized Ionic Liquid Block and Random Copolymers

    NASA Astrophysics Data System (ADS)

    Elabd, Yossef; Ye, Yuesheng; Choi, Jae-Hong; Winey, Karen

    2012-02-01

    Polymerized ionic liquid (PIL) block copolymers, a new type of solid-state polymer electrolyte, are of interest for energy conversion and storage devices, such as fuel cells, batteries, supercapacitors, and solar cells. In this study, a series of PIL diblock and random copolymers with various PIL compositions were synthesized. These consisted of an IL monomer and a non-ionic monomer, 1-[(2-methacryloyloxy)ethyl]-3-butylimidazolium bis(trifluoromethanesulfonyl)imide (MEBIm-TFSI) and methyl methacrylate (MMA), and 1-[(2-acryloyloxy)ethyl]-3-butylimidazolium bis(trifluoromethanesulfonyl)imide (AEBIm-TFSI) and styrene (S), respectively, were synthesized. The anion conductivity (ion transport) and morphology were measured in all of the polymers with EIS, SAXS/WAXS, and TEM. Ion transport in block copolymers are significantly higher than random copolymers at the same PIL composition and are highly dependent on the block copolymer nanostructure. The relationship between ion transport mechanisms and the phase behavior of these materials will be discussed.

  14. Perpendicular Orientation Control without Interfacial Treatment of RAFT-Synthesized High-χ Block Copolymer Thin Films with Sub-10 nm Features Prepared via Thermal Annealing.

    PubMed

    Nakatani, Ryuichi; Takano, Hiroki; Chandra, Alvin; Yoshimura, Yasunari; Wang, Lei; Suzuki, Yoshinori; Tanaka, Yuki; Maeda, Rina; Kihara, Naoko; Minegishi, Shinya; Miyagi, Ken; Kasahara, Yuusuke; Sato, Hironobu; Seino, Yuriko; Azuma, Tsukasa; Yokoyama, Hideaki; Ober, Christopher K; Hayakawa, Teruaki

    2017-03-17

    In this study, a series of perpendicular lamellae-forming poly(polyhedral oligomeric silsesquioxane methacrylate-block-2,2,2-trifluoroethyl methacrylate)s (PMAPOSS-b-PTFEMAs) was developed based on the bottom-up concept of creating a simple yet effective material by tailoring the chemical properties and molecular composition of the material. The use of silicon (Si)-containing hybrid high-χ block copolymers (BCPs) provides easy access to sub-10 nm feature sizes. However, as the surface free energies (SFEs) of Si-containing polymers are typically vastly lower than organic polymers, this tends to result in the selective segregation of the inorganic block onto the air interface and increased difficulty in controlling the BCP orientation in thin films. Therefore, by balancing the SFEs between the organic and inorganic blocks through the use of poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) on the organic block, a polymer with an SFE similar to Si-containing polymers, orientation control of the BCP domains in thin films becomes much simpler. Herein, perpendicularly oriented BCP thin films with a χeff value of 0.45 were fabricated using simple spin-coating and thermal annealing processes under ambient conditions. The thin films displayed a minimum domain size of L0 = 11 nm, as observed via atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Furthermore, directed self-assembly (DSA) of the BCP on a topographically prepatterned substrate using the grapho-epitaxy method was used to successfully obtain perpendicularly oriented lamellae with a half pitch size of ca. 8 nm.

  15. Synthesis of amphipathic block copolymers based on polyisobutylene and polyoxyethylene and their application in emulsion polymerization

    SciTech Connect

    Sar, B.

    1992-12-31

    Polymer colloids stabilized by polymeric surfactants are of great interest both commercially and academically. It has been found that these materials enhance latex stabilization in a number of applications. The polymeric surfactants are amphipathic block and graft copolymers containing both hydrophilic and hydrophobic moieties. The current study involved the synthesis of a series of amphipathic triblock copolymers, polyisobutylene-block-polyoxyethylene-block-polyisobutylene (PIB-b-POE-b-PIB), for use in the emulsion polymerization of styrene (STY), methyl methacrylate (MMA), and vinyl acetate (VAc). The stabilizing effectiveness of these triblock copolymers was studied as a function of their blocklength. When the molecular weight of the POE center block was changed from M{sub n} = 2,000 to 20,000 g/mole, stable lattices were obtained in emulsion polymerization with MMA, STY, and VAc as the monomers. In all cases, the polymerization rates remained constant, while the number of particles/volume decreased with increasing POE chain length. When the molecular weight of the PIB end blocks was changed from M{sub n} = 400 to 2,600 g/mole keeping the molecular weight of the POE center block constant at M{sub n} = 20,000 g/mole, the poly(methyl methacrylate) and poly(vinyl acetate) lattices exhibited similar behavior, i.e., the number of particles and particle sizes remained the same, but the rate of polymerization reached a maximum at 87 wt% POE content. In the case of poly(styrene) both the rate of polymerization and the number of particles remained constant. The emulsion polymerization of other monomers such as butadiene, acrylonitrile, methyl acrylate, ethyl acrylate, and butyl acrylate was carried out by using one triblock copolymer, i.e., PIB(400)-b-POE (8,000)-b-PIB-(400). Stable lattices were also formed in all cases.

  16. Magnetothermally responsive star-block copolymeric micelles for controlled drug delivery and enhanced thermo-chemotherapy

    NASA Astrophysics Data System (ADS)

    Deng, Li; Ren, Jie; Li, Jianbo; Leng, Junzhao; Qu, Yang; Lin, Chao; Shi, Donglu

    2015-05-01

    Magnetothermally responsive drug-loaded micelles were designed and prepared for cancer therapy. These specially designed micelles are composed of the thermo-responsive star-block copolymer poly(ε-caprolactone)-block-poly(2-(2-methoxyethoxy)ethyl methacrylate-co-oligo(ethylene glycol)methacrylate) and Mn, Zn doped ferrite magnetic nanoparticles (MZF-MNPs). The thermo-responses of 6sPCL-b-P(MEO2MA-co-OEGMA) copolymers were shown to be dependent on the MEO2MA to OEGMA ratio. The lower critical solution temperature (LCST) of the star-block copolymers was controlled at 43 °C by adjusting the feed molar ratios of MEO2MA/OEGMA at 92 : 8. With the anti-tumor drug doxorubicin (DOX) self-assembling into the carrier system, the thermo-responsive micelles exhibited excellent temperature-triggered drug release behavior. In vitro cytotoxicity results showed high biocompatibility of the polymer micelles. Efficient cellular proliferation inhibition by the drug-loaded micelles was found on the HepG2 cells under different treatments. The thermo-responsive polymer micelles are promising for controlled drug delivery in tumor therapy under an alternating magnetic field.

  17. Enhanced Bioactivity of α-Tocopheryl Succinate Based Block Copolymer Nanoparticles by Reduced Hydrophobicity.

    PubMed

    Palao-Suay, Raquel; Aguilar, María Rosa; Parra-Ruiz, Francisco J; Maji, Samarendra; Hoogenboom, Richard; Rohner, Nathan A; Thomas, Susan N; Román, Julio San

    2016-12-01

    Well-structured amphiphilic copolymers are necessary to obtain self-assembled nanoparticles (NPs) based on synthetic polymers. Highly homogeneous and monodispersed macromolecules obtained by controlled polymerization have successfully been used for this purpose. However, disaggregation of the organized macromolecules is desired when a bioactive element, such as α-tocopheryl succinate, is introduced in self-assembled NPs and this element must be exposed or released to exert its action. The aim of this work is to demonstrate that the bioactivity of synthetic NPs based on defined reversible addition-fragmentation chain transfer polymerization copolymers can be enhanced by the introduction of hydrophilic comonomers in the hydrophobic segment. The amphiphilic terpolymers are based on poly(ethylene glycol) (PEG) as hydrophilic block, and a hydrophobic block based on a methacrylic derivative of α-tocopheryl succinate (MTOS) and small amounts of 2-hydroxyethyl methacrylate (HEMA) (PEG-b-poly(MTOS-co-HEMA)). The introduction of HEMA reduces hydrophobicity and introduces "disorder" both in the homogeneous blocks and the compact core of the corresponding NPs. These NPs are able to encapsulate additional α-tocopheryl succinate (α-TOS) with high efficiency and their biological activity is much higher than that described for the unmodified copolymers, proposedly due to more efficient degradation and release of α-TOS, demonstrating the importance of the hydrophilic-hydrophobic balance.

  18. Magnetothermally responsive star-block copolymeric micelles for controlled drug delivery and enhanced thermo-chemotherapy.

    PubMed

    Deng, Li; Ren, Jie; Li, Jianbo; Leng, Junzhao; Qu, Yang; Lin, Chao; Shi, Donglu

    2015-06-07

    Magnetothermally responsive drug-loaded micelles were designed and prepared for cancer therapy. These specially designed micelles are composed of the thermo-responsive star-block copolymer poly(ε-caprolactone)-block-poly(2-(2-methoxyethoxy)ethyl methacrylate-co-oligo(ethylene glycol)methacrylate) and Mn, Zn doped ferrite magnetic nanoparticles (MZF-MNPs). The thermo-responses of 6sPCL-b-P(MEO2MA-co-OEGMA) copolymers were shown to be dependent on the MEO2MA to OEGMA ratio. The lower critical solution temperature (LCST) of the star-block copolymers was controlled at 43 °C by adjusting the feed molar ratios of MEO2MA/OEGMA at 92 : 8. With the anti-tumor drug doxorubicin (DOX) self-assembling into the carrier system, the thermo-responsive micelles exhibited excellent temperature-triggered drug release behavior. In vitro cytotoxicity results showed high biocompatibility of the polymer micelles. Efficient cellular proliferation inhibition by the drug-loaded micelles was found on the HepG2 cells under different treatments. The thermo-responsive polymer micelles are promising for controlled drug delivery in tumor therapy under an alternating magnetic field.

  19. Synergistic effect on corrosion resistance of Phynox substrates grafted with surface-initiated ATRP (co)polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) and 2-hydroxyethyl methacrylate (HEMA).

    PubMed

    Barthélémy, Bastien; Maheux, Simon; Devillers, Sébastien; Kanoufi, Frédéric; Combellas, Catherine; Delhalle, Joseph; Mekhalif, Zineb

    2014-07-09

    Phynox is of high interest for biomedical applications due to its biocompatibility and corrosion resistance. However, some Phynox applications require specific surface properties. These can be imparted with suitable surface functionalizations of its oxide layer. The present work investigates the surface-initiated atom transfer radical polymerization (ATRP) of 2-methacryloyoxyethyl phosphorylcholine (MPC), 2-hydroxyethyl methacrylate (HEMA), and ATRP copolymerization of (HEMA-co-MPC) (block and statistic copolymerization with different molar ratios) on grafted Phynox substrates modified with 11-(2-bromoisobutyrate)-undecyl-1-phosphonic acid (BUPA) as initiator. It is found that ATRP (co)polymerization of these monomers is feasible and forms hydrophilic layers, while improving the corrosion resistance of the system.

  20. A Place for Block Play.

    ERIC Educational Resources Information Center

    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…

  1. Flattening basic blocks.

    SciTech Connect

    Utke, J.; Mathematics and Computer Science

    2006-01-01

    The application of cross country elimination strategies requires access to the computational graph or at least subgraphs for certain scopes, e.g. a basic block. Under the presence of aliased variables the construction of these (sub)graphs encounters ambiguities. We propose an algorithm to construct ambiguity free subgraphs.

  2. Spice Blocks Melanoma Growth

    ERIC Educational Resources Information Center

    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…

  3. Ischemic Nerve Block.

    ERIC Educational Resources Information Center

    Williams, Ian D.

    This experiment investigated the capability for movement and muscle spindle function at successive stages during the development of ischemic nerve block (INB) by pressure cuff. Two male subjects were observed under six randomly ordered conditions. The duration of index finger oscillation to exhaustion, paced at 1.2Hz., was observed on separate…

  4. Hawaii Census 2000 Blocks

    EPA Pesticide Factsheets

    This data layer represents Census 2000 demographic data derived from the PL94-171 redistricting files and SF3. Census geographic entities include blocks, blockgroups and tracts. Tiger line files are the source of the geometry representing the Census blocks. Attributes include total population counts, racial/ethnic, and poverty/income information. Racial/ethnic classifications are represented in units of blocks, blockgroups and tracts. Poverty and income data are represented in units of blockgroups and tracts. Percentages of each racial/ethnic group have been calculated from the population counts. Total Minority counts and percentages were compiled from each racial/ethnic non-white category. Categories compiled to create the Total Minority count includes the following: African American, Asian, American Indian, Pacific Islander, White Hispanic, Other and all mixed race categories. The percentage poverty attribute represents the percent of the population living at or below poverty level. The per capita income attribute represents the sum of all income within the geographic entity, divided by the total population of that entity. Special fields designed to be used for EJ analysis have been derived from the PL data and include the following: Percentage difference of block, blockgroup and total minority from the state and county averages, percentile rank for each percent total minority within state and county entitie

  5. Concrete Block Pavements

    DTIC Science & Technology

    1983-03-01

    1967, Cedergren 1974, Federal Highway .’,U .. V,47 -’":: 37 Administration 1980). Block pavements have essentially the same prob- lems with moisture...Vicksburg, Miss. Cedergren , H. R. 1974. Drainage of Highway and Airfield Pavements, John Wiley and Sons, New VOk. I Cement and Concrete Association

  6. Signal Unification Block,

    DTIC Science & Technology

    A multichannel device is described for unifying the signals of thermocouples, tachometer generators and tensometers used in conducting tests on...various machines and mechanisms. The device is built on semiconductor instruments and has a block construction, permitting the easy alteration of the number of varieties of the signals being unified.

  7. Superparamagnetic poly(methyl methacrylate) nanoparticles surface modified with folic acid presenting cell uptake mediated by endocytosis

    NASA Astrophysics Data System (ADS)

    Feuser, Paulo Emilio; Jacques, Amanda Virtuoso; Arévalo, Juan Marcelo Carpio; Rocha, Maria Eliane Merlin; dos Santos-Silva, Maria Claudia; Sayer, Claudia; de Araújo, Pedro H. Hermes

    2016-04-01

    The encapsulation of superparamagnetic nanoparticles (MNPs) in polymeric nanoparticles (NPs) with modified surfaces can improve targeted delivery and induce cell death by hyperthermia. The goals of this study were to synthesize and characterize surface modified superparamagnetic poly(methyl methacrylate) with folic acid (FA) prepared by miniemulsion polymerization (MNPsPMMA-FA) and to evaluate their in vitro cytotoxicity and cellular uptake in non-tumor cells, murine fibroblast (L929) cells and tumor cells that overexpressed folate receptor (FR) β, and chronic myeloid leukemia cells in blast crisis (K562). Lastly, hemolysis assays were performed on human red blood cells. MNPsPMMA-FA presented an average mean diameter of 135 nm and a saturation magnetization (Ms) value of 37 emu/g of iron oxide, as well as superparamagnetic behavior. The MNPsPMMA-FA did not present cytotoxicity in L929 and K562 cells. Cellular uptake assays showed a higher uptake of MNPsPMMA-FA than MNPsPMMA in K562 cells when incubated at 37 °C. On the other hand, MNPsPMMA-FA showed a low uptake when endocytosis mechanisms were blocked at low temperature (4 °C), suggesting that the MNPsPMMA-FA uptake was mediated by endocytosis. High concentrations of MNPsPMMA-FA showed hemocompatibility when incubated for 24 h in human red blood cells. Therefore, our results suggest that these carrier systems can be an excellent alternative in targeted drug delivery via FR.

  8. Thermo-mechanical response of poly(methyl methacrylate) (PMMA) large volumes exposed to time-dependent environmental conditions

    NASA Astrophysics Data System (ADS)

    Fraldi, M.; Esposito, L.; Perrella, G.; Cutolo, A.

    2014-02-01

    Low thermal conductivity and elevated absorbance of large bulky volumes of poly(methyl methacrylate) (PMMA) exposed to moderately aggressive environmental conditions may cooperate to determine critical mechanical conditions, kindling unexpected high thermal stresses values which lead the material to failure. From the engineering point of view, this can be explained as the result of two concomitant phenomena which activate a cascade of events: very sharp thermal gradients engendered by transient thermal processes induced by cyclic environmental conditions, combined with significant bulk heat generation due to the high thermal inertia of massive PMMA volumes, in turn aggravating the steepness of the thermal gradients, may in fact ingenerate severe stress regimes, potentially undermining the structural stability of the material. Moving from these considerations, the present study is aimed to investigate possible rupture of PMMA blocks experiencing heating processes as a consequence of their exposure to outdoor cyclic environmental conditions. The problem is approached by means of both rigorous analytical arguments and the Finite Element based numerical methods, finally exploiting the theoretical outcomes to formulate a hypothesis which might explain the still unclear phenomenon of the sudden breaking of the PMMA structure, named Huge Wine Glass and designed by the world famous Japanese architect Toyo Ito, which occurred in Pescara (Italy) in 2009.

  9. Instantaneous Directional Growth of Block Copolymer Nanowires During Heterogeneous Radical Polymerization (HRP).

    PubMed

    Lu, Chunliang; Urban, Marek W

    2016-04-13

    Polymeric nanowires that consist of ultrahigh molecular weight block copolymers were instantaneously prepared via one-step surfactant-free heterogeneous radical polymerization (HRP). Under heterogeneous reaction and initiator-starvation conditions, the sequential copolymerization of hydrophilic and hydrophobic monomers facilitates the formation of amphiphilic ultrahigh molecular weight block copolymers, which instantaneously assemble to polymeric nanowires. As polymerization progresses, initially formed nanoparticles exhibit the directional growth due to localized repulsive forces of hydrophilic blocks and confinement of the hydrophobic blocks that adopt favorable high aspect ratio nanowire morphologies. Using one-step synthetic approach that requires only four ingredients (water as a solvent, two polymerizable monomers (one hydrophilic and one hydrophobic), and water-soluble initiator), block copolymer nanowires ∼70 nm in diameter and hundreds of microns in length are instantaneously grown. For example, when 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) and styrene (St) were copolymerized, high aspect ratio nanowires consist of ultrahigh (>10(6) g/mol) molecular weight pDMAEMA-b-St block copolymers and the presence of temperature responsive pDMAEMA blocks facilitates nanowire diameter changes as a function of temperature. These morphologies may serve as structural components of the higher order biological constructs at micro and larger length scales, ranging from single strand nanowires to engineered biomolecular networks capable of responding to diverse and transient environmental signals, and capable of dimensional changes triggered by external stimuli.

  10. High-concentration graphene dispersion stabilized by block copolymers in ethanol.

    PubMed

    Perumal, Suguna; Lee, Hyang Moo; Cheong, In Woo

    2017-07-01

    This article describes a comprehensive study for the preparation of graphene dispersions by liquid-phase exfoliation using amphiphilic diblock copolymers; poly(ethylene oxide)-block-poly(styrene) (PEO-b-PS), poly(ethylene oxide)-block-poly(4-vinylpyridine) (PEO-b-PVP), and poly(ethylene oxide)-block-poly(pyrenemethyl methacrylate) (PEO-b-PPy) with similar block lengths. Block copolymers were prepared from PEO using the Steglich coupling reaction followed by reversible addition-fragmentation chain transfer (RAFT) polymerization. Graphite platelets (G) and reduced graphene oxide (rGO) were used as graphene sources. The dispersion stability of graphene in ethanol was comparatively investigated by on-line turbidity, and the graphene concentration in the dispersions was determined gravimetrically. Our results revealed that the graphene dispersions with PEO-b-PVP were much more stable and included graphene with fewer defects than that with PEO-b-PS or PEO-b-PPy, as confirmed by turbidity and Raman analyses. Gravimetry confirmed that graphene concentrations up to 1.7 and 1.8mg/mL could be obtained from G and rGO dispersions, respectively, using PEO-b-PVP after one week. Distinctions in adhesion forces of PS, VP, PPy block units with graphene surface and the variation in solubility of the block copolymers in ethanol medium significantly affected the stability of the graphene dispersion.

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

    PubMed Central

    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. PMID:24955426

  12. Toughening epoxy resin with poly(methyl methacrylate)-grafted natural rubber

    SciTech Connect

    Rezaifard, A.H.; Hodd, K.A.; Barton, J.M.

    1993-12-31

    A novel rubber, poly(methyl methacrylate)-g-natural rubber (Hevea-plus MG), has been studied as a toughening agent for bisphenol A diglycidyl ether (Shell 828 epoxy resin) cured with piperidine. Effective dispersions of the rubber, in concentrations of 2-10 parts per hundred parts resin, were achieved by adjusting the solubility parameter of the epoxy to approximate that of poly(methyl methacrylate) by adding bisphenol A. The fracture energy of the rubber-modified resin was determined by compact tension tests (in the temperature range -60 to +40{degrees}C) and by Charpy impact tests. The poly(methyl methacrylate)-g-natural rubber was found to be an effective toughening agent for the epoxy resin at both low and high rates of strain. Possible fracture mechanisms are discussed. 22 refs., 16 figs., 5 tabs.

  13. Night-time atmospheric degradation of a series of butyl methacrylates

    NASA Astrophysics Data System (ADS)

    Teruel, Mariano A.; López, Rocío S. Pérez; Barnes, Ian; Blanco, María B.

    2016-11-01

    Rate coefficients for the reactions of NO3 with n-butyl methacrylate (k1), iso-butyl methacrylate (k2) and tert-butyl methacrylate (k3) have been determined at 298 K and atmospheric pressure using the relative rate method. The following rate coefficients (×10-15 cm3 molecule-1 s-1) were obtained for the first time: k1 = (5.5 ± 2.6), k2 = (5.8 ± 2.8) and k3 = (5.6 ± 2.5). The NO3 reactions of these compounds could contribute to the removal of NOx and as NOy reservoirs. The potential importance for the tropospheric nitrogen budget of these reactions is discussed and atmospheric lifetimes for the butyl esters are calculated.

  14. Development and characterization of thermoplastic films from sorghum distillers dried grains grafted with various methacrylates.

    PubMed

    Reddy, Narendra; Shi, Zhen; Temme, Lisa; Xu, Helan; Xu, Lan; Hou, Xiuliang; Yang, Yiqi

    2014-03-19

    Distillers Dried Grains (DDG) obtained during production of ethanol from grain sorghum were grafted with methacrylates and compression molded into films with good dry and wet tensile properties. Since sorghum DDG contains up to 45% proteins that are indigestible by animals, it is necessary to find alternative applications to make sorghum ethanol economically competitive. In this research, sorghum DDG was grafted with methyl, ethyl, and butyl methacrylates, the grafted DDG was compression molded into films, and the properties of the grafted DDG and films were studied. At a grafting ratio of 40%, butyl methacrylate (BMA) grafted films had a strength of 4.8 MPa and elongation of 1.8% when dry and 3.1 MPa and 8.1% when wet, indicating that the films had good strength and wet stability. Films developed from grafted DDG show the potential to overcome the brittleness and poor water stability of biopolymer-based films and be useful for various applications.

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

    PubMed

    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. Novel poly(methyl methacrylate)-based semi-interpenetrating polyelectrolyte gels for rechargeable lithium batteries

    NASA Astrophysics Data System (ADS)

    Kalapala, Saibabu; Easteal, Allan J.

    Novel semi-interpenetrating polymer gel electrolytes designed for use in rechargeable lithium polymer batteries are synthesised from methyl methacrylate and the lithium salt of 2-acrylamido-2-methylpropanesulfonic acid (LiAMPS). The gels are made by first synthesising linear chains of poly(LiAMPS) by free radical polymerisation of LiAMPS dissolved in dimethyl acetamide (DMA) or DMA/ethylene carbonate mixtures, then co-polymerisation of methyl methacrylate and a cross-linking monomer (tetraethyleneglycol diacrylate) to form the semi-interpenetrating network. The electrical conductivity of the gels is determined as a function of LiAMPS and methyl methacrylate (MMA) concentrations, cross-link density, and solvent composition. The conductivity ( σ) is found to be in the range 0.2 ≤ σ ≤ 0.8 mS cm -1 at ambient temperature (20 ± 1 °C).

  17. Basic study of a new denture base resin applying hydrophobic methacrylate monomer.

    PubMed

    Umemoto, K; Kurata, S

    1997-06-01

    To improve the water sorption of poly(methyl methacrylate), new hydrophobic monomers, such as norbonyl and phenyl methacrylate, were studied to determine the resin with lower water sorption with no decrease in mechanical property. Water sorption of the copolymers of the hydrophobic monomers and MMA decreased with the increase in the concentration of the monomers. Compressive and bending strength of the copolymers were higher than that of PMMA, and the elastic modulus in bending was the same as that of PMMA. In addition, the transverse-deflection values satisfied ADA specifications. Dynamic mechanical thermal analysis of the copolymers showed a similar tendency to that of PMMA in spite of the introduction of bulky groups, such as norbonyl and phenyl, in the polymer molecule. The polymerization shrinkage in volume was in the following order: norbonyl < phenyl < methyl methacrylate.

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

    PubMed

    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

  19. Assessment of the skin sensitising potency of the lower alkyl methacrylate esters.

    PubMed

    Kimber, Ian; Pemberton, Mark A

    2014-10-01

    There is continued interest in, and imperatives for, the classification of contact allergens according to their relative skin sensitising potency. However, achieving that end can prove problematic, not least when there is an apparent lack of concordance between experimental assessments of potency and the prevalence allergic contact dermatitis as judged by clinical experience. For the purpose of exploring this issue, and illustrating the important considerations that are required to reach sound judgements about potency categorisation, the lower alkyl methacrylate esters (LAM) have been employed here as a case study. Although the sensitising potential of methyl methacrylate (MMA) has been reviewed previously, there is available new information that is relevant for assessment of skin sensitising potency. Moreover, for the purposes of this article, analyses have been extended to include also other LAM for which relevant data are available: ethyl methacrylate (EMA), n-butyl methacrylate (nBMA), isobutyl methacrylate (iBMA), and 2-ethylhexyl methacrylate (EHMA). In addressing the skin sensitising activity of these chemicals and in drawing conclusions regarding relative potency, a number of sources of information has been considered, including estimates of potency derived from local lymph node assay (LLNA) data, the results of guinea pig assays, and data derived from in silico methods and from recently developed in vitro approaches. Moreover, clinical experience of skin sensitisation of humans by LAM has also been evaluated. The conclusion drawn is that MMA and other LAM are contact allergens, but that none of these chemicals has any more than weak skin sensitising potency. We have also explored here the possible bases for this modest sensitising activity. Finally, the nature of exposure to LAM has been reviewed briefly and on the basis of that information, together with an understanding of skin sensitising potency, a risk assessment has been prepared.

  20. Lipase catalyzed HEMA initiated ring-opening polymerization: in situ formation of mixed polyester methacrylates by transesterification.

    PubMed

    Takwa, Mohamad; Xiao, Yan; Simpson, Neil; Malmström, Eva; Hult, Karl; Koning, Cor E; Heise, Andreas; Martinelle, Mats

    2008-02-01

    2-Hydroxyethyl methacrylate (HEMA) was used as initiator for the enzymatic ring-opening polymerization (ROP) of omega-pentadecalactone (PDL) and epsilon-caprolactone (CL). The lipase B from Candida antarctica was found to catalyze the cleavage of the ester bond in the HEMA end group of the formed polyesters, resulting in two major transesterification processes, methacrylate transfer and polyester transfer. This resulted in a number of different polyester methacrylate structures, such as polymers without, with one, and with two methacrylate end groups. Furthermore, the 1,2-ethanediol moiety (from HEMA) was found in the polyester products as an integral part of HEMA, as an end group (with one hydroxyl group) and incorporated within the polyester (polyester chains acylated on both hydroxyl groups). After 72 h, as a result of the methacrylate transfer, 79% (48%) of the initial amount of the methacrylate moiety (from HEMA) was situated (acylated) on the end hydroxyl group of the PPDL (PCL) polyester. In order to prepare materials for polymer networks, fully dimethacrylated polymers were synthesized in a one-pot procedure by combining HEMA-initiated ROP with end-capping using vinyl methacrylate. The novel PPDL dimethacrylate (>95% incorporated methacrylate end groups) is currently in use for polymer network formation. Our results show that initiators with cleavable ester groups are of limited use to obtain well-defined monomethacrylated macromonomers due to the enzyme-based transesterification processes. On the other hand, when combined with end-capping, well-defined dimethacrylated polymers (PPDL, PCL) were prepared.