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Sample records for bent-shaped azobenzene monomers

  1. azobenzene

    Indian Academy of Sciences (India)

    2-hydroxybenzylideneamino)azobenzene having the flexible terminal chain of OCnH2n+1, in which n are even numbers ... base.12,13 Thus, in this work, we report the synthesis and ..... tion, the absence of a singlet at δ = 13.60 ppm indi-.

  2. Novel polymerizable bent-shaped monomeric molecules

    Czech Academy of Sciences Publication Activity Database

    Kozmik, V.; Kovářová, A.; Kuchař, M.; Svoboda, Jiří; Novotná, Vladimíra; Glogarová, Milada; Kroupa, Jan

    2006-01-01

    Roč. 33, č. 1 (2006), s. 41-56 ISSN 0267-8292 R&D Projects: GA ČR(CZ) GA202/05/0431; GA MŠk(CZ) OC D14.50 Institutional research plan: CEZ:AV0Z10100520 Keywords : mesogens * polymerizable * bent-shaped molecules * liquid crystals * ferroelectricity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.417, year: 2006

  3. New photoresponsive (meth)acrylate (co)polymers containing azobenzene pendant sidegroups with carboxylic and dimethylamino substituents .1. Synthesis and characterization of the monomers

    NARCIS (Netherlands)

    Haitjema, HJ; Buruma, R; VanEkenstein, GORA; Tan, YY; Challa, G

    1996-01-01

    New azobenzene-based (az.b.) monomers with CO2H (acid) or N(CH3)(2) (basic) substituents were synthesized. For some of these compounds new synthetic routes had to be developed, especially for the az.b. monomers with a CO2H substituent (azoacids) where their synthesis, purification and (thermal)

  4. Non-symmetrical bent-shaped compounds containing chiral moiety

    Czech Academy of Sciences Publication Activity Database

    Novotná, Vladimíra; Mieczkowska, B.; Hamplová, Věra; Domján, A.; Pociecha, D.; Kašpar, Miroslav; Fodor-Csorba, K.

    2012-01-01

    Roč. 39, č. 10 (2012), s. 1252-1260 ISSN 0267-8292 R&D Projects: GA ČR(CZ) GAP204/11/0723 Institutional research plan: CEZ:AV0Z10100520 Keywords : bent-shaped mesogen * columnar phase * ferroelectricity * polar switching Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.959, year: 2012 http://www.tandfonline.com/doi/abs/10.1080/02678292.2012.714485

  5. Bent Shaped 1,3,4-Oxadiazole/Thiadiazole heterocyclic rings ...

    Indian Academy of Sciences (India)

    Two series of bent shaped 1,3,4-oxadiazole/thiadiazole heterocyclic ring containing liquid crystalline (LC) compounds were synthesized and characterized by FT-IR, 1H, 13C-NMR and ESI-Mass spectro-scopic techniques. Liquid crystal properties were investigated by polarized optical microscopy and differential scanning ...

  6. 3-Aminophenol based bent-shaped liquid crystals with an amide linking group

    Czech Academy of Sciences Publication Activity Database

    Kozmik, V.; Horčic, M.; Svoboda, J.; Novotná, Vladimíra; Pociecha, D.

    2012-01-01

    Roč. 39, č. 8 (2012), s. 943-955 ISSN 0267-8292 R&D Projects: GA ČR(CZ) GAP204/11/0723 Institutional research plan: CEZ:AV0Z10100520 Keywords : liquid crystals * aminophenol * bent-shaped mesogen Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.959, year: 2012 http://dx.doi.org/10.1080/02678292.2012.687781

  7. Photochromic and fluorescent LC gels based on a bent-shaped azobenzene-containing gelator

    Czech Academy of Sciences Publication Activity Database

    Bobrovsky, A.; Shibaev, I.; Hamplová, Věra; Novotná, Vladimíra; Kašpar, Miroslav

    2015-01-01

    Roč. 5, č. 70 (2015), 56891-56895 ISSN 2046-2069 R&D Projects: GA ČR GA13-14133S Institutional support: RVO:68378271 Keywords : liquid crystals * photochromic LC- gels Subject RIV: CC - Organic Chemistry Impact factor: 3.289, year: 2015

  8. Long-Lived Triplet Excited States of Bent-Shaped Pentacene Dimers by Intramolecular Singlet Fission.

    Science.gov (United States)

    Sakuma, Takao; Sakai, Hayato; Araki, Yasuyuki; Mori, Tadashi; Wada, Takehiko; Tkachenko, Nikolai V; Hasobe, Taku

    2016-03-24

    Intramolecular singlet fission (ISF) is a promising photophysical process to construct more efficient light energy conversion systems as one excited singlet state converts into two excited triplet states. Herein we synthesized and evaluated bent-shaped pentacene dimers as a prototype of ISF to reveal intrinsic characters of triplet states (e.g., lifetimes of triplet excited states). In this study, meta-phenylene-bridged TIPS-pentacene dimer (PcD-3Ph) and 2,2'-bipheynyl bridged TIPS-pentacene dimer (PcD-Biph) were newly synthesized as bent-shaped dimers. In the steady-state spectroscopy, absorption and emission bands of these dimers were fully characterized, suggesting the appropriate degree of electronic coupling between pentacene moieties in these dimers. In addition, the electrochemical measurements were also performed to check the electronic interaction between two pentacene moieties. Whereas the successive two oxidation peaks owing to the delocalization were observed in a directly linked-pentacene dimer (PcD) by a single bond, the cyclic voltammograms in PcD-Biph and PcD-3Ph implied the weaker interaction compared to that of p-phenylene-bridged TIPS-pentacene dimer (PcD-4Ph) and PcD. The femtosecond and nanosecond transient absorption spectra clearly revealed the slower ISF process in bent-shaped pentacene dimers (PcD-Biph and PcD-3Ph), more notably, the slower relaxation of the excited triplet states in PcD-Biph and PcD-3Ph. Namely, the quantum yields of triplet states (ΦT) by ISF approximately remain constant (ca. 180-200%) in all dimer systems, whereas the lifetimes of the triplet excited states became much longer (up to 360 ns) in PcD-Biph as compared to PcD-4Ph (15 ns). Additionally, the lifetimes of the corresponding triplet states in PcD-Biph and PcD-3Ph were sufficiently affected by solvent viscosity. In particular, the lifetimes of PcD-Biph triplet state in THF/paraffin (1.0 μs) increased up to approximately three times as compared to that in THF

  9. Photoinduced Reversible Morphological Transformation of Azobenzene-Containing Pseudo-2D Polymers.

    Science.gov (United States)

    Li, Zili; Tang, Miao; Jiang, Chen; Bai, Ruke; Bai, Wei

    2018-05-02

    2D polymer sheets containing azobenzene are successfully prepared by a facile strategy of "2D self-assembly polymerization (2DSP)" via free radical polymerization in solution. A bola amphiphile containing azobenzene as a novel monomer is designed and synthesized. The results indicate that single-layer covalent pseudo-2D polymers on a micrometer scale are obtained after polymerization with vinyl monomers. Moreover, the 2D polymer sheets are highly sensitive to UV light due to incorporation of azobenzene groups into the polymer. Upon alternative irradiation with UV and visible light, the morphological transformation between sheets and rolled-up nanotubes can be achieved based on the reversible trans-to-cis photoisomerization of azobenzene units in the 2D polymer sheets. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Unusual polymorphism in new bent-shaped liquid crystals based on biphenyl as a central molecular core

    Directory of Open Access Journals (Sweden)

    Anna Kovářová

    2014-04-01

    Full Text Available Bent-shaped mesogens possessing a biphenyl as a central core have been synthesized and the role of the terminal chain and the orientation of the ester as a linkage group have been investigated. For the studied molecular core we have established that both parameters play an important role for the mesomorphic properties. The polyfluoroalkyl terminal chain supports the formation of mesophases, and the introduction of a chiral lactate terminal chain destabilizes mesophases for the first type of mutual orientation of ester groups, attached to the central core. On the contrary, for the opposite orientation of esters, the terminal chain has no effect on the mesomorphic properties, and columnar phases have been found for all compounds. A unique phase sequence has been found for the mesogen with the fluorinated chain. A generalized tilted smectics, SmCG, have been observed in a temperature interval between two different lamellar SmCP phases and characterized by X-ray and dielectric measurements. The dielectric spectroscopy data are unique and presented for the first time in the SmCG phase providing new information about the molecular dynamics.

  11. Broadband reflection of polymer-stabilized chiral nematic liquid crystals induced by a chiral azobenzene compound.

    Science.gov (United States)

    Chen, Xingwu; Wang, Ling; Chen, Yinjie; Li, Chenyue; Hou, Guoyan; Liu, Xin; Zhang, Xiaoguang; He, Wanli; Yang, Huai

    2014-01-21

    A chiral nematic liquid crystal-photopolymerizable monomer-chiral azobenzene compound composite was prepared and then polymerized under UV irradiation. The reflection wavelength of the composite can be extended to cover the 1000-2400 nm range and also be adjusted to the visible light region by controlling the concentration of chiral compounds.

  12. Biaxial and antiferroelectric structure of the orthogonal smectic phase of a bent-shaped molecule and helical structure in a chiral mixture system

    Science.gov (United States)

    Kang, Sungmin; Nguyen, Ha; Nakajima, Shunpei; Tokita, Masatoshi; Watanabe, Junji

    2013-05-01

    We examined the biaxial and antiferroelectric properties in the Smectic-APA (Sm-APA) phase of bent-shaped DC-S-8. The biaxiality, which results from the existence of a secondary director, was well established from birefringence observations in the homeotropically aligned Sm-APA. By entering into Sm-APA phase, the birefringence (Δn, difference between two refractive indices of short axes) continuously increased from 0 to 0.02 with decreasing temperature. The antiferroelectric switching and second harmonic generation (SHG) activity on the field-on state were also observed in the Sm-APA phase, and the evaluated spontaneous polarization (PS) value strongly depended on temperature. The temperature dependence of Δn and PS resembles each other and follows Haller's approximation, showing that the biaxiality is due to polar packing in which the molecules are preferentially packed with their bent direction arranged in the same direction, and that the phase transition of Sm-APA to Sm-A is second order. The biaxiality was further examined in chiral Sm-APA*. Doping with chiral components induced the helical twisting of the secondary director in the Sm-APA* phase, which was confirmed by observing the reflection of the circular dichroism (CD) bands in the homeotropically aligned cell. The helical pitch of Sm-APA* is tunable in the range of 300-700 nm wavelength with a variation in the chiral content of 5 to 10 weight (wt)%.

  13. New photoresponsive (meth)acrylate (co)polymers containing azobenzene pendant sidegroups with carboxylic and dimethylamino substituents .2. Synthesis and characterization of polymers and copolymers

    NARCIS (Netherlands)

    Haitjema, HJ; Buruma, R; VanEkenstein, GORA; Tan, YY; Challa, G

    1996-01-01

    The title (co)polymers, used for our investigations on their photoresponsive behaviour were obtained by free radical (co)polymerization. The monomer was either an acrylate or a methacrylate to which an azobenzene group, modified with a para-placed dimethylamino or a carboxylic pendant group, was

  14. Azobenzene Photoswitches for Staudinger-Bertozzi Ligation

    NARCIS (Netherlands)

    Szymanski, Wiktor; Wu, Bian; Poloni, Claudia; Janssen, Dick B.; Feringa, Ben L.

    2013-01-01

    A novel family of azobenzenes containing residues needed for aqueous Staudinger–Bertozzi ligation to azides was designed. The resulting photochromes show stable and reversible switching behavior in water, with a photostationary state (PSS) of up to 95:5 cis/trans. Applications in model systems

  15. Photoinduced Deformation of Azobenzene Polyester Films

    DEFF Research Database (Denmark)

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

    2000-01-01

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

  16. Unusual photoanisotropic alignment in amorphous azobenzene polymers

    DEFF Research Database (Denmark)

    Ramanujam, P.S.

    2015-01-01

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

  17. Graphene oxide catalyzed cis-trans isomerization of azobenzene

    Directory of Open Access Journals (Sweden)

    Dongha Shin

    2014-09-01

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

  18. DNA compaction by azobenzene-containing surfactant

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  19. The still unknown azobenzene - Wavelength dependent photoanisotropy in amorphous azobenzene polymers

    DEFF Research Database (Denmark)

    Ramanujam, P.S.; Jensen, Ole Bjarlin; Tidemand-Lichtenberg, Peter

    2013-01-01

    We demonstrate a new type of anisotropy in thin films of amorphous azobenzene polymers induced between 570 and 633 nm, where the absorbance in the film is on the order of 0.05. The anisotropy has a pronounced radial contribution. This observation points to an additional mechanism for the alignment...

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

    DEFF Research Database (Denmark)

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

    2006-01-01

    In this article, we describe fabrication of polarisation holographic optical elements in azobenzene polyesters. Both liquid crystalline and amorphous side-chain polyesters have been utilised. Diffractive optical elements such as lenses and gratings that are sensitive to the polarisation...... of the incident light have been fabricated with polarisation holography. Computer-generated optical elements and patterns have also been written with a single polarised laser beam. Recording of polarisation defects enabling easy visualisation is also shown to be feasible in azobenzene polyesters....

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

    DEFF Research Database (Denmark)

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

    1999-01-01

    Azobenzenes can serve as model compounds for the study of trans-cis isomerization in more complex molecules. We have performed time-resolved spectroscopy in solutions containing free azobenzene chromophores and diols with a view to obtaining the energy levels and lifetimes of the excited states....... A transition route based on experimental results for the theoretically calculated energy level scheme is proposed. Physical observations of surface relief in thin films of azobenzene polymers when irradiated with polarized light are reported. These include two beam polarization holographic observations...... and single beam transmission measurements through a mask, followed by atomic force microscope and profiler investigations. It is concluded that none of the prevalent theories can explain all the observed facts....

  2. Approximate photochemical dynamics of azobenzene with reactive force fields

    Science.gov (United States)

    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).

  3. Optically induced surface relief phenomena in azobenzene polymers

    DEFF Research Database (Denmark)

    Holme, NCR; Nikolova, Ludmila; Hvilsted, Søren

    1999-01-01

    Azobenzene polymers and oligomers show intriguing surface relief features when irradiated with polarized laser light. We show through atomic force microscopic investigation of side-chain azobenzene polymers after irradiation through an amplitude mask that large peaks or trenches result depending...... on the architecture of the polymer. Extensive mass transport over long distances has been observed, paving the way for easy replication of nanostructures. We also show that it is possible to store microscopic images as topographic features in the polymers just through polarized light irradiation. (C) 1999 American...... Institute of Physics....

  4. Direct and Versatile Synthesis of Red-Shifted Azobenzenes

    NARCIS (Netherlands)

    Hansen, Mickel J.; Lerch, Michael M.; Szymanski, Wiktor; Feringa, Ben L.

    2016-01-01

    A straightforward synthesis of azobenzenes with bathochromically-shifted absorption bands is presented. It employs an ortho-lithiation of aromatic substrates, followed by a coupling reaction with aryldiazonium salts. The products are obtained with good to excellent yields after simple purification.

  5. Photoinduced Circular Anisotropy in Side-Chain Azobenzene Polyesters

    DEFF Research Database (Denmark)

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

    1997-01-01

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

  6. Photoinduced macroscopic chiral structures in a series of azobenzene copolyesters

    DEFF Research Database (Denmark)

    Nedelchev, L.; Nikolova, L.; Matharu, A.

    2002-01-01

    A study of the propagation of elliptically polarized light and the resulting formation of macroscopic chiral structures in a series of azobenzene side-chain copolyesters, in which the morphology is varied from liquid crystalline to amorphous, is reported. Real-time measurements are presented...

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

    Science.gov (United States)

    Sasai, Ryo; Shinomura, Hisashi

    2013-02-01

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

  8. Mechanically induced cis to trans reisomerization of azobenzene

    Science.gov (United States)

    Turansky, Robert; Konopka, Martin; Stich, Ivan; Marx, Dominik

    2007-03-01

    Using density functional techniques we study mechanochemistry of the azobenzene molecule. Azobenzene is an optically switchable molecule. Laser light is normally used to achieve molecular switching between the cis and trans isomers. We use mechanochemistry to achieve the switching. Thiolate-gold bond can used to exert mechanical energy on the molecule bonded between two gold electrodes in static AFM apparatus. Our model consists of two realistic gold electrodes bridged by dithioazobenzene. We find that pulling the transisomer leads just to formation of gold nanowires and mechanical breakage of the electrodes. However, mechanochemistry with modest applied forces leads to cis trans reisomerization via rotation mechanism. Contrary, use of simple constraints instead of realistic gold electrodes, leads to cis trans reisomerization, albeit with significantly larger applied forces and via inversion mechanism. Important experimental and theoretical ramifications of these simulations will be discussed.

  9. Propagation of polarized light through azobenzene polyester films

    DEFF Research Database (Denmark)

    Nedelchev, L; Matharu, A; Nikolova, Ludmila

    2002-01-01

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

  10. Light intensity dependent optical rotation in azobenzene polymers

    Science.gov (United States)

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

    2006-05-01

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

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

    International Nuclear Information System (INIS)

    Sasai, Ryo; Shinomura, Hisashi

    2013-01-01

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

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

    DEFF Research Database (Denmark)

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

    1998-01-01

    The microscopic properties of azobenzene chromophores are important for a correct description of optical storage systems based on photoinduced anisotropy in azobenzene polymers. A quantum model of these properties is presented and verified by comparison to experimental absorption spectra for trans...

  13. Monomers and Monomer Mixtures Used in Impregnation of Fibrous Materials

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1968-10-15

    Some important properties of monomers and polymers in relation to their use for reinforcement of fibrous materials are listed. Some monomers and their properties important in impregnation of fibrous materials are also listed. In general it is not advantageous to use a pure monomer for impregnation but rather a mixture of monomers or a mixture of a monomer and a low molecular weight polymer such as unsaturated polyester. Some of these mixtures which have been well studied in connection with WPC are listed together with some of their properties when used in WPC. Other monomer mixtures may well come in question and other monomers can probably be used. For instance, it is reported from Japan that the cheap monomer ethyleneoxide, which cannot be polymerized by gamma radiation as such, can be polymerized (in bulk) as a mixture with methylmethacrylate. Good results with WPC have generally been obtained without swelling agents but more is grafted if some swelling agent is used, and it is possible that a swelling agent might be useful in the case of fibre-boards. Solvents, plasticizers, crosslinkable natural resins, aromatic chlorinated hydrocarbons, and retardants can be added, and with their use the properties of WPC can be widely modified. For example, a chlorinated wax can act as retardant, can reduce the total dose of radiation and can increase the flame resistance simultaneously.

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

    International Nuclear Information System (INIS)

    Feng Wen-Ke; Wang Shu-Feng; Gong Qi-Huang; Feng Yi-Yu; Feng Wei; Yi Wen-Hui

    2010-01-01

    This paper studies the intramolecular photoinduced electron-transfer (PET) of covalent bonded azobenzene-perylene diimide (AZO-PDI) in solvents by using steady-state and time-resolved fluorescence spectroscopy together with ultrafast transient absorption spectroscopic techniques. Fast fluorescence quenching is observed when AZO-PDI is excited at characteristic wavelengths of AZO and perylene moieties. Reductive electron-transfer with transfer rate faster than 10 11 s −1 is found. This PET process is also consolidated by femtosecond transient absorption spectra

  15. Photoresponsive Block Copolymers Containing Azobenzenes and Other Chromophores

    Directory of Open Access Journals (Sweden)

    Takaomi Kobayashi

    2010-01-01

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

  16. Rewritable azobenzene polyester for polarization holographic data storage

    DEFF Research Database (Denmark)

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

    2000-01-01

    Optical storage properties of thin azobenzene side-chain polyester films were examined by polarization holographic measurements. The new amorphous polyester film is the candidate material for the purpose of rewritable holographic memory system. Temporal formation of anisotropic and topographic...... gratings was studied in case of films with and without a hard protective layer. We showed that the dominant contribution to the diffraction efficiency comes from the anisotropy in case of expositions below 1 sec even for high incident intensity. The usage of the same wavelength for writing, reading...

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

    Directory of Open Access Journals (Sweden)

    Yagang Zhang

    2012-04-01

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

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

    Science.gov (United States)

    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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Compound grating structures in photonic crystals for resonant excitation of azobenzene

    DEFF Research Database (Denmark)

    Jahns, Sabrina; Kallweit, Christine; Adam, Jost

    Photo-switchable molecules such as azobenzene are of high interest for “smart” surfaces. Such “smart” surfaces respond to external light excitation by changing their macroscopic properties. The absorbance of light on a single normal path through a layer of azobenzene immobilized on a surface......-difference time-domain (FDTD) calculations for determination of resonance positions and electric field strengths in compound grating structures. By superimposing two single-period gratings a photonic crystal can be designed supporting multiple guided mode resonances suitable to switch azobenzenes between...

  20. Ionic Liquid Epoxy Resin Monomers

    Science.gov (United States)

    Paley, Mark S. (Inventor)

    2013-01-01

    Ionic liquid epoxide monomers capable of reacting with cross-linking agents to form polymers with high tensile and adhesive strengths. Ionic liquid epoxide monomers comprising at least one bis(glycidyl) N-substituted nitrogen heterocyclic cation are made from nitrogen heterocycles corresponding to the bis(glycidyl) N-substituted nitrogen heterocyclic cations by a method involving a non-nucleophilic anion, an alkali metal cation, epichlorohydrin, and a strong base.

  1. Synthesis and Characterization of Photo-Responsive Thermotropic Liquid Crystals Based on Azobenzene

    Directory of Open Access Journals (Sweden)

    Runmiao Yang

    2018-03-01

    Full Text Available A series of new thermotropic liquid crystals (LCs containing azobenzene units was synthesized. The structures of the compounds were characterized by means of NMR and FTIR spectroscopy. Their mesomorphic behaviors were investigated via differential scanning calorimetry (DSC and polarizing optical microscopy (POM. Based on the POM and DSC measurements, the optical properties of the Razo-ester were tested using UV-vis spectroscopy. The azobenzene side chain displayed a strong ability to influence the formation of thermotropic LCs.

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

    International Nuclear Information System (INIS)

    Liu, Rong-Hua; Li, Wen-Wei; Sheng, Guo-Ping; Tong, Zhong-Hua; Lam, Michael Hon-Wah; Yu, Han-Qing

    2015-01-01

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

  3. Photosensitive Layer-by-Layer Assemblies Containing Azobenzene Groups: Synthesis and Biomedical Applications

    Directory of Open Access Journals (Sweden)

    Uichi Akiba

    2017-10-01

    Full Text Available This review provides an overview of the syntheses of photosensitive layer-by-layer (LbL films and microcapsules modified with azobenzene derivatives and their biomedical applications. Photosensitive LbL films and microcapsules can be prepared by alternate deposition of azobenzene-bearing polymers and counter polymers on the surface of flat substrates and microparticles, respectively. Azobenzene residues in the films and microcapsules exhibit trans-to-cis photoisomerization under UV light, which causes changes in the physical or chemical properties of the LbL assemblies. Therefore, azobenzene-functionalized LbL films and microcapsules have been used for the construction of photosensitive biomedical devices. For instance, cell adhesion on the surface of a solid can be controlled by UV light irradiation by coating the surface with azobenzene-containing LbL films. In another example, the ion permeability of porous materials coated with LbL films can be regulated by UV light irradiation. Furthermore, azobenzene-containing LbL films and microcapsules have been used as carriers for drug delivery systems sensitive to light. UV light irradiation triggers permeability changes in the LbL films and/or decomposition of the microcapsules, which results in the release of encapsulated drugs and proteins.

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

    DEFF Research Database (Denmark)

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

    2002-01-01

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

  5. Antimicrobial azobenzene compounds and their potential use in biomaterials

    Science.gov (United States)

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

    2016-04-01

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

  6. In situ immobilization on the silica gel surface and adsorption capacity of polymer-based azobenzene on toxic metal ions

    Science.gov (United States)

    Savchenko, Irina; Yanovska, Elina; Sternik, Dariusz; Kychkyruk, Olga; Ol'khovik, Lidiya; Polonska, Yana

    2018-03-01

    In situ immobilization of poly[(4-methacryloyloxy-(4'-carboxy)azobenzene] on silica gel surface has been performed by radical polymerization of monomer. The fact of polymer immobilization is confirmed by IR spectroscopy. TG and DSC-MS analysis showed that the mass of the immobilized polymer was 10.61%. The SEM-microphotograph-synthesized composite analysis showed that the immobilized polymer on the silica gel surface is placed in the form of fibers. It has been found that the synthesized composite exhibits the sorption ability in terms of microquantities of Cu(II), Cd(II), Pb(II), Mn(II) and Fe(III) ions in a neutral aqueous medium. The quantitative sorption of microquantities of Pb(II) and Fe(III) ions has been recorded. It has been found that immobilization of the silica gel surface leads to an increase in its sorption capacitance for Fe(III), Cu(II) and Pb(II) ions by half.

  7. Super electron donor-mediated reductive transformation of nitrobenzenes: a novel strategy to synthesize azobenzenes and phenazines.

    Science.gov (United States)

    Nozawa-Kumada, Kanako; Abe, Erina; Ito, Shungo; Shigeno, Masanori; Kondo, Yoshinori

    2018-05-02

    The transformation of nitrobenzenes into azobenzenes by pyridine-derived super electron donor 2 is described. This method provides an efficient synthesis of azobenzenes because of not requiring the use of expensive transition-metals, toxic or flammable reagents, or harsh conditions. Moreover, when using 2-fluoronitrobenzenes as substrates, phenazines were found to be obtained. The process affords a novel synthesis of phenazines.

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

    Science.gov (United States)

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

    2013-11-19

    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 10(2) mm/s) and powers (as much as 1 kW/m(3)). The contactless, ultra-fast actuation is observed at irradiation intensities 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.

  9. Photomechanical Deformation of Azobenzene-Functionalized Polyimides Synthesized with Bulky Substituents (Postprint)

    Science.gov (United States)

    2017-12-06

    comparative UV − vis result (Figure S6, Supporting Information) that azoCBODA-BPADA has the lowest absorbance change for its azobenzene trans−cis...or trans−cis−trans reorientation processes upon irradiation of 365 nm UV or blue-green light (440−530 nm), respectively. Exposure of these materials...to UV light induces a trans−cis isomerization, resulting in a length reduction of the molecular axis of azobenzene from 9 Å (trans) to 5.5 Å (cis).10

  10. Azobenzene Pd(II) complexes with N^N- and N^O-type ligands

    Science.gov (United States)

    Nikolaeva, M. V.; Puzyk, An. M.; Puzyk, M. V.

    2017-05-01

    Methods of synthesis of cyclometalated azobenzene palladium(II) complexes of [Pd(N^N)Azb]ClO4 and [Pd(N^O)Azb]ClO4 types (where Azb- is the deprotonated form of azobenzene; N^N is 2NH3, ethylenediamine, or 2,2'-bipyridine; and (N^O)- is the deprotonated form of amino acid (glycine, α-alanine, β-alanine, tyrosine, or tryptophan)) are developed. The electronic absorption and the electrochemical properties of these complexes are studied.

  11. The growth and electronic structure of azobenzene-based functional molecules on layered crystals

    International Nuclear Information System (INIS)

    Iwicki, J; Ludwig, E; Buck, J; Kalläne, M; Kipp, L; Rossnagel, K; Köhler, F; Herges, R

    2012-01-01

    In situ ultraviolet photoelectron spectroscopy is used to study the growth of ultrathin films of azobenzene-based functional molecules (azobenzene, Disperse Orange 3 and a triazatriangulenium platform with an attached functional azo-group) on the layered metal TiTe 2 and on the layered semiconductor HfS 2 at liquid nitrogen temperatures. Effects of intermolecular interactions, of the substrate electronic structure, and of the thermal energy of the sublimated molecules on the growth process and on the adsorbate electronic structure are identified and discussed. A weak adsorbate-substrate interaction is particularly observed for the layered semiconducting substrate, holding the promise of efficient molecular photoswitching.

  12. Photoinduced changes of surface topography in amorphous, liquid-crystalline, and crystalline films of bent-core azobenzene-containing substance

    Czech Academy of Sciences Publication Activity Database

    Bobrovsky, A.; Mochalov, K.; Oleinikov, V.; Solovyeva, D.; Shibaev, V.; Bogdanova, Y.; Hamplová, Věra; Kašpar, Miroslav; Bubnov, Alexej

    2016-01-01

    Roč. 120, č. 22 (2016), 5073-5082 ISSN 1520-6106 R&D Projects: GA ČR GA16-12150S; GA MŠk(CZ) LH15305 Institutional support: RVO:68378271 Keywords : liquid crystals * azo group * bent-shaped material * nematic * photo-optical behaviour Subject RIV: JJ - Other Materials Impact factor: 3.177, year: 2016

  13. Azobenzene versus 3,3',5,5'-tetra-tert-butyl-azobenzene (TBA) at Au(111): characterizing the role of spacer groups.

    Science.gov (United States)

    McNellis, Erik R; Bronner, Christopher; Meyer, Jörg; Weinelt, Martin; Tegeder, Petra; Reuter, Karsten

    2010-06-28

    We present large-scale density-functional theory (DFT) calculations and temperature programmed desorption measurements to characterize the structural, energetic and vibrational properties of the functionalized molecular switch 3,3',5,5'-tetra-tert-butyl-azobenzene (TBA) adsorbed at Au(111). Particular emphasis is placed on exploring the accuracy of the semi-empirical dispersion correction approach to semi-local DFT (DFT-D) in accounting for the substantial van der Waals component in the surface bonding. In line with previous findings for benzene and pure azobenzene at coinage metal surfaces, DFT-D significantly overbinds the molecule, but seems to yield an accurate adsorption geometry as far as can be judged from the experimental data. Comparing the trans adsorption geometry of TBA and azobenzene at Au(111) reveals a remarkable insensitivity of the structural and vibrational properties of the -N[double bond, length as m-dash]N- moiety. This questions the established view of the role of the bulky tert-butyl-spacer groups for the switching of TBA in terms of a mere geometric decoupling of the photochemically active diazo-bridge from the gold substrate.

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

    DEFF Research Database (Denmark)

    Sánchez, C; Alcalá, R; Hvilsted, Søren

    2001-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-08-04

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

  16. Thermal isomerization of azobenzenes: on the performance of Eyring transition state theory

    Science.gov (United States)

    Rietze, Clemens; Titov, Evgenii; Lindner, Steven; Saalfrank, Peter

    2017-08-01

    The thermal Z\\to E (back-)isomerization of azobenzenes is a prototypical reaction occurring in molecular switches. It has been studied for decades, yet its kinetics is not fully understood. In this paper, quantum chemical calculations are performed to model the kinetics of an experimental benchmark system, where a modified azobenzene (AzoBiPyB) is embedded in a metal-organic framework (MOF). The molecule can be switched thermally from cis to trans, under solvent-free conditions. We critically test the validity of Eyring transition state theory for this reaction. As previously found for other azobenzenes (albeit in solution), good agreement between theory and experiment emerges for activation energies and activation free energies, already at a comparatively simple level of theory, B3LYP/6-31G* including dispersion corrections. However, theoretical Arrhenius prefactors and activation entropies are in qualitiative disagreement with experiment. Several factors are discussed that may have an influence on activation entropies, among them dynamical and geometric constraints (imposed by the MOF). For a simpler model—Z\\to E isomerization in azobenzene—a systematic test of quantum chemical methods from both density functional theory and wavefunction theory is carried out in the context of Eyring theory. Also, the effect of anharmonicities on activation entropies is discussed for this model system. Our work highlights capabilities and shortcomings of Eyring transition state theory and quantum chemical methods, when applied for the Z\\to E (back-)isomerization of azobenzenes under solvent-free conditions.

  17. Photopiezoelectric Composites of Azobenzene-Functionalized Polyimides and Polyvinylidene Fluoride (Postprint)

    Science.gov (United States)

    2014-10-01

    as evident in the calculated chromophore number density (CND) as well as the measured absorption coeffi cient (α) over the range of azobenzene...Hiraoka , S. Kubo , J.-I. Mamiya , M. Kinoshita , T. Ikeda , A. Shishido , ACS Macro Lett. 2011 , 1 , 96 . [16] J. Cviklinski , A

  18. Surface active monomers synthesis, properties, and application

    CERN Document Server

    Borzenkov, Mykola

    2014-01-01

    This brief includes information on the background?of and development of synthesis of various types of surface active monomers. The authors explain the importance of utilization of surface active monomers for creation of surface active polymers? and the various biomedical applications of such compounds . This brief introduces techniques for the synthesis of novel types of surface active monomers, their colloidal and polymerizable properties and application for needs of medicine and biology.

  19. Monomers capable of forming four hydrogen bridges and supramolecular polymers formed by copolymerization of these monomers with regular monomers

    NARCIS (Netherlands)

    2004-01-01

    The invention relates to the synthesis of polymers containing self-complementary quadruple hydrogen groups by copolymerizing monomers containing a quadruple hydrogen bonding group with one or more monomers of choice. The resulting polymers show unique new characteristics due to the presence of

  20. Controlled Sol-Gel Transitions of a Thermoresponsive Polymer in a Photoswitchable Azobenzene Ionic Liquid as a Molecular Trigger.

    Science.gov (United States)

    Wang, Caihong; Hashimoto, Kei; Tamate, Ryota; Kokubo, Hisashi; Watanabe, Masayoshi

    2018-01-02

    Producing ionic liquids (ILs) that function as molecular trigger for macroscopic change is a challenging issue. Photoisomerization of an azobenzene IL at the molecular level evokes a macroscopic response (light-controlled mechanical sol-gel transitions) for ABA triblock copolymer solutions. The A endblocks, poly(2-phenylethyl methacrylate), show a lower critical solution temperature in the IL mixture containing azobenzene, while the B midblock, poly(methyl methacrylate), is compatible with the mixture. In a concentrated polymer solution, different gelation temperatures were observed in it under dark and UV conditions. Light-controlled sol-gel transitions were achieved by a photoresponsive solubility change of the A endblocks upon photoisomerization of the azobenzene IL. Therefore, an azobenzene IL as a molecular switch can tune the self-assembly of a thermoresponsive polymer, leading to macroscopic light-controlled sol-gel transitions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Conserving Coherence and Storing Energy during Internal Conversion: Photoinduced Dynamics of cis- and trans-Azobenzene Radical Cations

    KAUST Repository

    Munkerup, Kristin; Romanov, Dmitri A.; Bohinski, Timothy; Stephansen, Anne B.; Levis, Robert J.; Sø lling, Theis Ivan

    2017-01-01

    Light harvesting via energy storage in azobenzene has been a key topic for decades, and the process of energy distribution over the molecular degrees of freedom following photoexcitation remains to be understood. Dynamics of a photoexcited system

  2. Step growth of two flexible ABf monomers

    DEFF Research Database (Denmark)

    Cameron, Colin; Fawcett, Allan H.; Hetherington, Cecil R.

    2000-01-01

    A three-dimensional lattice model was used to simulate the competition between the growth of hyperbranched structures and cycle formation that occurs when flexible ABf monomers undergo step growth. The monomers in the model are mapped onto several lattice sites. The effect of functionality...

  3. Azobenzene as a photoregulator covalently attached to RNA: a quantum mechanics/molecular mechanics-surface hopping dynamics study.

    Science.gov (United States)

    Mondal, Padmabati; Granucci, Giovanni; Rastädter, Dominique; Persico, Maurizio; Burghardt, Irene

    2018-05-28

    The photoregulation of nucleic acids by azobenzene photoswitches has recently attracted considerable interest in the context of emerging biotechnological applications. To understand the mechanism of photoinduced isomerisation and conformational control in these complex biological environments, we employ a Quantum Mechanics/Molecular Mechanics (QM/MM) approach in conjunction with nonadiabatic Surface Hopping (SH) dynamics. Two representative RNA-azobenzene complexes are investigated, both of which contain the azobenzene chromophore covalently attached to an RNA double strand via a β-deoxyribose linker. Due to the pronounced constraints of the local RNA environment, it is found that trans -to- cis isomerization is slowed down to a time scale of ∼10-15 picoseconds, in contrast to 500 femtoseconds in vacuo , with a quantum yield reduced by a factor of two. By contrast, cis -to- trans isomerization remains in a sub-picosecond regime. A volume-conserving isomerization mechanism is found, similarly to the pedal-like mechanism previously identified for azobenzene in solution phase. Strikingly, the chiral RNA environment induces opposite right-handed and left-handed helicities of the ground-state cis -azobenzene chromophore in the two RNA-azobenzene complexes, along with an almost completely chirality conserving photochemical pathway for these helical enantiomers.

  4. Photoisomers of Azobenzene Star with a Flat Core: Theoretical Insights into Multiple States from DFT and MD Perspective.

    Science.gov (United States)

    Koch, Markus; Saphiannikova, Marina; Santer, Svetlana; Guskova, Olga

    2017-09-21

    This study focuses on comparing physical properties of photoisomers of an azobenzene star with benzene-1,3,5-tricarboxamide core. Three azobenzene arms of the molecule undergo a reversible trans-cis isomerization upon UV-vis light illumination giving rise to multiple states from the planar all-trans one, via two mixed states to the kinked all-cis isomer. Employing density functional theory, we characterize the structural and photophysical properties of each state indicating a role the planar core plays in the coupling between azobenzene chromophores. To characterize the light-triggered switching of solvophilicity/solvophobicity of the star, the difference in solvation free energy is calculated for the transfer of an azobenzene star from its gas phase to implicit or explicit solvents. For the latter case, classical all-atom molecular dynamics simulations of aqueous solutions of azobenzene star are performed employing the polymer consistent force field to shed light on the thermodynamics of explicit hydration as a function of the isomerization state and on the structuring of water around the star. From the analysis of two contributions to the free energy of hydration, the nonpolar van der Waals and the electrostatic terms, it is concluded that isomerization specificity largely determines the polarity of the molecule and the solute-solvent electrostatic interactions. This convertible hydrophilicity/hydrophobicity together with readjustable occupied volume and the surface area accessible to water, affects the self-assembly/disassembly of the azobenzene star with a flat core triggered by light.

  5. Photoswitching in azobenzene self-assembled monolayers capped on zinc oxide: nanodots vs nanorods.

    Science.gov (United States)

    Shah, Syed Mujtaba; Martini, Cyril; Ackermann, Jörg; Fages, Frédéric

    2012-02-01

    We report the synthesis and spectroscopic characterization of nanohybrid structures consisting of an azobenzene compound grafted on the surface of zinc oxide nanoparticles. Characteristic bathochromic shifts indicate that the azobenzene photochromic molecules self-assemble onto the surface of the nanocrystals. The extent of packing is dependent on the shape of the nanoparticle. ZnO nanorods, with flat facets, enable a tighter organization of the molecules in the self-assembled monolayer than in the case of nanodots that display a more curvated shape. Consistently, the efficiency of photochromic switching of the self-assembled monolayer on ZnO nanoparticles is also shown to be strongly affected by nanoparticle shape. Copyright © 2011 Elsevier Inc. All rights reserved.

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

    Science.gov (United States)

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

    2016-08-01

    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.

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

    Directory of Open Access Journals (Sweden)

    Xingmao Jiang

    2011-01-01

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

  8. Photoinduced anisotropy in a family of amorphous azobenzene polyesters for optical storage

    DEFF Research Database (Denmark)

    Nedelchev, Lian; Matharu, Avtar S.; Hvilsted, Søren

    2003-01-01

    of E1aX polymers characterized by two-ring aromatic substituent in the main chain is a good candidate for optical data storage media. A recording energy of approximately 2 J/cm(2) is sufficient to induce high refractive-index modulations of Deltan = 0.13 in these materials, which is retained even......We investigate parameters associated with optical data storage in a variety of amorphous side-chain azobenzene-containing polyesters denoted as E1aX. The polyesters possess a common cyano-substituted azobenzene chromophore as a side chain, but differ in their main-chain polyester composition....... Seventeen different polymers from the E1aX family divided into four classes, depending on the type of the main-chain substituent (one-, two-, and three-ring aromatic or alicyclic) have been thoroughly investigated. Various parameters characterizing the photoinduced birefringence in these materials...

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

    Directory of Open Access Journals (Sweden)

    Jaume García-Amorós

    2012-07-01

    Full Text Available Photochromic switches that are able to transmit information in a quick fashion have attracted a growing interest within materials science during the last few decades. Although very fast photochromic switching materials working within hundreds of nanoseconds based on other chromophores, such as spiropyranes, have been successfully achieved, reaching such fast relaxation times for azobenzene-based photochromic molecular switches is still a challenge. This review focuses on the most recent achievements on azobenzene-based light-driven real-time information-transmitting systems. Besides, the main relationships between the structural features of the azo-chromophore and the thermal cis-to-trans isomerisation, the kinetics and mechanism are also discussed as a key point for reaching azoderivatives endowed with fast thermal back-isomerisation kinetics.

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

    DEFF Research Database (Denmark)

    Pedersen, M; Hvilsted, Søren; Holme, NCR

    1999-01-01

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

  11. Remote control of soft nano-objects by light using azobenzene containing surfactants

    Science.gov (United States)

    Santer, Svetlana

    2018-01-01

    We review recent progress in the field of light responsive soft nano-objects. These are systems the shape, size, surface area and surface energy of which can be easily changed by low-intensity external irradiation. Here we shall specifically focus on microgels, DNA molecules, polymer brushes and colloidal particles. One convenient way to render these objects photosensitive is to couple them via ionic and/or hydrophobic interactions with azobenzene containing surfactants in a non-covalent way. The advantage of this strategy is that these surfactants can make any type of charged object light responsive without the need for possibly complicated (and irreversible) chemical conjugation. In the following, we will exclusively discuss only photosensitive surfactant systems. These contain a charged head and a hydrophobic tail into which an azobenzene group is incorporated, which can undergo reversible photo-isomerization from a trans- to a cis-configuration under UV illumination. These kinds of photo-isomerizations occur on a picosecond timescale and are fully reversible. The two isomers in general possess different polarity, i.e. the trans-state is less polar with a dipole moment of usually close to 0 Debye, while the cis-isomer has a dipole moment up to 3 Debye or more, depending on additional phenyl ring substituents. As part of the hydrophobic tail of a surfactant molecule, the photo-isomerization also changes the hydrophobicity of the molecule as a whole and hence its solubility, surface energy, and strength of interaction with other substances. Being a molecular actuator, which converts optical energy in to mechanical work, the azobenzene group in the shape of surfactant molecule can be utilized in order to actuate matter on larger time and length scale. In this paper we show several interesting examples, where azobenzene containing surfactants play the role of a transducer mediating between different states of size, shape, surface energy and spatial arrangement of

  12. Photoswitchable nanoporous films by loading azobenzene in metal-organic frameworks of type HKUST-1.

    Science.gov (United States)

    Müller, Kai; Wadhwa, Jasmine; Singh Malhi, Jasleen; Schöttner, Ludger; Welle, Alexander; Schwartz, Heidi; Hermann, Daniela; Ruschewitz, Uwe; Heinke, Lars

    2017-07-13

    Photoswitchable metal-organic frameworks (MOFs) enable the dynamic remote control of their key properties. Here, a readily producible approach is presented where photochromic molecules, i.e. azobenzene (AB) and o-tetrafluoroazobenzene (tfAB), are loaded in MOF films of type HKUST-1. These nanoporous films, which can be reversibly switched with UV/visible or only visible light, have remote-controllable guest uptake properties.

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

    Science.gov (United States)

    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.

  14. Circularly Polarized Light with Sense and Wavelengths To Regulate Azobenzene Supramolecular Chirality in Optofluidic Medium.

    Science.gov (United States)

    Wang, Laibing; Yin, Lu; Zhang, Wei; Zhu, Xiulin; Fujiki, Michiya

    2017-09-20

    Circularly polarized light (CPL) as a massless physical force causes absolute asymmetric photosynthesis, photodestruction, and photoresolution. CPL handedness has long been believed to be the determining factor in the resulting product's chirality. However, product chirality as a function of the CPL handedness, irradiation wavelength, and irradiation time has not yet been studied systematically. Herein, we investigate this topic using achiral polymethacrylate carrying achiral azobenzene as micrometer-size aggregates in an optofluidic medium with a tuned refractive index. Azobenzene chirality with a high degree of dissymmetry ratio (±1.3 × 10 -2 at 313 nm) was generated, inverted, and switched in multiple cycles by irradiation with monochromatic incoherent CPL (313, 365, 405, and 436 nm) for 20 s using a weak incoherent light source (≈ 30 μW·cm -2 ). Moreover, the optical activity was retained for over 1 week in the dark. Photoinduced chirality was swapped by the irradiating wavelength, regardless of whether the CPL sense was the same. This scenario is similar to the so-called Cotton effect, which was first described in 1895. The tandem choice of both CPL sense and its wavelength was crucial for azobenzene chirality. Our experimental proof and theoretical simulation should provide new insight into the chirality of CPL-controlled molecules, supramolecules, and polymers.

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

    Science.gov (United States)

    Toshchevikov, V; Saphiannikova, M; Heinrich, G

    2009-04-16

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

  16. Enhanced Deformation of Azobenzene-Modified Liquid Crystal Polymers under Dual Wavelength Exposure: A Photophysical Model

    Science.gov (United States)

    Liu, Ling; Onck, Patrick R.

    2017-08-01

    Azobenzene-embedded liquid crystal polymers can undergo mechanical deformation in response to ultraviolet (UV) light. The natural rodlike trans state azobenzene absorbs UV light and isomerizes to a bentlike cis state, which disturbs the order of the polymer network, leading to an anisotropic deformation. The current consensus is that the magnitude of the photoinduced deformation is related to the statistical building up of molecules in the cis state. However, a recent experimental study [Liu and Broer, Nat. Commun. 6 8334 (2015)., 10.1038/ncomms9334] shows that a drastic (fourfold) increase of the photoinduced deformation can be generated by exposing the samples simultaneously to 365 nm (UV) and 455 nm (visible) light. To elucidate the physical mechanism that drives this increase, we develop a two-light attenuation model and an optomechanical constitutive relation that not only accounts for the statistical accumulation of cis azobenzenes, but also for the dynamic trans-cis-trans oscillatory isomerization process. Our experimentally calibrated model predicts that the optimal single-wavelength exposure is 395 nm light, a pronounced shift towards the visible spectrum. In addition, we identify a range of optimal combinations of two-wavelength lights that generate a favorable response for a given amount of injected energy. Our model provides mechanistic insight into the different (multi)wavelength exposures used in experiments and, at the same time, opens new avenues towards enhanced, multiwavelength optomechanical behavior.

  17. Light-gated molecular brakes based on pentiptycene-incorporated azobenzenes.

    Science.gov (United States)

    Tan, Wei Shyang; Chuang, Po-Ya; Chen, Chia-Huei; Prabhakar, Chetti; Huang, Shing-Jong; Huang, Shou-Ling; Liu, Yi-Hung; Lin, Ying-Chih; Peng, Shie-Ming; Yang, Jye-Shane

    2015-04-01

    Three azobenzene derivatives (2 R, 2 OR, and 2 NR) that differed in their terminal substituent (alkyl, alkyloxy, and dialkylamino, respectively) have been synthesized and investigated as molecular brakes, in which the rigid H-shaped pentiptycene group functioned as a rotor and the dinitrophenyl group as a "brake pad". The E and Z isomers of these compounds corresponded to the "brake-off" and "brake-on" states, respectively. The rotation rate of the rotor was evaluated by VT NMR spectroscopy for the brake-on state and by DFT calculations for the brake-off state. The difference between the rotation rates for the rotor in the two states was as large as eight orders of magnitude at ambient temperature. Photochemical switching of the azobenzene moieties afforded efficiencies of 55-67%. A combination of photochemical E→Z and thermal Z→E isomerization promoted the switching efficiency up to 78%. The terminal substituent affected both the photochemical and thermal switching efficiencies. Solvent polarity also played an important role in the lifetimes of the Z isomers. These azobenzene systems displayed similar braking powers but superior switching efficiencies to the stilbene analogue (1O R; ca. 60% vs 20%). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Li, Juan [Physik Department and NIM, Walter Schottky Institute, Technische Universität München, Am Coulombwall 4, Garching D-85748 (Germany); Physik Department E20, Technische Universität München, James-Franck-St. 1, Garching D-85748 (Germany); Wierzbowski, Jakob; Ceylan, Özlem; Klein, Julian; Anh, Tuan Le; Meggendorfer, Felix; Finley, Jonathan J.; Margapoti, Emanuela, E-mail: emanuela.margapoti@wsi.tum.de [Physik Department and NIM, Walter Schottky Institute, Technische Universität München, Am Coulombwall 4, Garching D-85748 (Germany); Nisic, Filippo; Dragonetti, Claudia [Dipartimento di Chimica, Università degli Studi di Milano and UdR dell' INSTM di Milano, Via Golgi 19, I-20133 Milano (Italy); Palma, Carlos-Andres; Barth, Johannes V. [Physik Department E20, Technische Universität München, James-Franck-St. 1, Garching D-85748 (Germany)

    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.

  20. Valve seat pores sealed with thermosetting monomer

    Science.gov (United States)

    Olmore, A. B.

    1966-01-01

    Hard anodic coating provides a smooth wear resistant value seating surface on a cast aluminum alloy valve body. Vacuum impregnation with a thermosetting monomer, diallyl phthalate, seals the pores on the coating to prevent galvanic corrosion.

  1. Photopolymerizable silicone monomers, oligomers, and resins

    International Nuclear Information System (INIS)

    Jacobine, A.F.; Nakos, S.T.

    1992-01-01

    The purpose of this chapter is to acquaint the general photopolymer researcher with the historical development of the chemistry and technology of photopolymerizable silicone monomers, fluids, and resins. The current status of research in these areas is assessed. The focus of this chapter is not only on the polymer chemistry and application of this technology, but also on important aspects of the synthetic chemistry involved in the preparation of UV-curable silicone monomers, oligomers, and resins. 236 refs., 6 tabs

  2. Effects of monomer shape on the formation of aggregates from a power law monomer distribution

    International Nuclear Information System (INIS)

    Perry, J; Kimery, J; Matthews, L S; Hyde, T W

    2013-01-01

    The coagulation of dust aggregates is an important process in many physical systems such as the Earth's upper atmosphere, comet tails and protoplanetary discs. Numerical models which study the aggregation in these systems typically involve spherical monomers. There is evidence, however, via the polarization of sunlight in the interstellar medium, as well as optical and LIDAR observations of high-altitude particles in Earth's atmosphere (70–100 km), which indicate that dust monomers may not necessarily be spherical. This study investigates the influence of different ellipsoidal monomer shapes on the morphology of aggregates given various distributions of monomer sizes. Populations of aggregates are grown from a single monomer using a combination of ballistic particle–cluster aggregation and ballistic cluster–cluster aggregation regimes incorporating the rotation of monomers and aggregates. The resulting structures of the aggregates are then compared via the compactness factor, geometric cross-section and friction time. (paper)

  3. Synthesis of the diazonium (perfluoroalkyl) benzenesulfonimide monomer from Nafion monomer for proton exchange membrane fuel cells

    Science.gov (United States)

    Mei, Hua; D'Andrea, Dan; Nguyen, Tuyet-Trinh; Nworie, Chima

    2014-02-01

    One diazonium (perfluoroalkyl) benzenesulfonimide monomer, perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonyl imide, has been synthesized from Nafion monomer for the first time. With trifluorovinyl ether and diazonium precursors, the partially-fluorinated diazonium PFSI monomer can be polymerized and will provide chemically bonding with carbon electrode in proton exchange membrane fuel cells. A systematic study of the synthesis and characterization of this diazonium PFSI monomer has been conducted by varying reaction conditions. The optimized synthesis method has been established in the lab.

  4. Preparation of supramolecular polymers by copolymerization of monomers containing quadruple hydrogen bonding units with regular monomers

    NARCIS (Netherlands)

    2004-01-01

    The invention relates to the synthesis of polymers containing self-complementary quadruple hydrogen groups by copolymerizing monomers containing a quadruple hydrogen bonding group with one or more monomers of choice. The resulting polymers show unique new characteristics due to the presence of

  5. Preparation of supramolecular polymers by copolymerization of monomers containing quadruple hydrogen bonding units with regular monomers

    NARCIS (Netherlands)

    2004-01-01

    The invention relates to the synthesis of polymers contg. self-complementary quadruple H groups by copolymg. monomers contg. a quadruple H bonding group with ³1 monomers of choice. The resulting polymers show unique new characteristics due to the presence of addnl. phys. interactions between the

  6. Thermodynamics of monomer partitioning in polymer latices: effect of molar volume of the monomers

    NARCIS (Netherlands)

    Schoonbrood, H.A.S.; German, A.L.

    1994-01-01

    A model of the thermodn. of partitioning of moderately water-sol. monomers in polymer latex systems is developed to show deviations that occur when the molar vols. of the monomers are not similar. The model, as well as expts. with Me acrylate and cyclohexyl methacrylate in polystyrene latex systems,

  7. Scattering Studies of Hydrophobic Monomers in Liposomal Bilayers: An Expanding Shell Model of Monomer Distribution

    International Nuclear Information System (INIS)

    Richter, Andrew; Dergunov, Sergey; Ganus, Bill; Thomas, Zachary; Pingali, Sai Venkatesh; Urban, Volker S.; Liu, Yun; Porcar, Lionel; Pinkhassik, Eugene

    2011-01-01

    Hydrophobic monomers partially phase separate from saturated lipids when loaded into lipid bilayers in amounts exceeding a 1:1 monomer/lipid molar ratio. This conclusion is based on the agreement between two independent methods of examining the structure of monomer-loaded bilayers. Complete phase separation of monomers from lipids would result in an increase in bilayer thickness and a slight increase in the diameter of liposomes. A homogeneous distribution of monomers within the bilayer would not change the bilayer thickness and would lead to an increase in the liposome diameter. The increase in bilayer thickness, measured by the combination of small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS), was approximately half of what was predicted for complete phase separation. The increase in liposome diameter, measured by dynamic light scattering (DLS), was intermediate between values predicted for a homogeneous distribution and complete phase separation. Combined SANS, SAXS, and DLS data suggest that at a 1.2 monomer/lipid ratio approximately half of the monomers are located in an interstitial layer sandwiched between lipid sheets. These results expand our understanding of using self-assembled bilayers as scaffolds for the directed covalent assembly of organic nanomaterials. In particular, the partial phase separation of monomers from lipids corroborates the successful creation of nanothin polymer materials with uniform imprinted nanopores. Pore-forming templates do not need to span the lipid bilayer to create a pore in the bilayer-templated films.

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

    DEFF Research Database (Denmark)

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

    2001-01-01

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

  9. Holographic recording of surface relief gratings in stilbene azobenzene derivatives at 633 nm

    International Nuclear Information System (INIS)

    Ozols, A; Saharov, D; Kokars, V; Kampars, V; Maleckis, A; Mezinskis, G; Pludons, A

    2010-01-01

    Holographic recording in stilbene azobenzene derivatives by He-Ne 633 nm laser light has been experimentally studied. It was found that surface relief gratings (SRG) can be recorded by red light. Usually shorter wavelengths are used to induce the trans-cis photo-isomerization in organic materials. SRG with 2 μm period and an amplitude of 130 nm have been recorded with 0.88 W/cm 2 light in about 20 minutes in amorphous films of 3-(4-(bis(2-(trityloxy)ethyl)amino)phenyl)-2-(4-(2-bromo-4-nitrophenyl) diazenyl)phenyl)acrylonitrile spin-coated on glass substrates. Self-diffraction efficiency up to 17.4% and specific recording energy down to 114 J/(cm 2 %) were measured. The recorded SRG were stable as proved by subsequent AFM measurements. The photo-induced changes in absorption spectra did not reveal noticeable signs of trans-cis transformations. Rather, spectrally uniform bleaching of the films took place. We conclude that a photothermally stimulated photo-destruction of chromophores is responsible for the SRG recording. The recording of stable SRG in the stilbene azobenzene derivatives we studied is accompanied by the recording of relaxing volume-phase gratings due to the photo-orientation of chromophores by the linearly polarized recording light. It should also be noted that holographic recording efficiency in stilbene azobenzene derivatives exhibit an unusual non-monotonic sample storage-time dependence presumably caused by the peculiarities of structural relaxation of the films.

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

    DEFF Research Database (Denmark)

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

    2000-01-01

    Biphotonic holographic gratings have been recorded in a side-chain azobenzene liquid crystalline polyester using a blue incoherent source and a He-Ne laser. Intensity gratings and the appearance of surface relief have been observed when two linearly polarized beams from a He-Ne laser are made...... to interfere on a film illuminated with blue light. Polarized holographic gratings are also created with two orthogonally circularly polarized He-Ne beams. All these gratings are stable in darkness but can be erased with blue light. (C) 2000 American Institute of Physics....

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

    DEFF Research Database (Denmark)

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

    2008-01-01

    . At the air-water interface, the amphiphilic azobenzenes form noncrystalline but stable Langmuir films that display an unusual reversible monolayer collapse close to 35 mN/m. The structures and phase transitions were studied by X-ray reflectivity (XR) and grazing-incidence X-ray diffraction, both utilizing...... synchrotron radiation. Compression beyond the collapse point does not change the XR data, showing that the film is unchanged at the molecular level, even at areas less than half of that of the collapse. This leads to the conclusion that few macroscopic collapse sites are responsible for reversibly removing...

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

    DEFF Research Database (Denmark)

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

    2004-01-01

    light that yields the films into the isotropic state at room temperature (RT) was compared with the quenching from temperatures above the isotropic transition temperature Ti. UV–visible spectra of the thermally quenched films show the presence of aggregates when measured at RT. We have found that UV......Birefringence induced in a series of liquid crystalline side-chain azobenzene polyesters with different substituent groups was investigated under irradiation with 488 and 633 nm linearly polarized lights. Two different initial conditions have been used: the effect of a previous irradiation with UV...

  13. Surface relief grating formation on a single crystal of 4-(dimethylamino)azobenzene

    International Nuclear Information System (INIS)

    Nakano, Hideyuki; Tanino, Takahiro; Shirota, Yasuhiko

    2005-01-01

    Surface relief grating (SRG) formation on an organic single crystal by irradiation with two coherent laser beams has been demonstrated by using 4-(dimethylamino)azobenzene (DAAB). It was found that the SRG formation was greatly depending upon both the coordination of the crystal and the polarization of the writing beams. The dependence of the polarization of writing beams on the SRG formation using the single crystal was found to be quite different from that reported for amorphous polymers and photochromic amorphous molecular materials, suggesting that the mechanism of the SRG formation on the organic crystal is somewhat different from that on amorphous materials

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

    International Nuclear Information System (INIS)

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

    2005-01-01

    Birefringence (Δn) 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 Δn can be reversed again, by simply heating up the film to 100 deg. C. This change of Δn 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 Δn values can be obtained

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2015-10-01

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

  17. Radiation cured and monomer modified silicon elastomers

    International Nuclear Information System (INIS)

    Eldred, R.J.

    1979-01-01

    A method is described for the production of a tear resistant silicone elastomer, which has improved elongation properties. This elastomer is the radiation induced reaction product of a noncured methyl vinyl silicone resin (VMQ) and uniformly dispersed therein a blend of a polyfunctional acrylic crosslinking monomer and a filler

  18. New monomers for high performance polymers

    Science.gov (United States)

    Gratz, Roy F.

    1993-01-01

    This laboratory has been concerned with the development of new polymeric materials with high thermo-oxidative stability for use in the aerospace and electronics industries. Currently, there is special emphasis on developing matrix resins and composites for the high speed civil transport (HSCT) program. This application requires polymers that have service lifetimes of 60,000 hr at 350 F (177 C) and that are readily processible into void-free composites, preferably by melt-flow or powder techniques that avoid the use of high boiling solvents. Recent work has focused on copolymers which have thermally stable imide groups separated by flexible arylene ether linkages, some with trifluoromethyl groups attached to the aromatic rings. The presence of trifluoromethyl groups in monomers and polymers often improves their solubility and processibility. The goal of this research was to synthesize several new monomers containing pendant trifluoromethyl groups and to incorporate these monomers into new imide/arylene ether copolymers. Initially, work was begun on the synthesis of three target compounds. The first two, 3,5-dihydroxybenzo trifluoride and 3-amino 5-hydroxybenzo trifluoride, are intermediates in the synthesis of more complex monomers. The third, 3,5-bis (3-amino-phenoxy) benzotrifluoride, is an interesting diamine that could be incorporated into a polyimide directly.

  19. Softening and elution of monomers in ethanol

    DEFF Research Database (Denmark)

    Benetti, Ana Raquel; Asmussen, Erik; Munksgaard, E Christian

    2009-01-01

    The purpose of this study was to investigate the effect of light-curing protocol on softening and elution of monomers in ethanol as measured on a model polymer. It was a further aim to correlate the measured values with previously reported data on degree of conversion and glass transition...

  20. Synergetic interaction between neighbouring platinum monomers in CO2 hydrogenation

    Science.gov (United States)

    Li, Hongliang; Wang, Liangbing; Dai, Yizhou; Pu, Zhengtian; Lao, Zhuohan; Chen, Yawei; Wang, Menglin; Zheng, Xusheng; Zhu, Junfa; Zhang, Wenhua; Si, Rui; Ma, Chao; Zeng, Jie

    2018-05-01

    Exploring the interaction between two neighbouring monomers has great potential to significantly raise the performance and deepen the mechanistic understanding of heterogeneous catalysis. Herein, we demonstrate that the synergetic interaction between neighbouring Pt monomers on MoS2 greatly enhanced the CO2 hydrogenation catalytic activity and reduced the activation energy relative to isolated monomers. Neighbouring Pt monomers were achieved by increasing the Pt mass loading up to 7.5% while maintaining the atomic dispersion of Pt. Mechanistic studies reveal that neighbouring Pt monomers not only worked in synergy to vary the reaction barrier, but also underwent distinct reaction paths compared with isolated monomers. Isolated Pt monomers favour the conversion of CO2 into methanol without the formation of formic acid, whereas CO2 is hydrogenated stepwise into formic acid and methanol for neighbouring Pt monomers. The discovery of the synergetic interaction between neighbouring monomers may create a new path for manipulating catalytic properties.

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

    DEFF Research Database (Denmark)

    Åstrand, Per-Olof; Ramanujam, P.S.; Hvilsted, Søren

    2000-01-01

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

  2. An analysis of the anisotropic and topographic gratings in a side-chain liquid crystalline azobenzene polyester

    DEFF Research Database (Denmark)

    Holme, N.C.R.; Nikolova, L.; Ramanujam, P.S.

    1997-01-01

    We have examined in detail the formation of surface relief structures in azobenzene polyesters formed by polarization holography with orthogonally circularly polarized laser beams, We show that it is possible to separate the contribution to the diffraction efficiency into an anisotropic part...

  3. 10,000 optical write, read, and erase cycles in an azobenzene sidechain liquid-crystalline polyester

    DEFF Research Database (Denmark)

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

    1996-01-01

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

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

    Science.gov (United States)

    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...

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

    International Nuclear Information System (INIS)

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

    2011-01-01

    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. Prediction of the maximum absorption wavelength of azobenzene dyes by QSPR tools

    Science.gov (United States)

    Xu, Xuan; Luan, Feng; Liu, Huitao; Cheng, Jianbo; Zhang, Xiaoyun

    2011-12-01

    The maximum absorption wavelength ( λmax) of a large data set of 191 azobenzene dyes was predicted by quantitative structure-property relationship (QSPR) tools. The λmax was correlated with the 4 molecular descriptors calculated from the structure of the dyes alone. The multiple linear regression method (MLR) and the non-linear radial basis function neural network (RBFNN) method were applied to develop the models. The statistical parameters provided by the MLR model were R2 = 0.893, Radj2=0.893, qLOO2=0.884, F = 1214.871, RMS = 11.6430 for the training set; and R2 = 0.849, Radj2=0.845, qext2=0.846, F = 207.812, RMS = 14.0919 for the external test set. The RBFNN model gave even improved statistical results: R2 = 0.920, Radj2=0.919, qLOO2=0.898, F = 1664.074, RMS = 9.9215 for the training set, and R2 = 0.895, Radj2=0.892, qext2=0.895, F = 314.256, RMS = 11.6427 for the external test set. This theoretical method provides a simple, precise and an alternative method to obtain λmax of azobenzene dyes.

  7. A mononuclear uranium(IV) single-molecule magnet with an azobenzene radical ligand

    Energy Technology Data Exchange (ETDEWEB)

    Antunes, Maria A.; Coutinho, Joana T.; Santos, Isabel C.; Marcalo, Joaquim; Almeida, Manuel; Pereira, Laura C.J. [C" 2TN, Instituto Superior Tecnico, Universidade de Lisboa, Bobadela (Portugal); Baldovi, Jose J.; Gaita-Arino, Alejandro; Coronado, Eugenio [Instituto de Ciencia Molecular, Universitat de Valencia, Paterna (Spain)

    2015-12-01

    A tetravalent uranium compound with a radical azobenzene ligand, namely, [{(SiMe_2NPh)_3-tacn}U{sup IV}(η{sup 2}-N{sub 2}Ph{sub 2{sup .}})] (2), was obtained by one-electron reduction of azobenzene by the trivalent uranium compound [U{sup III}{(SiMe_2NPh)_3-tacn}] (1). Compound 2 was characterized by single-crystal X-ray diffraction and {sup 1}H NMR, IR, and UV/Vis/NIR spectroscopy. The magnetic properties of 2 and precursor 1 were studied by static magnetization and ac susceptibility measurements, which for the former revealed single-molecule magnet behaviour for the first time in a mononuclear U{sup IV} compound, whereas trivalent uranium compound 1 does not exhibit slow relaxation of the magnetization at low temperatures. A first approximation to the magnetic behaviour of these compounds was attempted by combining an effective electrostatic model with a phenomenological approach using the full single-ion Hamiltonian. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Optoelectronic properties of four azobenzene-based iminopyridine ligands for photovoltaic application

    Directory of Open Access Journals (Sweden)

    Aziz El alamy

    2017-11-01

    Full Text Available Because of organic π-conjugated materials’ optoelectronic properties and potential applications in a wide range of electronic and optoelectronic devices, such as organic solar cells, these materials, including both polymers and oligomers, have been widely studied in recent years. This work reposts a theoretical study using the DFT method on four azobenzene-based iminopyridines. The theoretical ground-state geometry, electronic structure and optoelectronic parameters (highest occupied molecular orbital (HOMO, lowest unoccupied molecular orbital (LUMO energy levels, open-circuit voltage (Voc and oscillator strengths (O.S of the studied molecules were obtained using the density functional theory (DFT and time-dependent (TDDFT approaches. The effects of the structure length and substituents on the geometric and optoelectronic properties of these materials are discussed to investigate the relationship between the molecular structure and the optoelectronic properties. The results of this study are consistent with the experimental ones and suggest that these materials as good candidates for use in photovoltaic devices. Keywords: π-conjugated materials, azobenzene, optoelectronic properties, DFT calculations, HOMO-LUMO gap

  9. Photokopolimerisasi monomer akrilat degan kulit kras sapi

    Directory of Open Access Journals (Sweden)

    Dwi Wahini Nurhajati

    1997-06-01

    Full Text Available The research on photocopolymerization of acrylate monomer with cow crust hide had object to observe the resulted copolymer onto cow crust hide. Crust hides, saturated with aqueous emulsions containing 25 wt % of n-butyl acrylate (n-BA or tripropylene glycol diacrylate (TPGDA were irradiated by cobalt – 60 gamma rays with doses ranges from 5 to 25 kGy. The irradiated hides were washed with water, dried in air and extracted in soxhlet apparatus for 48 hours to remove homopolymer. The highest yield of photocopolymerization of n – butyl acrylate monomer with crust hides was found 17,7878% at dose 25 kGy, and for photocopolymerization of tripropylene glycol diacrylate with crust hides was found 39,4245% at dose 20 kGy.

  10. Radiation crosslinking of PVC with polyfunctional monomers

    International Nuclear Information System (INIS)

    Dobo, J.; Takacs, E.; Csato, P.

    1984-01-01

    The radiation crosslinking of PVC in the presence of ethylene glycol dimethacrylate (EGDM) and of trimethylol propane trimethacrylate (TMPTM) was investigated. The effect of PVC powders of different types on the polymerization rate of these monomers was studied by a Calvet-type microcalorimeter. In the milled PVC sheets containing 50 part EGDM a high concentration of trapped free radicals was found by ESR after 16 months storage. (author)

  11. Elution of Monomers from Provisional Composite Materials

    Directory of Open Access Journals (Sweden)

    Simon Daniel Schulz

    2015-01-01

    Full Text Available The aim of this study was to evaluate the elution of substances from different materials used for the manufacturing of temporary indirect restorations, after storage in saliva and ethanol 75%. 10 samples of three chemically cured materials (Protemp 3 Garant, Systemp.c&b, and Trim and one light-cured material (Clip F were stored in saliva and ethanol 75% for 24 h, 7, and days 28 days. From the storage media at each time period, samples were prepared and analysed by LC-MS/MS, in order to access the elution of monomers. The results differed among the materials (P ≤ 0.05. No monomers were detected in the samples of Protemp 3 Garant and Clip F. Substances were detected only in ethanol samples of Systemp.c&b and Trim. The amount of BisGMA, TEGDMA, and UDMA 2 released from Systemp.c&b was higher compared to Trim. Storage time affected the release of substances (P ≤ 0.05. The highest release was observed within the first 24 h. It can be concluded that provisional resin composite materials do not show high release of monomers and this release is material dependent. However, the detection of additional peaks during the analysis, suggesting the formation of by-products of the eluted substances, may not be in favour of these materials with respect to their toxicity.

  12. 21 CFR 888.4220 - Cement monomer vapor evacuator.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Cement monomer vapor evacuator. 888.4220 Section... (CONTINUED) MEDICAL DEVICES ORTHOPEDIC DEVICES Surgical Devices § 888.4220 Cement monomer vapor evacuator. (a) Identification. A cement monomer vapor evacuator is a device intended for use during surgery to contain or remove...

  13. Thermodynamics of swelling of latex particles with two monomers

    NARCIS (Netherlands)

    Maxwell, I.A.; Kurja, J.; van Doremaele, G.H.J.; German, A.L.

    1992-01-01

    The partitioning of 2 monomers between the latex particle, monomer droplet, and aq. phases of an emulsion polymer latex are measured at satn. swelling of the latex particle phase (corresponding to intervals I and II of an emulsion polymn.). The monomer (Me acrylate, Bu acrylate, styrene) and polymer

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

    International Nuclear Information System (INIS)

    Sanchez, C.; Alcala, R.; Hvilsted, S.; Ramanujam, P. S.

    2001-01-01

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

  15. Magnetic and optical bistability in tetrairon(III) single molecule magnets functionalized with azobenzene groups.

    Science.gov (United States)

    Prasad, Thazhe Kootteri; Poneti, Giordano; Sorace, Lorenzo; Rodriguez-Douton, Maria Jesus; Barra, Anne-Laure; Neugebauer, Petr; Costantino, Luca; Sessoli, Roberta; Cornia, Andrea

    2012-07-21

    Tetrairon(III) complexes known as "ferric stars" have been functionalized with azobenzene groups to investigate the effect of light-induced trans-cis isomerization on single-molecule magnet (SMM) behaviour. According to DC magnetic data and EPR spectroscopy, clusters dispersed in polystyrene (4% w/w) exhibit the same spin (S = 5) and magnetic anisotropy as bulk samples. Ligand photoisomerization, achieved by irradiation at 365 nm, has no detectable influence on static magnetic properties. However, it induces a small but significant acceleration of magnetic relaxation as probed by AC susceptometry. The pristine behaviour can be almost quantitatively recovered by irradiation with white light. Our studies demonstrate that magnetic and optical bistability can be made to coexist in SMM materials, which are of current interest in molecular spintronics.

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

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Pedersen, M; Holme, NCR

    1998-01-01

    A flexible azobenzene side-chain liquid crystalline (SCLC) polyester architecture employed for reversible optical storage is described. The modular design allows four structural parameters to be individually modified. These parameters: i- the methylene side-chain spacer length, ii- the substituent......,000 are routinely obtained by melt transesterification of the novel diols and selected diacid precursors (parameter iii). Prominent storage features include no prealignment of thin SCLC polyester films prior to the writing process, and sensitivity in a broad laser wavelength window (415-532 nm). Additionally...... sign of fatigue. The non-destructive read out is performed with red light (600-750 nm). Finally, erasing the information can be achieved by heating the polyester film to 80 degrees C or irradiating it briefly with UV-light. In the latter case at least 10,000 write, read and erase cycles are possible...

  17. Dielectric investigations under irradiation of photo chromic copolymers with azobenzene moieties in the side group

    International Nuclear Information System (INIS)

    Turky, G.; Stumpe, J.; Schonhals, A.

    2005-01-01

    Photo chromic polymers are promising materials for optical switching and image storage because the orientation of mesogens in thin films of these materials can be modified by light. Real time dielectric spectroscopy is applied to study the time dependence of the light induced trans/cis-isomerization process for polymethacrylate copolymer system. For the investigated azobenzene group it was found that the dipole moment of the Z state is greater than that of E state. Therefore normalized . increases with increasing irradiation time (E/Z isomerization) at different considered wavelengths. A steady state is reached after about 10000 s. The effect of irradiation reduces at longer and shorter wavelengths. Stretched exponential equation was used to describe the effect of irradiation time on the normalized permittivity

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

    DEFF Research Database (Denmark)

    Naydenova, I; Nikolova, L; Todorov, T

    1998-01-01

    We investigate the polarization properties of holographic gratings in side-chain azobenzene polyesters in which an anisotropic grating that is due to photoinduced linear and circular birefringence is recorded in the volume of the material and a relief grating appears on the surface. A theoretical...... model is proposed to explain the experimental results, making it possible to understand the influence of the different photoinduced effects. It is shown that at low intensity the polarization properties of the diffraction at these gratings are determined by the interaction of the linear and circular...... photobirefringences, and at larger intensity the influence of the surface relief dominates the effect of the circular anisotropy. Owing to the high recording efficiency of the polyesters, the +/-1-order diffracted waves change the polarization interference pattern during the holographic recording, resulting...

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

    Science.gov (United States)

    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.

  20. Kinetics of monomer biodegradation in soil.

    Science.gov (United States)

    Siotto, Michela; Sezenna, Elena; Saponaro, Sabrina; Innocenti, Francesco Degli; Tosin, Maurizio; Bonomo, Luca; Mezzanotte, Valeria

    2012-01-01

    In modern intensive agriculture, plastics are used in several applications (i.e. mulch films, drip irrigation tubes, string, clips, pots, etc.). Interest towards applying biodegradable plastics to replace the conventional plastics is promising. Ten monomers, which can be applied in the synthesis of potentially biodegradable polyesters, were tested according to ASTM 5988-96 (standard respirometric test to evaluate aerobic biodegradation in soil by measuring the carbon dioxide evolution): adipic acid, azelaic acid, 1,4-butanediol, 1,2-ethanediol, 1,6-hexanediol, lactic acid, glucose, sebacic acid, succinic acid and terephthalic acid. Eight replicates were carried out for each monomer for 27-45 days. The numerical code AQUASIM was applied to process the CO₂ experimental data in order to estimate values for the parameters describing the different mechanisms occurring to the monomers in soil: i) the first order solubilization kinetic constant, K(sol) (d⁻¹); ii) the first order biodegradation kinetic constant, K(b) (d⁻¹); iii) the lag time in biodegradation, t(lag) (d); and iv) the carbon fraction biodegraded but not transformed into CO₂, Y (-). The following range of values were obtained: [0.006 d⁻¹, 6.9 d⁻¹] for K(sol), [0.1 d⁻¹, 1.2 d⁻¹] for K(b), and [0.32-0.58] for Y; t(lag) was observed for azelaic acid, 1,2-ethanediol, and terephthalic acid, with estimated values between 3.0 e 4.9 d. Copyright © 2011 Elsevier Ltd. All rights reserved.

  1. Temporal formation of optical anisotropy and surface relief during polarization holographic recording in polymethylmethacrylate with azobenzene side groups

    Science.gov (United States)

    Sasaki, Tomoyuki; Izawa, Masahiro; Noda, Kohei; Nishioka, Emi; Kawatsuki, Nobuhiro; Ono, Hiroshi

    2014-03-01

    The formation of polarization holographic gratings with both optical anisotropy and surface relief (SR) deformation was studied for polymethylmethacrylate with azobenzene side groups. Temporal contributions of isotropic and anisotropic phase gratings were simultaneously determined by observing transitional intensity and polarization states of the diffraction beams and characterizing by means of Jones calculus. To clarify the mechanism of SR deformation, cross sections of SR were characterized based on the optical gradient force model; experimental observations were in good agreement with the theoretical expectation. We clarified that the anisotropic phase change originating in the reorientation of the azobenzene side groups was induced immediately at the beginning of the holographic recording, while the response time of the isotropic phase change originating in the molecular migration due to the optical gradient force was relatively slow.

  2. Controllable Negative Differential Resistance Behavior of an Azobenzene Molecular Device Induced by Different Molecule-Electrode Distances

    International Nuclear Information System (INIS)

    Fan Zhi-Qiang; Zhang Zhen-Hua; Qiu Ming; Deng Xiao-Qing; Tang Gui-Ping

    2012-01-01

    We report the ab initio calculations of transport behaviors of an azobenzene molecular device which is similar to the experimental configurations. The calculated results show that the transport behaviors of the device are sensitive to the molecule-electrode distance and the currents will drop rapidly when the molecule-electrode distance changes from 1.7 Å to 2.0 Å. More interestingly, the negative differential resistance behavior can be found in our device. Nevertheless, it is not the inherent property of an azobenzene molecular device but an effect of the molecule-electrode distance. Detailed analyses of the molecular projected self-consistent Hamiltonian states and the transmission spectra of the system reveal the physical mechanism of these behaviors. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  3. Excited-state Raman spectroscopy with and without actinic excitation: S1 Raman spectra of trans-azobenzene

    International Nuclear Information System (INIS)

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

    2014-01-01

    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 1 and S 0 spectra of trans-azobenzene in n-hexane. The S 1 spectra were also measured conventionally, upon nπ* (S 0 → S 1 ) actinic excitation. The results are discussed and compared to earlier reports

  4. Photoorientation phenomena and structural properties of photochromic liquid crystalline azobenzene-containing polymethacrylate films with different spacer lengths

    Czech Academy of Sciences Publication Activity Database

    Bobrovsky, A.; Shibaev, V.; Piryazev, A.; Anokhin, D.V.; Ivanov, D.A.; Sinitsyna, O.; Hamplová, Věra; Kašpar, Miroslav; Bubnov, Alexej M.

    2017-01-01

    Roč. 218, č. 16 (2017), s. 1-10, č. článku 1700127. ISSN 1022-1352 R&D Projects: GA ČR GA16-12150S; GA MŠk(CZ) LH15305 Institutional support: RVO:68378271 Keywords : photoorientation phenomena * azobenzene * photo-optical properties * liquid crystal * photochromic materials Subject RIV: JJ - Other Materials OBOR OECD: Nano-materials (production and properties) Impact factor: 2.500, year: 2016

  5. Copolymerization of Carbon–carbon Double-bond Monomer (Styrene with Cyclic Monomer (Tetrahydrofuran

    Directory of Open Access Journals (Sweden)

    Sari Fouad

    2012-12-01

    Full Text Available We reported in this work that the cationic copolymerization in one step takes place between carbon–carbon double-bond monomer styrene with cyclic monomer tetrahydrofuran. The comonomers studied belong to different families: vinylic and cyclic ether. The reaction is initiated with maghnite-H+ an acid exchanged montmorillonite as acid solid ecocatalyst. Maghnite-H+ is already used as catalyst for polymerization of many vinylic and heterocyclic monomers. The oxonium ion of tetrahydrofuran and carbonium ion of styrene propagated the reaction of copolymerization. The acetic anhydride is essential for the maintenance of the ring opening of tetrahydrofuran and the entry in copolymerization. The temperature was kept constant at 40°C in oil bath heating for 6 hours. A typical reaction product was analyzed by 1H-NMR, 13C-NMR and IR and the formation of the copolymer was confirmed. The reaction was proved by matched with analysis. The maghnite-H+ allowed us to obtain extremely pure copolymer in good yield by following a simples operational conditions. Copyright © 2012 by BCREC UNDIP. All rights reservedReceived: 29th October 2012; Revised: 29th November 2012; Accepted: 29th November 2012[How to Cite: S. Fouad, M.I. Ferrahi, M. Belbachir. (2012. Copolymerization of Carbon–carbon Double-bond Monomer (Styrene with Cyclic Monomer (Tetrahydrofuran. Bulletin of Chemical Reaction Engineering & Catalysis, 7(2: 165-171. (doi:10.9767/bcrec.7.2.4074.165-171][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.2.4074.165-171 ] | View in 

  6. Design of Tail-Clamp Peptide Nucleic Acid Tethered with Azobenzene Linker for Sequence-Specific Detection of Homopurine DNA

    Directory of Open Access Journals (Sweden)

    Shinjiro Sawada

    2017-10-01

    Full Text Available DNA carries genetic information in its sequence of bases. Synthetic oligonucleotides that can sequence-specifically recognize a target gene sequence are a useful tool for regulating gene expression or detecting target genes. Among the many synthetic oligonucleotides, tail-clamp peptide nucleic acid (TC-PNA offers advantages since it has two homopyrimidine PNA strands connected via a flexible ethylene glycol-type linker that can recognize complementary homopurine sequences via Watson-Crick and Hoogsteen base pairings and form thermally-stable PNA/PNA/DNA triplex structures. Here, we synthesized a series of TC-PNAs that can possess different lengths of azobenzene-containing linkers and studied their binding behaviours to homopurine single-stranded DNA. Introduction of azobenzene at the N-terminus amine of PNA increased the thermal stability of PNA-DNA duplexes. Further extension of the homopyrimidine PNA strand at the N-terminus of PNA-AZO further increased the binding stability of the PNA/DNA/PNA triplex to the target homopurine sequence; however, it induced TC-PNA/DNA/TC-PNA complex formation. Among these TC-PNAs, 9W5H-C4-AZO consisting of nine Watson-Crick bases and five Hoogsteen bases tethered with a beta-alanine conjugated azobenzene linker gave a stable 1:1 TC-PNA/ssDNA complex and exhibited good mismatch recognition. Our design for TC-PNA-AZO can be utilized for detecting homopurine sequences in various genes.

  7. Understanding the effects of packing and chemical terminations on the optical excitations of azobenzene-functionalized self-assembled monolayers

    Science.gov (United States)

    Cocchi, Caterina; Draxl, Claudia

    2017-10-01

    In a first-principles study based on many-body perturbation theory, we analyze the optical excitations of azobenzene-functionalized self-assembled monolayers (SAMs) with increasing packing density and different terminations, considering for comparison the corresponding gas-phase molecules and dimers. Intermolecular coupling increases with the density of the chromophores independently of the functional groups. The intense π → π* resonance that triggers photo-isomerization is present in the spectra of isolated dimers and diluted SAMs, but it is almost completely washed out in tightly packed architectures. Intermolecular coupling is partially inhibited by mixing differently functionalized azobenzene derivatives, in particular when large groups are involved. In this way, the excitation band inducing the photo-isomerization process is partially preserved and the effects of dense packing partly counterbalanced. Our results suggest that a tailored design of azobenzene-functionalized SAMs which optimizes the interplay between the packing density of the chromophores and their termination can lead to significant improvements in the photo-switching efficiency of these systems.

  8. Interference of functional monomers with polymerization efficiency of adhesives.

    Science.gov (United States)

    Hanabusa, Masao; Yoshihara, Kumiko; Yoshida, Yasuhiro; Okihara, Takumi; Yamamoto, Takatsugu; Momoi, Yasuko; Van Meerbeek, Bart

    2016-04-01

    The degree of conversion (DC) of camphorquinone/amine-based adhesives is affected by acidic functional monomers as a result of inactivation of the amine co-initiator through an acid-base reaction. During bonding, functional monomers of self-etch adhesives chemically interact with hydroxyapatite (HAp). Here, we tested in how far the latter interaction of functional monomers with HAp counteracts the expected reduction in DC of camphorquinone/amine-based adhesives. The DC of three experimental adhesive formulations, containing either of the two functional monomers [10-methacryloyloxydecyl dihydrogen phosphate (10-MDP) or 4-methacryloxyethyl trimellitic acid anhydride (4-META)] or no functional monomer (no-FM; control), was measured with and without HAp powder added to the adhesive formulations. Both the variables 'functional monomer' and 'HAp' were found to be significant, with the functional monomer reducing the DC and HAp counteracting this effect. It is concluded that the functional monomers 10-MDP and 4-META interfere with the polymerization efficiency of adhesives. This interference is less prominent in the presence of HAp, which would clinically correspond to when these two functional monomers of the adhesive simultaneously interact with HAp in tooth tissue. © 2016 Eur J Oral Sci.

  9. The effect of monomer molecular weight on grafting reaction

    International Nuclear Information System (INIS)

    Wu Minghong; Ding Zhongli; Ma Zueteh

    1995-01-01

    In this paper, some condensed ethylene glycol acrylate monomers with different molecular weight being grafted to the PE film by means of pre-irradiation is reported. The effect of molecular weight of monomer on grafting reaction and the hydrophilicity of grafting sample have been discussed. The experimental results show: molar degrees of grafting decreased non-linearly with the increasement of molecular weight of monomer, the grafting reaction of polymer is greater effected by the swelling degree of PE film, the greater the swelling degree of grafting material, the higher the grating degree grafting is, the initial rate of grafting reaction decreased with the increasement of molecular weight of monomer. (author)

  10. Partial swelling of latex particles by two monomers

    NARCIS (Netherlands)

    Noel, E.F.J.; Maxwell, I.A.; German, A.L.

    1993-01-01

    The swelling of polymeric latex particles with solvent and monomer is of great importance for the emulsion polymn. process in regard to compn. drift and rate of polymn. For the monomer combination, Me acrylate-vinyl acetate, both satn. and partial swelling were detd. exptl. Theories for satn.

  11. Characterization of Binary Organogels Based on Some Azobenzene Compounds and Alkyloxybenzoic Acids with Different Chain Lengths

    Directory of Open Access Journals (Sweden)

    Yongmei Hu

    2014-01-01

    Full Text Available In this work the gelation behaviors of binary organogels composed of azobenzene amino derivatives and alkyloxybenzoic acids with different lengths of alkyl chains in various organic solvents were investigated and characterized. The corresponding gelation behaviors in 20 solvents were characterized and shown as new binary organic systems. It showed that the lengths of substituent alkyl chains in compounds have played an important role in the gelation formation of gelator mixtures in present tested organic solvents. Longer methylene chains in molecular skeletons in these gelators seem more suitable for the gelation of present solvents. Morphological characterization showed that these gelator molecules have the tendency to self-assemble into various aggregates from lamella, wrinkle, and belt to dot with change of solvents and gelator mixtures. Spectral characterization demonstrated different H-bond formation and hydrophobic force existing in gels, depending on different substituent chains in molecular skeletons. Meanwhile, these organogels can self-assemble to form monomolecular or multilayer nanostructures owing to the different lengths of due to alkyl substituent chains. Possible assembly modes for present xerogels were proposed. The present investigation is perspective to provide new clues for the design of new nanomaterials and functional textile materials with special microstructures.

  12. Optical alignment control of polyimide molecules containing azobenzene in the backbone structure

    International Nuclear Information System (INIS)

    Sakamoto, Kenji; Usami, Kiyoaki; Sasaki, Toru; Kanayama, Takashi; Ushioda, Sukekatsu

    2004-01-01

    Using polarized infrared absorption spectroscopy, we have determined the orientation of the polyimide backbone structure in photo-alignment films for liquid crystals (LC). The polyimide used in this study contains azobenzene in the backbone structure. Photo-alignment treatment was performed on the corresponding polyamic acid film, using a light source of wavelength 340-500 nm. The polyamic acid film (∼16 nm thick) was first irradiated at normal incidence with linearly polarized light (LP-light) of 156 J/cm 2 , and then oblique angle irradiation of unpolarized light (UP-light) was performed in the plane of incidence perpendicular to the polarization direction of the LP-light. The UP-light exposure was varied up to 882 J/cm 2 . We found that the average inclination angle of the polyimide backbone structure, measured from the surface plane, increases almost linearly with UP-light exposure. On the other hand, the in-plane anisotropy induced by the first irradiation with LP-light decreases with the increase of UP-light exposure

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

    Science.gov (United States)

    Liu, Jun-na; Chen, Zhi-rong; Yuan, Shen-feng

    2005-01-01

    The geometries of azobenzene compounds are optimized with B3LYP/6-311G* method, and analyzed with nature bond orbital, then their visible absorption maxima are calculated with TD-DFT method and ZINDO/S method respectively. The results agree well with the observed values. It was found that for the calculation of visible absorption using ZINDO/S method could rapidly yield better results by adjusting OWFπ-π (the relationship between π-π overlap weighting factor) value than by the TD-DFT method. The method of regression showing the linear relationship between OWFπ-π and BLN-N (nitrogen-nitrogen bond lengths) as OWF π-π=−8.1537+6.5638BL N-N, can be explained in terms of quantum theory, and also be used for prediction of visible absorption maxima of other azobenzne dyes in the same series. This study on molecules’ orbital geometry indicates that their visible absorption maxima correspond to the electron transition from HOMO (the highest occupied molecular orbital) to LUMO (the lowest unoccupied molecular orbital). PMID:15909349

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

    Directory of Open Access Journals (Sweden)

    Sheyda R Frolova

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

  15. Motion of Adsorbed Nano-Particles on Azobenzene Containing Polymer Films

    Directory of Open Access Journals (Sweden)

    Sarah Loebner

    2016-12-01

    Full Text Available We demonstrate in situ recorded motion of nano-objects adsorbed on a photosensitive polymer film. The motion is induced by a mass transport of the underlying photoresponsive polymer material occurring during irradiation with interference pattern. The polymer film contains azobenzene molecules that undergo reversible photoisomerization reaction from trans- to cis-conformation. Through a multi-scale chain of physico-chemical processes, this finally results in the macro-deformations of the film due to the changing elastic properties of polymer. The topographical deformation of the polymer surface is sensitive to a local distribution of the electrical field vector that allows for the generation of dynamic changes in the surface topography during irradiation with different light interference patterns. Polymer film deformation together with the motion of the adsorbed nano-particles are recorded using a homemade set-up combining an optical part for the generation of interference patterns and an atomic force microscope for acquiring the surface deformation. The particles undergo either translational or rotational motion. The direction of particle motion is towards the topography minima and opposite to the mass transport within the polymer film. The ability to relocate particles by photo-induced dynamic topography fluctuation offers a way for a non-contact simultaneous manipulation of a large number of adsorbed particles just in air at ambient conditions.

  16. Optothermal Switching of Cholesteric Liquid Crystals: A Study of Azobenzene Derivatives and Laser Wavelengths

    Directory of Open Access Journals (Sweden)

    Tai-Chieh Huang

    2015-09-01

    Full Text Available The laser-initiated thermal (optothermal switching of cholesteric liquid crystals (CLCs is characterized by using different azobenzene (Azo derivatives and laser wavelengths. Under 405-nm laser irradiation, Azo-doped CLCs undergo phase transition from cholesteric to isotropic. No cis-to-trans photoisomerization occurs when the 405-nm laser irradiation is blocked because only a single laser is used. The fast response of Azo-doped CLCs under the on–off switching of the 405-nm laser occurs because of the optothermal effect of the system. The 660-nm laser, which cannot be used as irradiation to generate the trans–cis photoisomerization of Azo, is used in Anthraquinone (AQ-Azo-doped CLCs to examine the optothermal effect of doped Azo. The results show that the LC-like Azo derivative bearing two methyl groups ortho to the Azo moiety (A4 can greatly lower the clearing temperature and generate large amount of heat in AQ-A4-doped CLCs.

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

    International Nuclear Information System (INIS)

    Fernández, Raquel; Mondragon, Iñaki; Sanfelice, Rafaela C.; Pavinatto, Felippe J.; Oliveira, Osvaldo N.; Oyanguren, Patricia; Galante, María J.

    2013-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-04-01

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

  19. Oligonucleotides with 1,4-dioxane-based nucleotide monomers

    DEFF Research Database (Denmark)

    Madsen, Andreas S; Wengel, Jesper

    2012-01-01

    An epimeric mixture of H-phosphonates 5R and 5S has been synthesized in three steps from known secouridine 1. Separation of the epimers has been accomplished by RP-HPLC, allowing full characterization and incorporation of monomers X and Y into 9-mer oligonucleotides using H-phosphonates building...... blocks 5R and 5S, respectively. A single incorporation of either monomer X or monomer Y in the central position of a DNA 9-mer results in decreased thermal affinity toward both DNA and RNA complements (ΔT(m) = -3.5 °C/-3.5 °C for monomer X and ΔT(m) = -11.0 °C/-6.5 °C for monomer Y). CD measurements do...

  20. Coupling Reagent for UV/vis Absorbing Azobenzene-Based Quantitative Analysis of the Extent of Functional Group Immobilization on Silica.

    Science.gov (United States)

    Choi, Ra-Young; Lee, Chang-Hee; Jun, Chul-Ho

    2018-05-18

    A methallylsilane coupling reagent, containing both a N-hydroxysuccinimidyl(NHS)-ester group and a UV/vis absorbing azobenzene linker undergoes acid-catalyzed immobilization on silica. Analysis of the UV/vis absorption band associated with the azobenzene group in the adduct enables facile quantitative determination of the extent of loading of the NHS groups. Reaction of NHS-groups on the silica surface with amine groups of GOx and rhodamine can be employed to generate enzyme or dye-immobilized silica for quantitative analysis.

  1. Conserving Coherence and Storing Energy during Internal Conversion: Photoinduced Dynamics of cis- and trans-Azobenzene Radical Cations

    KAUST Repository

    Munkerup, Kristin

    2017-10-24

    Light harvesting via energy storage in azobenzene has been a key topic for decades, and the process of energy distribution over the molecular degrees of freedom following photoexcitation remains to be understood. Dynamics of a photoexcited system can exhibit high degrees of non-ergodicity when it is driven by just a few degrees of freedom. Typically, an internal conversion leads to the loss of such localization of dynamics, as the intramolecular energy becomes statistically redistributed over all molecular degrees of freedom. Here, we present a unique case where the excitation energy remains localized even subsequent to internal conversion. Strong-field ionization is used to prepare cis- and trans-azobenzene radical cations on the D1 surface with little excess energy, at the equilibrium neutral geometry. These D1 ions are preferably formed because in this case D1 and D0 switch place in the presence of the strong laser field. The post-ionization dynamics is dictated by the potential energy landscape. The D1 surface is steep downhill along the cis/trans isomerization coordinate and towards a common minimum shared by the two isomers in the region of D1/D0 conical intersection. Coherent cis/trans torsional motion along this coordinate is manifested in the ion transients by a cosine modulation. In this scenario, D0 becomes populated with molecules that are energized mainly along the cis-trans isomerization coordinate, with the kinetic energy above the cis-trans inter-conversion barrier. These activated azobenzene molecules easily cycle back and forth along the D0 surface, and give rise to several periods of modulated signal before coherence is lost. This persistent localization of the internal energy during internal conversion is provided by the steep downhill potential energy surface, small initial internal energy content, and a strong hole-lone pair interaction that drives the molecule along the cis-trans isomerization coordinate to facilitate the transition between

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

    International Nuclear Information System (INIS)

    Kempe, Christian; Rutloh, Michael; Stumpe, Joachim

    2003-01-01

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

  3. Highly Efficient Synthesis of Allopurinol Locked Nucleic Acid Monomer by C6 Deamination of 8-Aza-7-bromo-7-deazaadenine Locked Nucleic Acid Monomer

    DEFF Research Database (Denmark)

    Kosbar, Tamer Reda El-Saeed; Sofan, M.; Abou-Zeid, L.

    2013-01-01

    An allopurinol locked nucleic acid (LNA) monomer was prepared by a novel strategy through C6 deamination of the corresponding 8-aza-7-bromo-7-deazaadenine LNA monomer with aqueous sodium hydroxide. An 8-aza-7-deazaadenine LNA monomer was also synthesized by a modification of the new synthetic...... the required LNA monomers....

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

    Energy Technology Data Exchange (ETDEWEB)

    Dobryakov, A. L.; Quick, M.; Ioffe, I. N.; Granovsky, A. A.; Ernsting, N. P.; Kovalenko, S. A. [Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, D-12489 Berlin (Germany)

    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.

  5. Redesign of the monomer-monomer interface of Cre recombinase yields an obligate heterotetrameric complex.

    Science.gov (United States)

    Zhang, Chi; Myers, Connie A; Qi, Zongtai; Mitra, Robi D; Corbo, Joseph C; Havranek, James J

    2015-10-15

    Cre recombinase catalyzes the cleavage and religation of DNA at loxP sites. The enzyme is a homotetramer in its functional state, and the symmetry of the protein complex enforces a pseudo-palindromic symmetry upon the loxP sequence. The Cre-lox system is a powerful tool for many researchers. However, broader application of the system is limited by the fixed sequence preferences of Cre, which are determined by both the direct DNA contacts and the homotetrameric arrangement of the Cre monomers. As a first step toward achieving recombination at arbitrary asymmetric target sites, we have broken the symmetry of the Cre tetramer assembly. Using a combination of computational and rational protein design, we have engineered an alternative interface between Cre monomers that is functional yet incompatible with the wild-type interface. Wild-type and engineered interface halves can be mixed to create two distinct Cre mutants, neither of which are functional in isolation, but which can form an active heterotetramer when combined. When these distinct mutants possess different DNA specificities, control over complex assembly directly discourages recombination at unwanted half-site combinations, enhancing the specificity of asymmetric site recombination. The engineered Cre mutants exhibit this assembly pattern in a variety of contexts, including mammalian cells. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

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

    Science.gov (United States)

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

    2015-11-01

    Here, we have designed and synthesized a novel cationic amphiphilic stimuli-responsive azobenzene-aminoglycoside (a small molecule) conjugate, Azo-AG 5, and characterized it by UV and FTIR. Light responsive nature of Azo-AG 5 was assessed under UV-vis light. Self- assembly of Azo-AG 5 in aqueous solutions into nanostructures and their ability to act as drug carrier were also investigated. The nanostructures of Azo-AG 5 showed average hydrodynamic diameter of ∼ 255 nm with aminoglycoside moiety (neomycin) and 4-dimethylaminoazobenzene forming hydrophilic shell and hydrophobic core, respectively. In the hydrophobic core, eosin and aspirin were successfully encapsulated. Dynamic light scattering (DLS) measurements demonstrated that the nanoassemblies showed expansion and contraction on successive UV and visible light irradiations exhibiting reversible on-off switch for controlling the drug release behavior. Similar behavior was observed when these nanostructures were subjected to pH-change. In vitro drug release studies showed a difference in UV and visible light-mediated release pattern. It was observed that the release rate under UV irradiation was comparatively higher than that observed under visible light. Further, azoreductase-mediated cleavage of the azo moiety in Azo-AG 5 nanoassemblies resulted in the dismantling of the structures into aggregated microstructures. Azo-AG 5 nanostructures having positive surface charge (+9.74 mV) successfully interacted with pDNA and retarded its mobility on agarose gel. Stimuli responsiveness of nanostructures and their on-off switch like behavior ensure the great potential as controlled drug delivery systems and in other biomedical applications such as colon-specific delivery and gene delivery. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Synthesis of New Vinyl Monomers for Chemical Agent Sensing Applications

    National Research Council Canada - National Science Library

    Hogen-Esch, Thieo

    2001-01-01

    The synthesis of styrene momomer p-vinylbenzoylacetophenone (monomer i) has been carried by the acetylation of 2- chloroethylbenzene and base elimination of the resulting 4-acetyl-2-chloroethylbenzene to give 4-acetylstyrene...

  8. Synthesis and thermal behavior of telechelic poly(butadiene)diols with azobenzene-based liquid-crystalline units in side chains

    Czech Academy of Sciences Publication Activity Database

    Poláková, Lenka; Sedláková, Zdeňka; Látalová, Petra

    2010-01-01

    Roč. 64, č. 4 (2010), s. 315-326 ISSN 0170-0839 R&D Projects: GA ČR GA202/09/2078 Institutional research plan: CEZ:AV0Z40500505 Keywords : azobenzene mesogens * radical addition * poly(butadiene)diols Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.215, year: 2010

  9. Atomic force and optical near-field microscopic investigations of polarization holographic gratings in a liquid crystalline azobenzene side-chain polyester

    DEFF Research Database (Denmark)

    Ramanujam, P.S.; Holme, N.C.R.; Hvilsted, S.

    1996-01-01

    Atomic force and scanning near-field optical microscopic investigations have been carried out on a polarization holographic grating recorded in an azobenzene side-chain Liquid crystalline polyester. It has been found that immediately following laser irradiation, a topographic surface grating...

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

    Czech Academy of Sciences Publication Activity Database

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

    2015-01-01

    Roč. 27, č. 13 (2015), s. 134208 ISSN 0953-8984 R&D Projects: GA ČR(CZ) GA14-02079S Institutional support: RVO:68378271 Keywords : photoisomerization * azobenzene * metal -organic frameworks * molecular switches Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.209, year: 2015

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

    Directory of Open Access Journals (Sweden)

    A. Schuler

    2017-01-01

    Full Text Available 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.

  12. A reversible conductivity modulation of azobenzene-based ionic liquids in aqueous solutions using UV/vis light.

    Science.gov (United States)

    Li, Zhiyong; Yuan, Xiaoqing; Feng, Ying; Chen, Yongkui; Zhao, Yuling; Wang, Huiyong; Xu, Qingli; Wang, Jianji

    2018-05-09

    Photo-induced conductivity modulation of stimuli-responsive materials is of great importance from the viewpoint of fundamental research and technology. In this work, 5 new kinds of azobenzene-based photo-responsive ionic liquids were synthesized and characterized, and UV/vis light modulation of their conductivity was investigated in an aqueous solution. The factors affecting the conductivity modulation of the photo-responsive fluids, such as photo-isomerization efficiency, photo-regulation aggregation, concentration and chemical structure of the ionic liquids, were examined systematically. It was found that the conductivity of the ionic liquids in water exhibited a significant increase upon UV light irradiation and the ionic liquids with a shorter alkyl spacer in the cation showed a more remarkable photo-induced conductivity enhancement with a maximum increase of 150%. In addition, the solution conductivity was restored (or very close) to the initial value upon an alternative irradiation with visible light. Thus, the solution conductivity can be modulated using alternative irradiation with UV and visible light. Although the reversible photo-isomerization of the azobenzene group under UV/vis irradiation is the origin of the conductivity modulation, the photo-regulated aggregation of the ionic liquid in water is indispensable for the maximum degree of conductivity modulation because UV irradiation can weaken, even break the aggregated cis-isomers of the ionic liquids in an aqueous solution.

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

    International Nuclear Information System (INIS)

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

    2011-01-01

    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.

  14. Monomer-dependent secondary nucleation in amyloid formation.

    Science.gov (United States)

    Linse, Sara

    2017-08-01

    Secondary nucleation of monomers on the surface of an already existing aggregate that is formed from the same kind of monomers may lead to autocatalytic amplification of a self-assembly process. Such monomer-dependent secondary nucleation occurs during the crystallization of small molecules or proteins and self-assembled materials, as well as in protein self-assembly into fibrous structures. Indications of secondary nucleation may come from analyses of kinetic experiments starting from pure monomers or monomers supplemented with a low concentration of pre-formed aggregates (seeds). More firm evidence requires additional experiments, for example those employing isotope labels to distinguish new aggregates arising from the monomer from those resulting from fragmentation of the seed. In cases of amyloid formation, secondary nucleation leads to the formation of toxic oligomers, and inhibitors of secondary nucleation may serve as starting points for therapeutic developments. Secondary nucleation displays a high degree of structural specificity and may be enhanced by mutations or screening of electrostatic repulsion.

  15. Polymerization of impregnated monomer in wood by microwave irradiation

    International Nuclear Information System (INIS)

    Kawase, Kaoru; Hayakawa, Kiyoshi

    1976-01-01

    The manufacturing of a wood-plastic combination (WPC) by irradiation of microwave (2,450 and 915 +- 50 MHz) or gamma-ray was carried out. After the impregnation of dry woods (Hinoki: Chamaecyparis obtusa Endl., Buna: Acer mono Maxim., and Kaede: Fagus crenata Blume) with the mixture of the vinyl monomers and chemical reagents, the monomer in wood was polymerized by irradiation. In case of polymerization with microwave (2,450 MHz) the effect of oxygen was not recognized, but in the case of gamma-ray the rate of polymerization remarkably decreased in the presence of oxygen. The polymerization of various monomers was carried out also in the air, and the conversions of styrene, methyl-, ethyl-, n-propyl-, and n-butyl-methacrylate were 51.8 -- 89.1%, but that of vinyl acetate was lower (4.3 -- 8.2%). The conversion of monomers with irradiation of 915 MHz microwave was very low (2.6 -- 33.5%). The conversion of monomers increased when toluylene diisocyanate was added in the monomers. The percentage of extraction with hot benzene of WPC (chip) decreased by the addition of toluylene diisocyanate. It was concluded from C.H.N. analyses that the reaction took place among the wood, toluylene diisocyanate and methyl methacrylate. (auth.)

  16. Perturbation of the Monomer-Monomer Interfaces of the Benzoylformate Decarboxylase Tetramer

    Energy Technology Data Exchange (ETDEWEB)

    Andrews, Forest H.; Rogers, Megan P.; Paul, Lake N.; McLeish, Michael J. [IUPUI; (Purdue)

    2014-08-14

    The X-ray structure of benzoylformate decarboxylase (BFDC) from Pseudomonas putida ATCC 12633 shows it to be a tetramer. This was believed to be typical of all thiamin diphosphate-dependent decarboxylases until recently when the structure of KdcA, a branched-chain 2-keto acid decarboxylase from Lactococcus lactis, showed it to be a homodimer. This lent credence to earlier unfolding experiments on pyruvate decarboxylase from Saccharomyces cerevisiae that indicated that it might be active as a dimer. To investigate this possibility in BFDC, we sought to shift the equilibrium toward dimer formation. Point mutations were made in the noncatalytic monomer–monomer interfaces, but these had a minimal effect on both tetramer formation and catalytic activity. Subsequently, the R141E/Y288A/A306F variant was shown by analytical ultracentrifugation to be partially dimeric. It was also found to be catalytically inactive. Further experiments revealed that just two mutations, R141E and A306F, were sufficient to markedly alter the dimer–tetramer equilibrium and to provide an ~450-fold decrease in kcat. Equilibrium denaturation studies suggested that the residual activity was possibly due to the presence of residual tetramer. The structures of the R141E and A306F variants, determined to <1.5 Å resolution, hinted that disruption of the monomer interfaces will be accompanied by movement of a loop containing Leu109 and Leu110. As these residues contribute to the hydrophobicity of the active site and the correct positioning of the substrate, it seems that tetramer formation may well be critical to the catalytic activity of BFDC.

  17. In-vitro transdentinal diffusion of monomers from adhesives.

    Science.gov (United States)

    Putzeys, Eveline; Duca, Radu Corneliu; Coppens, Lieve; Vanoirbeek, Jeroen; Godderis, Lode; Van Meerbeek, Bart; Van Landuyt, Kirsten L

    2018-06-01

    Biocompatibility of adhesives is important since adhesives may be applied on dentin near the pulp. Accurate knowledge of the quantity of monomers reaching the pulp is important to determine potential side effects. The aim of this study was to assess the transdentinal diffusion of residual monomers from dental adhesive systems using an in-vitro pulp chamber model. Dentin disks with a thickness of 300 µm were produced from human third molars. These disks were fixed between two open-ended glass tubes, representing an in-vitro pulp chamber. The etch-and-rinse adhesive OptiBond FL and the self-etch adhesive Clearfil SE Bond were applied to the dentin side of the disks, while on in the pulpal side, the glass tube was filled with 600 µL water. The transdentinal diffusion of different monomers was quantified using ultra-performance liquid chromatography-tandem mass spectrometry. The monomers HEMA, CQ, BisGMA, GPDM, 10-MDP and UDMA eluted from the dental materials and were able to diffuse through the dentin disks to a certain extent. Compounds with a lower molecular weight (uncured group: HEMA 7850 nmol and CQ 78.2 nmol) were more likely to elute and diffuse compared to monomers with a higher molecular weight (uncured group: BisGMA 0.42 nmol). When the adhesives were left uncured, diffusion was up to 10 times higher compared to the cured conditions. This in-vitro research resulted in the quantification of various monomers able to diffuse through dentin and therefore contributes to a more detailed understanding about the potential exposure of the dental pulp to monomers from dental adhesives. Biocompatibility of adhesives is important since adhesives may be applied on dentin near the pulp, where tubular density and diameter are greatest. Copyright © 2018. Published by Elsevier Ltd.

  18. In situ polymerization of vinyl monomers in polyester yarns

    International Nuclear Information System (INIS)

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

    1978-01-01

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

  19. The radiation grafting of vinyl monomers to cotton fabrics

    International Nuclear Information System (INIS)

    Shiraishi, N.; Williams, J.L.; Stannett, V.

    1982-01-01

    Cobalt 60 γ and electron beam radiation were used to graft diethylphosphatoethyl methacrylate, pure and in 90:10 methanol solution, to cotton cloth. This monomer, with an 11.64% phosphorus content, was especially developed by the Scott Paper Co. to develop fire retardancy. A simple pad and squeeze application followed by direct irradiation under a nitrogen atmosphere was used. Although excess monomer could be removed by washing with water, no solvent for the polymer was found so only the total 'add-ons' could be measured. With 60 Co irradiation, total polymerization was obtained with more than 1 Mrad but with electron beam irradiation only about 50% conversion was obtained even with 10 Mrad. No acceleration in the rates could be achieved with the viscous pure monomer as opposed to in solution. Yields adequate to impart reasonable fire retardancy could, however, be obtained with about 3 Mrad with electrons. No noticeable degradation of the polymer occurred at the doses used. (author)

  20. In situ polymerization of monomers for polyphenylquinoxaline/graphite

    Science.gov (United States)

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

    1973-01-01

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

  1. Evaluation of level of impregnation monomers in hydrotalcite

    International Nuclear Information System (INIS)

    Carmo, Danieli M. do; Machado, Jacson S.C.; Oliveira, Marcelo F.L.; Oliveira, Marcia G.; Soares, Bluma G.

    2011-01-01

    To evaluate the impregnation degree of 1,6-hexamethylene diisocyanate and 1,4-butanediol monomers in hydrotalcite clays it was prepared dispersions with mixing ratio 1:100 (clay/monomer), using the Ultraturrax and Ultrasound. Subsequently the samples were characterized by Fourier Transform Infrared Spectroscopy and X-ray Diffraction. Swelling tests and Tyndall effect were used to illustrate the different dispersions. The results indicated a strong interaction between the hydrotalcite with 1,6-hexamethylene diisocyanate, favoring the formation of intercalated structures. (author)

  2. Studies on curing effect of phosphite monomer by EB radiation in the air

    International Nuclear Information System (INIS)

    Xiao, B.; Zhou, Y.; Li, S.; Luo, M.; Wang, X.; Zhao, P.

    2000-01-01

    A new type phosphite active monomer was synthesized. The resisting oxygen inhibition effect of this monomer and the effects of irradiation dose and concentration of phosphite active monomer on curing were studied. At the same time, curing results were analysed, through gel content and IR spectrum. The excellent resisting oxygen inhibition result of this phosphite active monomer was shown by experiments. EB radiation curing in the air was successfully carried out by the phosphite active monomer. (author)

  3. Dynamic actuation of glassy polymersomes through isomerization of a single azobenzene unit at the block copolymer interface

    Science.gov (United States)

    Molla, Mijanur Rahaman; Rangadurai, Poornima; Antony, Lucas; Swaminathan, Subramani; de Pablo, Juan J.; Thayumanavan, S.

    2018-06-01

    Nature has engineered exquisitely responsive systems where molecular-scale information is transferred across an interface and propagated over long length scales. Such systems rely on multiple interacting, signalling and adaptable molecular and supramolecular networks that are built on dynamic, non-equilibrium structures. Comparable synthetic systems are still in their infancy. Here, we demonstrate that the light-induced actuation of a molecularly thin interfacial layer, assembled from a hydrophilic- azobenzene -hydrophobic diblock copolymer, can result in a reversible, long-lived perturbation of a robust glassy membrane across a range of over 500 chemical bonds. We show that the out-of-equilibrium actuation is caused by the photochemical trans-cis isomerization of the azo group, a single chemical functionality, in the middle of the interfacial layer. The principles proposed here are implemented in water-dispersed nanocapsules, and have implications for on-demand release of embedded cargo molecules.

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

    International Nuclear Information System (INIS)

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

    2006-01-01

    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 ' -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 2 (t) using the optical polarized absorption measurement is also investigated

  5. Simulation of the photodynamics of azobenzene on its first excited state: Comparison of full multiple spawning and surface hopping treatments

    International Nuclear Information System (INIS)

    Toniolo, A.; Ciminelli, C.; Persico, M.; Martinez, T.J.

    2005-01-01

    We have studied the cis→trans and trans→cis photoisomerization of azobenzene after n→π* excitation using the full multiple spawning (FMS) method for nonadiabatic wave-packet dynamics with potential-energy surfaces and couplings determined 'on the fly' from a reparametrized multiconfigurational semiempirical method. We compare the FMS results with a previous direct dynamics treatment using the same potential-energy surfaces and couplings, but with the nonadiabatic dynamics modeled using a semiclassical surface hopping (SH) method. We concentrate on the dynamical effects that determine the photoisomerization quantum yields, namely, the rate of radiationless electronic relaxation and the character of motion along the reaction coordinate. The quantal and semiclassical results are in good general agreement, confirming our previous analysis of the photodynamics. The SH method slightly overestimates the rate of excited state decay, leading in this case to lower quantum yields

  6. Influence of vinyl chloride monomer and vinyl chloride monomer derivatives on hepatic DNA synthesis

    International Nuclear Information System (INIS)

    Brenner, E.A.

    1982-01-01

    Vinyl chloride monomer (VCM) is used extensively in the chemical industry, mainly in the production of polyvinyl chloride. It has recently been found to cause hepatic angiosarcoma. As VCM has also been shown to be mutagenic after metabolic activation the effect of VCM on DNA synthesis was investigated. [ 3 H]Thymidine incorporation into DNA was used to measure the rate of DNA synthesis in regenerating rat liver. A possible direct toxic effect of VCM or its metabolites on liver cell metabolism was examined by two unrelated techniques, viz. the measurement of adenine nucleotide concentrations in regenerating livers and the influence on transmembrane potentials in hepatocytes. The distribution of radioactivity in subcellular fractions following [ 14 C]VCM administration suggested microsomal conversion of VCM to an active form which was selectively retained in the nuclear fraction. Measurement of the activities of thymidine kinase and DNA polymerase in regenerating liver indicated that the induction of these enzymes which normally occurs after partial hepatectomy was not prevented by VCM treatment. Three techniques were used to test the hypothesis that the retardation in DNA synthesis was due to DNA damage: the prophage lambda induction test for DNA damage, autoradiographic detection of unscheduled thymidine incorporation into DNA, and detection of DNA strand breaks in alkaline sucrose gradients. All three provided evidence of DNA damage and led to the development of a novel technique to confirm these findings. This involved centrifugation in neutral sucrose gradients on intact double-stranded DNA contained in hepatocyte nucleoids and showed conclusively that VCM administration causes DNA strand breaks. Subsequent repair of DNA was also assessed by this technique. The site of the VCM/metabolite: DNA reaction was characterized by DNA thermal denaturation and renaturation studies

  7. Base-catalyzed depolymerization of lignin : separation of monomers

    Energy Technology Data Exchange (ETDEWEB)

    Vigneault, A. [Sherbrooke Univ., PQ (Canada). Dept. of Chemical Engineering; Johnson, D.K. [National Renewable Energy Laboratory, Golden, CO (United States); Chornet, E. [Sherbrooke Univ., PQ (Canada). Dept. of Chemical Engineering; National Renewable Energy Laboratory, Golden, CO (United States)

    2007-12-15

    Biofuels produced from residual lignocellulosic biomass range from ethanol to biodiesel. The use of lignin for the production of alternate biofuels and green chemicals has been studied with particular emphasis on the structure of lignin and its oxyaromatic nature. In an effort to fractionate lignocellulosic biomass and valorize specific constitutive fractions, the authors developed a strategy for the separation of 12 added value monomers produced during the hydrolytic base catalyzed depolymerization (BCD) of a Steam Exploded Aspen Lignin. The separation strategy was similar to vanillin purification to obtain pure monomers, but combining more steps after the lignin depolymerization such as acidification, batch liquid-liquid-extraction (LLE), followed by vacuum distillation, liquid chromatography (LC) and crystallization. The purpose was to develop basic data for an industrial size process flow diagram, and to evaluate both the monomer losses during the separation and the energy requirements. Experimentally testing of LLE, vacuum distillation and flash LC in the laboratory showed that batch vacuum distillation produced up to 4 fractions. Process simulation revealed that a series of 4 vacuum distillation columns could produce 5 distinct monomer streams, of which 3 require further chromatography and crystallization operations for purification. 22 refs., 4 tabs., 8 figs.

  8. Two Populations Mean-Field Monomer-Dimer Model

    Science.gov (United States)

    Alberici, Diego; Mingione, Emanuele

    2018-04-01

    A two populations mean-field monomer-dimer model including both hard-core and attractive interactions between dimers is considered. The pressure density in the thermodynamic limit is proved to satisfy a variational principle. A detailed analysis is made in the limit of one population is much smaller than the other and a ferromagnetic mean-field phase transition is found.

  9. The LOMOsup(R) process: a solution for residual monomers

    International Nuclear Information System (INIS)

    Derbyshire, R.L.

    1979-01-01

    Regulatory activity over the last several years has addressed the potential problems associated with the migration of residual monomers from a number of commodity food packages. Regardless of the outcome of current debates, it will always be desirable to reduce monomer levels to as low a level as economically practicable so that they do not become indirect additives. The LOMO process is a body of technology inclusive of an ionizing radiation treatment which can result in sharp reduction of residual monomer levels in commodity plastic resins. The process may be applicable to factory intermediates, raw resins, or finished articles. Depending upon the individual system and its monomers, LOMO treatment can result in reductions to levels which press today's analytical test capability. Industrial radiation processing is normally accomplished with electron beam accelerators. Electron beam processing continues to gain in understanding and acceptance as one of the very few basic methods by which energy can be imparted to an industrial process system. Typically, whole factories are constructed around one accelerator. (author)

  10. Complex-radical copolymerization of vinyl monomers on organoelemental initiators

    International Nuclear Information System (INIS)

    Grishin, D.F.

    1993-01-01

    Data on regularities of the initiation and growth of the (co)polymerization of polar vinyl series monomers on organo-elemental initiator, organo-boron in particular, are generalized. The effect of organo-metallic compounds and some phenol type inhibitors on the rate of acrylate (co)polymerization is analyzed from view of the change of electroacceptor properties (electrophilicity) of macroradicals

  11. Low temperature irradiation of vitrifiable mixtures of unsaturated monomers

    International Nuclear Information System (INIS)

    Kaetsu, I.; Ito, A.; Hayashi, K.

    1975-01-01

    A specific mixture containing at least one polymerizable unsaturated monomer which is not vitrifiable by itself can advantageously be polymerized by irradiating the mixture at a temperature not higher than 100 0 C above glass transition temperature of the mixture with an ionizing radiation and/or a light. 12 claims, 6 drawings, figures

  12. 21 CFR 864.7300 - Fibrin monomer paracoagulation test.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Fibrin monomer paracoagulation test. 864.7300 Section 864.7300 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES HEMATOLOGY AND PATHOLOGY DEVICES Hematology Kits and Packages § 864.7300 Fibrin...

  13. Facile synthesis of allyl resinate monomer in an aqueous solution ...

    Indian Academy of Sciences (India)

    The synthesized monomer product appeared as a viscous liquid, with a viscosity of 460 mPa·s at 25◦C and a density of ... ated under high reaction temperature, which reduces the ... The use of DMF as an organic solvent also comes with.

  14. Step growth of an AB2 monomer, with cycle formation

    DEFF Research Database (Denmark)

    Cameron, Colin; Fawcett, Allan H.; Hetherington, Cecil R.

    1998-01-01

    A computer-based lattice model of the step growth reaction of an AB2 monomer, the next elaborate system after an AB monomer, has been devised that allows the simultaneous and explicit occurrence of inter- and intramolecular reactions of A and B groups of the flexible and moving molecules according...... with fractal characteristics. Growth stops when each molecule contains a cycle. For the model explored, in which six lattice sites are used for each monomer, the limiting value of the number average degree of polymerization, 〈x〉n,∞, is 14.6(±0.3) (after infinite time). The occurrence within the system of rings...... of m residues (m=1,2,3,...) is found to depend upon m and the extent of reaction of the A groups, pa, according to Rm=C0pm am-2.71, the constant C0 reflecting the structure of the lattice and the monomer, and being shown to determine the final degree of polymerization. The exponent of the integers m...

  15. Monomer-Polymer Chemistry and the Impregnation Process

    Energy Technology Data Exchange (ETDEWEB)

    Stannett, V. [North Carolina State University, Raleigh, NC (United States)

    1968-10-15

    A brief outline of early polymerization techniques is followed by a description of polymerization process chemistry, impregnation and polymerization methods and criteria for the choice of monomer. General considerations, including the effects of polymerization inhibitors, swelling agents, radiation dose rate and sample thickness, are enumerated. (author)

  16. In situ atomic force microscopy studies of reversible light-induced switching of surface roughness and adhesion in azobenzene-containing PMMA films

    International Nuclear Information System (INIS)

    Mueller, M.; Gonzalez-Garcia, Y.; Pakula, C.; Zaporojtchenko, V.; Strunskus, T.; Faupel, F.; Herges, R.; Zargarani, D.; Magnussen, O.M.

    2011-01-01

    Thin films in the range 40-80 nm of a blend of PMMA with an azobenzene derivative have been studied directly during UV and blue light irradiation by atomic force microscopy (AFM), revealing highly reversible changes in the surface roughness and the film adhesion. UV light induces an ∼80% increase in surface roughness, whereas illumination by blue light completely reverses these changes. Based on the observed surface topography and transition kinetics a reversible mass flow mechanisms is suggested, where the polarity changes upon switching trigger a wetting-dewetting transition in a surface segregation layer of the chromophore. Similar AFM measurements of the pull-off force indicate a decrease upon UV and an increase after blue light illumination with a complex kinetic behavior: a rapid initial change, attributed to the change in the cis isomer fraction of the azobenzene derivative, and a more gradual change, indicative of slow structural reorganization.

  17. Binding interactions between suberin monomer components and pesticides

    Energy Technology Data Exchange (ETDEWEB)

    Olivella, M.À., E-mail: angels.olivella@udg.edu [Department of Chemical Engineering, Escola Politècnica Superior, Universitat de Girona, Maria Aurèlia Capmany, 61, 17071 Girona (Spain); Bazzicalupi, C.; Bianchi, A. [Department of Chemistry “Ugo Schiff”, University of Florence, Via della Lastruccia, 3, 50019 Sesto Fiorentino (Italy); Río, J.C. del [Instituto de Recursos Naturales y Agrobiología de Sevilla, Consejo Superior de Investigaciones Científicas, P.O. Box 1052, 41080 Seville (Spain); Fiol, N.; Villaescusa, I. [Department of Chemical Engineering, Escola Politècnica Superior, Universitat de Girona, Maria Aurèlia Capmany, 61, 17071 Girona (Spain)

    2015-09-15

    Understanding the role of biomacromolecules and their interactions with pollutants is a key for elucidating the sorption mechanisms and making an accurate assessment of the environmental fate of pollutants. The knowledge of the sorption properties of the different constituents of these biomacromolecules may furnish a significant contribution to this purpose. Suberin is a very abundant biopolymer in higher plants. In this study, suberin monomers isolated from cork were analyzed by thermally-assisted methylation with tetramethylammonium hydroxide (TMAH) in a pyrolysis unit coupled to gas chromatography–mass spectrometry (GC/MS). The isolated monomer mixture was used to study the sorption of three pesticides (isoproturon, methomyl and oxamyl). The modes of pesticide–sorbent interactions were analyzed by means of two modeling calculations, the first one representing only the mixture of suberin monomers used in the sorption study, and the second one including glycerol to the mixture of suberin monomers, as a building block of the suberin molecule. The results indicated that the highest sorption capacity exhibited by the sorbent was for isoproturon (33%) being methomyl and oxamyl sorbed by the main suberin components to a lesser extent (3% and < 1%, respectively). In addition to van der Waals interactions with the apolar region of sorbent and isoproturon, modeling calculations evidenced the formation of a hydrogen bond between the isoproturon NH group and a carboxylic oxygen atom of a suberin monomer. In the case of methomyl and oxamyl only weak van der Waals interactions stabilize the pesticide–sorbent adducts. The presence of glycerol in the model provoked significant changes in the interactions with isoproturon and methomyl. - Highlights: • Suberin has low affinity to retain pesticides of aliphatic character. • Suberin has a moderate affinity to adsorb isoproturon. • Modeling calculations show that apolar portion of suberin interacts with isoproturon.

  18. Binding interactions between suberin monomer components and pesticides

    International Nuclear Information System (INIS)

    Olivella, M.À.; Bazzicalupi, C.; Bianchi, A.; Río, J.C. del; Fiol, N.; Villaescusa, I.

    2015-01-01

    Understanding the role of biomacromolecules and their interactions with pollutants is a key for elucidating the sorption mechanisms and making an accurate assessment of the environmental fate of pollutants. The knowledge of the sorption properties of the different constituents of these biomacromolecules may furnish a significant contribution to this purpose. Suberin is a very abundant biopolymer in higher plants. In this study, suberin monomers isolated from cork were analyzed by thermally-assisted methylation with tetramethylammonium hydroxide (TMAH) in a pyrolysis unit coupled to gas chromatography–mass spectrometry (GC/MS). The isolated monomer mixture was used to study the sorption of three pesticides (isoproturon, methomyl and oxamyl). The modes of pesticide–sorbent interactions were analyzed by means of two modeling calculations, the first one representing only the mixture of suberin monomers used in the sorption study, and the second one including glycerol to the mixture of suberin monomers, as a building block of the suberin molecule. The results indicated that the highest sorption capacity exhibited by the sorbent was for isoproturon (33%) being methomyl and oxamyl sorbed by the main suberin components to a lesser extent (3% and < 1%, respectively). In addition to van der Waals interactions with the apolar region of sorbent and isoproturon, modeling calculations evidenced the formation of a hydrogen bond between the isoproturon NH group and a carboxylic oxygen atom of a suberin monomer. In the case of methomyl and oxamyl only weak van der Waals interactions stabilize the pesticide–sorbent adducts. The presence of glycerol in the model provoked significant changes in the interactions with isoproturon and methomyl. - Highlights: • Suberin has low affinity to retain pesticides of aliphatic character. • Suberin has a moderate affinity to adsorb isoproturon. • Modeling calculations show that apolar portion of suberin interacts with isoproturon.

  19. Cis-to- Trans Isomerization of Azobenzene Derivatives Studied with Transition Path Sampling and Quantum Mechanical/Molecular Mechanical Molecular Dynamics.

    Science.gov (United States)

    Muždalo, Anja; Saalfrank, Peter; Vreede, Jocelyne; Santer, Mark

    2018-04-10

    Azobenzene-based molecular photoswitches are becoming increasingly important for the development of photoresponsive, functional soft-matter material systems. Upon illumination with light, fast interconversion between a more stable trans and a metastable cis configuration can be established resulting in pronounced changes in conformation, dipole moment or hydrophobicity. A rational design of functional photosensitive molecules with embedded azo moieties requires a thorough understanding of isomerization mechanisms and rates, especially the thermally activated relaxation. For small azo derivatives considered in the gas phase or simple solvents, Eyring's classical transition state theory (TST) approach yields useful predictions for trends in activation energies or corresponding half-life times of the cis isomer. However, TST or improved theories cannot easily be applied when the azo moiety is part of a larger molecular complex or embedded into a heterogeneous environment, where a multitude of possible reaction pathways may exist. In these cases, only the sampling of an ensemble of dynamic reactive trajectories (transition path sampling, TPS) with explicit models of the environment may reveal the nature of the processes involved. In the present work we show how a TPS approach can conveniently be implemented for the phenomenon of relaxation-isomerization of azobenzenes starting with the simple examples of pure azobenzene and a push-pull derivative immersed in a polar (DMSO) and apolar (toluene) solvent. The latter are represented explicitly at a molecular mechanical (MM) and the azo moiety at a quantum mechanical (QM) level. We demonstrate for the push-pull azobenzene that path sampling in combination with the chosen QM/MM scheme produces the expected change in isomerization pathway from inversion to rotation in going from a low to a high permittivity (explicit) solvent model. We discuss the potential of the simulation procedure presented for comparative calculation of

  20. Macroradical initiated polymerisation of acrylic and methacrylic monomers.

    Science.gov (United States)

    Mijangos, Irene; Guerreiro, António; Piletska, Elena; Whitcombe, Michael J; Karim, Kal; Chianella, Iva; Piletsky, Sergey

    2009-10-01

    An approach has been developed for the grafting of monomers onto poly(trimethylolpropane trimethacrylate) (polyTRIM) particles using 2,2-diethyl dithiocarbamic acid benzyl ester (DDCABE) as an initiator. A set of polymers was prepared with this technique over different lengths of time and the kinetics of the reaction studied experimentally. It was found that the grafting of initiator to the polymeric support followed a second order reaction, while the subsequent addition of monomers from solution into the polyTRIM macroradicals followed a first order reaction. The living nature of the iniferter modified macroradicals permits easy consecutive grafting of multiple polymeric layers, allowing straightforward functionalisation of particles. However, the effectiveness of the grafted initiator decreased with each cycle of polymerisation. This technique can be used for a wide range of applications in analytical and biochemistry.

  1. Calculation of vibrational spectra for dioxouranium monochloride monomer and dimers

    Science.gov (United States)

    Umreiko, D. S.; Shundalau, M. B.; Zazhogin, A. P.; Komyak, A. I.

    2010-09-01

    Structural models were built and spectral characteristics were calculated based on ab initio calculations for the monomer and dimers of dioxouranium monochoride UO2Cl. The calculations were carried out in the effective core potential LANL2DZ approximation for the uranium atom and all-electron basis sets using DFT methods for oxygen and chlorine atoms (B3LYP/cc-pVDZ). The monomer UO2Cl was found to possess an equilibrium planar (close to T-shaped) configuration with C2v symmetry. The obtained spectral characteristics were analyzed and compared with experimental data. The adequacy of the proposed models and the qualitative agreement between calculation and experiment were demonstrated.

  2. In situ polymerization of monomers for polyphenylquinoxaline-graphite fiber composites

    Science.gov (United States)

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

    1974-01-01

    In situ polymerization of monomers was used to prepare graphite-fiber-reinforced polyphenylquinoxaline composites. Six different monomer combinations were investigated. Composite mechanical property retention characteristics were determined at 316 C (600 F) over an extended time period.

  3. Functionalized Nanoporous Polymer Membranes with Well-Defined Pore Architectures via Lyotropic Liquid-Crystalline Monomers

    National Research Council Canada - National Science Library

    Gin, Douglas

    1997-01-01

    .... Two lyotropic liquid-crystalline monomer platforms have been synthesized. The interchannel separations in the polymerizable materials can be varied in the 30-40 A range by the choice of counterion on the ionic headgroup of the monomers...

  4. Ortho-substituted triptycene-based diamines, monomers, and polymers, methods of making and uses thereof

    KAUST Repository

    Ghanem, Bader Saleh

    2017-04-13

    Described herein are ortho-dimethyl-substituted and tetramethyi-substituted triptycene-containing diamine monomers and microporous triptycene-based poiyimides and poiyamides, and methods of making the monomers and polymers.

  5. Ortho-substituted triptycene-based diamines, monomers, and polymers, methods of making and uses thereof

    KAUST Repository

    Ghanem, Bader Saleh; Pinnau, Ingo

    2017-01-01

    Described herein are ortho-dimethyl-substituted and tetramethyi-substituted triptycene-containing diamine monomers and microporous triptycene-based poiyimides and poiyamides, and methods of making the monomers and polymers.

  6. Structure of human insulin monomer in water/acetonitrile solution

    Energy Technology Data Exchange (ETDEWEB)

    Bocian, Wojciech; Sitkowski, Jerzy; Bednarek, Elzbieta [National Medicines Institute (Poland); Tarnowska, Anna; Kawecki, Robert [Institute of Organic Chemistry Polish Academy of Sciences (Poland); Kozerski, Lech [National Medicines Institute (Poland)], E-mail: lkoz@icho.edu.pl

    2008-01-15

    Here we present evidence that in water/acetonitrile solvent detailed structural and dynamic information can be obtained for important proteins that are naturally present as oligomers under native conditions. An NMR-derived human insulin monomer structure in H{sub 2}O/CD{sub 3}CN, 65/35 vol%, pH 3.6 is presented and compared with the available X-ray structure of a monomer that forms part of a hexamer (Acta Crystallogr. 2003 Sec. D59, 474) and with NMR structures in water and organic cosolvent. Detailed analysis using PFGSE NMR, temperature-dependent NMR, dilution experiments and CSI proves that the structure is monomeric in the concentration and temperature ranges 0.1-3 mM and 10-30 deg. C, respectively. The presence of long-range interstrand NOEs, as found in the crystal structure of the monomer, provides the evidence for conservation of the tertiary structure. Starting from structures calculated by the program CYANA, two different molecular dynamics simulated annealing refinement protocols were applied, either using the program AMBER in vacuum (AMBER{sub V}C), or including a generalized Born solvent model (AMBER{sub G}B)

  7. Structure of human insulin monomer in water/acetonitrile solution

    International Nuclear Information System (INIS)

    Bocian, Wojciech; Sitkowski, Jerzy; Bednarek, Elzbieta; Tarnowska, Anna; Kawecki, Robert; Kozerski, Lech

    2008-01-01

    Here we present evidence that in water/acetonitrile solvent detailed structural and dynamic information can be obtained for important proteins that are naturally present as oligomers under native conditions. An NMR-derived human insulin monomer structure in H 2 O/CD 3 CN, 65/35 vol%, pH 3.6 is presented and compared with the available X-ray structure of a monomer that forms part of a hexamer (Acta Crystallogr. 2003 Sec. D59, 474) and with NMR structures in water and organic cosolvent. Detailed analysis using PFGSE NMR, temperature-dependent NMR, dilution experiments and CSI proves that the structure is monomeric in the concentration and temperature ranges 0.1-3 mM and 10-30 deg. C, respectively. The presence of long-range interstrand NOEs, as found in the crystal structure of the monomer, provides the evidence for conservation of the tertiary structure. Starting from structures calculated by the program CYANA, two different molecular dynamics simulated annealing refinement protocols were applied, either using the program AMBER in vacuum (AMBER V C), or including a generalized Born solvent model (AMBER G B)

  8. Characterisation of polyhydroxyalkanoate copolymers with controllable four-monomer composition.

    Science.gov (United States)

    Dai, Yu; Lambert, Lynette; Yuan, Zhiguo; Keller, Jurg

    2008-03-20

    Polyhydroxyalkanoate (PHA) copolymers comprising the four monomers 3-hydroxybutyrate (3HB), 3-hydroxyvalerate (3HV), 3-hydroxy-2-methylvalerate (3HMV) and 3-hydroxy-2-methylbutyrate (3HMB) were generated using the recently discovered Defluviicoccus vanus-related glycogen accumulating organisms (DvGAOs) under anaerobic conditions without applying any nutrient limitations. The composition could be manipulated in a defined range by modifying the ratio of propionate and acetate provided in the feed stream. The PHAs produced were characterised as random copolymers (from propionate alone) or a mixture of random copolymers (from mixture of propionate and acetate) through microstructure analysis using 13C NMR spectroscopy. The sequence distribution of all eight comonomer pairs in the carbonyl region of 3HB and 3HV was identified and assigned with confidence utilising two-dimensional heteronuclear multiple bond coherence (HMBC) spectroscopy. Weight average molecular weights were in the range 390-560 kg/mol. Differential scanning calorimetry (DSC) traces showed that the melting temperature (Tm) varied between 70 and 161 degrees C and glass transition temperature (Tg) ranged from -8 to 0 degrees C. The incorporation of considerable amounts of 3HMV and 3HMB monomer units introduced additional "defects" into the PHBV copolymer structure and hence greatly lowered the crystallinity. The data indicate the potential of these four-monomer PHAs to be employed for practical applications, considering their favourable properties and the cost-effective production process using a mixed culture and simple carbon sources.

  9. Thermodynamics of swelling of latex particles with two monomers: a sensitivity analysis

    NARCIS (Netherlands)

    Maxwell, I.A.; Noel, E.F.J.; Schoonbrood, H.A.S.; German, A.L.

    1993-01-01

    A sensitivity anal. is performed to det. at what conditions the simplified model for swelling of latex particles by two monomers or two solvents is valid. This model proposes that, inter alia, the fractions of two monomers in the latex particles and in the monomer droplets are equal. The model is a

  10. The comparison of spectra and dyeing properties of new azonaphthalimide with analogues azobenzene dyes on natural and synthetic polymers

    Directory of Open Access Journals (Sweden)

    Mozhgan Hosseinnezhad

    2017-05-01

    Full Text Available The aim of the present research was to prepare new acid dyes based on naphthalimides. In this respect a series of monoazo acid dyes have been obtained using 4-amino-N-methyl (alternatively N-butyl-1,8-naphthalimide, aniline and p-nitroaniline as diazo components. 2-Naphthol-6-sulfonic acid (Schaeffer’s acid and 1-naphthol-8-amino-3,6-disulfonic acid (H-acid were used as coupling components. The spectrophotometric properties of the synthesized dyes were investigated in various solvents and compared with analogues azobenzene dyes. It is found, when acid dyes are applied in various solvents and different pH, additional bathochromically shifted bands of different intensity appear in the electronic spectra. This effect is caused by the occurrence of the equilibrium of azo and hydrazone forms in the dyes. The synthesized acid dyes were applied on wool fabrics in order to consider their dyeing properties, fastnesses and the obtainable color gamut. The synthesized dyes represented that they have the ability of dyeing wool and polyamide fabrics and give red to violet hues with good wash, medium light, and good milling and perspiration fastnesses.

  11. Excitation mechanism in the photoisomerization of a surface-bound azobenzene derivative: Role of the metallic substrate

    Science.gov (United States)

    Hagen, Sebastian; Kate, Peter; Leyssner, Felix; Nandi, Dhananjay; Wolf, Martin; Tegeder, Petra

    2008-10-01

    Two-photon photoemission spectroscopy is employed to elucidate the electronic structure and the excitation mechanism in the photoinduced isomerization of the molecular switch tetra-tert-butyl-azobenzene (TBA) adsorbed on Au(111). Our results demonstrate that the optical excitation and the mechanism of molecular switching at a metal surface is completely different compared to the corresponding process for the free molecule. In contrast to direct (intramolecular) excitation operative in the isomerization in the liquid phase, the conformational change in the surface-bound TBA is driven by a substrate-mediated charge transfer process. We find that photoexcitation above a threshold hν ≈2.2 eV leads to hole formation in the Au d-band followed by a hole transfer to the highest occupied molecular orbital of TBA. This transiently formed positive ion resonance subsequently results in a conformational change. The photon energy dependent photoisomerization cross section exhibit an unusual shape for a photochemical reaction of an adsorbate on a metal surface. It shows a thresholdlike behavior below hν ≈2.2 eV and above hν ≈4.4 eV. These thresholds correspond to the minimum energy required to create single or multiple hot holes in the Au d-bands, respectively. This study provides important new insights into the use of light to control the structure and function of molecular switches in direct contact with metal electrodes.

  12. Photo-switching of a non-ionic azobenzene amphiphile in Langmuir and Langmuir-Blodgett films.

    Science.gov (United States)

    Piosik, Emilia; Kotkowiak, Michał; Korbecka, Izabela; Galewski, Zbigniew; Martyński, Tomasz

    2017-08-30

    The concept of programmable and reconfigurable soft matter has emerged in science in the last few decades and can be realized by photoisomerization of azobenzene derivatives. This possibility results in great application potential of these compounds in optical storage devices, molecular junctions of electronic devices, command layers of liquid crystal displays or holographic gratings. In this paper, we present the results of a study on the organization and isomerization of the non-ionic and amphiphilic methyl 4-[(E)-2-[4-(nonyloxy)phenyl]diazen-1-yl]benzoate (LCA) in a 2D layer architecture of Langmuir and Langmuir-Blodgett (LB) films supported by spectroscopic studies on LCA chloroform solutions. Our investigation has shown a significantly different molecular organization of LCA depending on the ratio of trans and cis isomers in the monolayers. Taking advantage of a relatively low packing density and aggregation strength in the cis-LCA monolayer, we demonstrated the reversible isomerization in the LB film initially formed of LCA molecules in the cis form, while in the trans-LCA monolayer this effect was not observed. Our approach allows the formation of a switchable monolayer made of the amphiphilic LCA showing liquid crystalline properties without introducing an ionic group into the molecule structure, mixing with another compound or changing the subphase pH to provide free space for the molecules' isomerization.

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

    Science.gov (United States)

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

    2015-12-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Heinemann, Nils, E-mail: heinemann@physik.uni-kiel.de [Institut fuer Experimentelle und Angewandte Physik, Christian-Albrechts-Universitaet zu Kiel, Leibnizstr. 19, 24098 Kiel (Germany); Grunau, Jan; Leissner, Till; Andreyev, Oleksiy; Kuhn, Sonja; Jung, Ulrich [Institut fuer Experimentelle und Angewandte Physik, Christian-Albrechts-Universitaet zu Kiel, Leibnizstr. 19, 24098 Kiel (Germany); Zargarani, Dordaneh; Herges, Rainer [Otto-Diels-Institut fuer Organische Chemie, Christian-Albrechts-Universitaet zu Kiel, Otto-Hahn-Platz 4, 24098 Kiel (Germany); Magnussen, Olaf; Bauer, Michael [Institut fuer Experimentelle und Angewandte Physik, Christian-Albrechts-Universitaet zu Kiel, Leibnizstr. 19, 24098 Kiel (Germany)

    2012-06-19

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

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

    Science.gov (United States)

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

    2016-12-12

    A novel amphiphilic dendron (AZOC 8 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 AZOC 8 GAc/α-CD. The supra-dendron showed similar gelation behavior to that of AZOC 8 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. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Excitation mechanism in the photoisomerization of a surface-bound azobenzene derivative: Role of the metallic substrate

    International Nuclear Information System (INIS)

    Hagen, Sebastian; Kate, Peter; Leyssner, Felix; Nandi, Dhananjay; Wolf, Martin; Tegeder, Petra

    2008-01-01

    Two-photon photoemission spectroscopy is employed to elucidate the electronic structure and the excitation mechanism in the photoinduced isomerization of the molecular switch tetra-tert-butyl-azobenzene (TBA) adsorbed on Au(111). Our results demonstrate that the optical excitation and the mechanism of molecular switching at a metal surface is completely different compared to the corresponding process for the free molecule. In contrast to direct (intramolecular) excitation operative in the isomerization in the liquid phase, the conformational change in the surface-bound TBA is driven by a substrate-mediated charge transfer process. We find that photoexcitation above a threshold hν≅2.2 eV leads to hole formation in the Au d-band followed by a hole transfer to the highest occupied molecular orbital of TBA. This transiently formed positive ion resonance subsequently results in a conformational change. The photon energy dependent photoisomerization cross section exhibit an unusual shape for a photochemical reaction of an adsorbate on a metal surface. It shows a thresholdlike behavior below hν≅2.2 eV and above hν≅4.4 eV. These thresholds correspond to the minimum energy required to create single or multiple hot holes in the Au d-bands, respectively. This study provides important new insights into the use of light to control the structure and function of molecular switches in direct contact with metal electrodes.

  17. Radiation induced ionic polymerisation and grafting of vinyl monomers

    International Nuclear Information System (INIS)

    Stannett, V.T.

    1981-01-01

    Some special aspects of the radiation induced ionic polymerisation and grafting of vinyl monomers will be described. In particular the effects of solvents on the cationic polymerisation of the vinyl ethers will be discussed in detail. The unequivocal free ion nature of the polymerisation makes such information of considerable general interest. Estimates of the propagation rate constants with free cation polymerisation in solvents of different dielectric constants and solvation powers will be presented. Finally, some observations on the radiation induced graft polymerisation of ethyl vinyl ether to poly(vinyl chloride) and to polypropylene will be presented. (author)

  18. Radiation vulcanization of ethylene-propylene rubber with polyfunctional monomers

    Energy Technology Data Exchange (ETDEWEB)

    Jinhua, Wang; Yoshii, Fumio; Makuuchi, Keizo

    2001-01-01

    This paper reports on the sensitizing efficiency of several polyfunctional monomers to radiation vulcanization of ethylene-propylene rubber. And the results show that triethyleneglycol dimethacrylate (TEGDMA) gave the best results. TEGDMA not only lowers the vulcanization dose (D{sub v}), but also increases the tensile strength greatly. The content of TEGDMA does not affect the D{sub v} of TEGDMA-EPM, but affects the tensile strength at the D{sub v}. At best content (0.04 mol/100 g EPM), the tensile strength is increased from 6.0 to 12 MPa, and the elongation is 790% at the D{sub v}. (author)

  19. Breathing zone concentrations of methylmethacrylate monomer during joint replacement operations

    DEFF Research Database (Denmark)

    Darre, E; Jørgensen, L G; Vedel, P

    1992-01-01

    By use of a methylmethacrylate (MMA) Dräger tube and bellow bump, the breathing zone concentrations of MMA monomer were measured for the operating surgeon during cementation of the components of hip and knee joint prostheses. The highest recordings (50-100 p.p.m.) were encountered during cementat...... cementation of the acetabular cups with conventional polymethylmethacrylate cement. Such exposure could be eliminated by the use of personal protection equipment, local punctual field suction or change to a MMA/n-decylmethacrylate/isobornylmethacrylate bone cement....

  20. Shelf Life of PMR Polyimide Monomer Solutions and Prepregs Extended

    Science.gov (United States)

    Alston, William B.; Scheiman, Daniel A.

    2000-01-01

    PMR (Polymerization of Monomeric Reactants) technology was developed in the mid-1970's at the NASA Glenn Research Center at Lewis Field for fabricating high-temperature stable polyimide composites. This technology allowed a solution of polyimide monomers or prepreg (a fiber, such as glass or graphite, impregnated with PMR polyimide monomers) to be thermally cured without the release of volatiles that cause the formation of voids unlike the non-PMR technology used for polyimide condensation type resins. The initial PMR resin introduced as PMR 15 is still commercially available and is used worldwide by aerospace industries as the state-of-the-art resin for high-temperature polyimide composite applications. PMR 15 offers easy composite processing, excellent composite mechanical property retention, a long lifetime at use temperatures of 500 to 550 F, and relatively low cost. Later, second-generation PMR resin versions, such as PMR II 50 and VCAP 75, offer improvements in the upper-use temperature (to 700 F) and in the useful life at temperature without major compromises in processing and property retention but with significant increases in resin cost. Newer versions of nontoxic (non-methylene dianiline) PMR resins, such as BAX PMR 15, offer similar advantages as originally found for PMR 15 but also with significant increases in resin cost. Thus, the current scope of the entire PMR technology available meets a wide range of aeronautical requirements for polymer composite applications.

  1. Monomer-dimer problem on random planar honeycomb lattice

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Haizhen [School of Mathematical Sciences, Xiamen University, Xiamen 361005, Fujian (China); Department of Mathematics, Qinghai Normal University, Xining 810008, Qinghai (China); Zhang, Fuji; Qian, Jianguo, E-mail: jqqian@xmu.edu.cn [School of Mathematical Sciences, Xiamen University, Xiamen 361005, Fujian (China)

    2014-02-15

    We consider the monomer-dimer (MD) problem on a random planar honeycomb lattice model, namely, the random multiple chain. This is a lattice system with non-periodic boundary condition, whose generating process is inspired by the growth of single walled zigzag carbon nanotubes. By applying algebraic and combinatorial techniques we establish a calculating expression of the MD partition function for bipartite graphs, which corresponds to the permanent of a matrix. Further, by using the transfer matrix argument we show that the computing problem of the permanent of high order matrix can be converted into some lower order matrices for this family of lattices, based on which we derive an explicit recurrence formula for evaluating the MD partition function of multiple chains and random multiple chains. Finally, we analyze the expectation of the number of monomer-dimer arrangements on a random multiple chain and the asymptotic behavior of the annealed MD entropy when the multiple chain becomes infinite in width and length, respectively.

  2. Elution of monomer from different bulk fill dental composite resins.

    Science.gov (United States)

    Cebe, Mehmet Ata; Cebe, Fatma; Cengiz, Mehmet Fatih; Cetin, Ali Rıza; Arpag, Osman Fatih; Ozturk, Bora

    2015-07-01

    The purpose of this study was to evaluate the elution of Bis-GMA, TEGDMA, HEMA, and Bis-EMA monomers from six bulk fill composite resins over four different time periods, using HPLC. Six different composite resin materials were used in the present study: Tetric Evo Ceram Bulk Fill (Ivoclar Vivadent, Amherst, NY), X-tra Fill (VOCO, Cuxhaven, Germany), Sonic Fill (Kerr, Orange, CA, USA), Filtek Bulk Fill (3M ESPE Dental Product, St. Paul, MN), SDR (Dentsply, Konstanz, Germany), EQUIA (GC America INC, Alsip, IL). The samples (4mm thickness, 5mm diameter) were prepared and polymerized for 20s with a light emitted diode unit. After fabrication, each sample was immediately immersed in 75wt% ethanol/water solution used as extraction fluid and stored in the amber colored bottles at room temperature. Ethanol/water samples were taken (0.5mL) at predefined time intervals:10m (T1), 1h (T2), 24h (T3) and 30 days (T4). These samples were analyzed by HPLC. The obtained data were analyzed with one-way ANOVA and Tukey HSD at significance level of pcomposites (pcomposite resins in all time periods and the amount of eluted monomers was increased with time. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  3. High performance dental resin composites with hydrolytically stable monomers.

    Science.gov (United States)

    Wang, Xiaohong; Huyang, George; Palagummi, Sri Vikram; Liu, Xiaohui; Skrtic, Drago; Beauchamp, Carlos; Bowen, Rafael; Sun, Jirun

    2018-02-01

    The objectives of this project were to: 1) develop strong and durable dental resin composites by employing new monomers that are hydrolytically stable, and 2) demonstrate that resin composites based on these monomers perform superiorly to the traditional bisphenol A glycidyl dimethacrylate/triethylene glycol dimethacrylate (Bis-GMA/TEGDMA) composites under testing conditions relevant to clinical applications. New resins comprising hydrolytically stable, ether-based monomer, i.e., triethylene glycol divinylbenzyl ether (TEG-DVBE), and urethane dimethacrylate (UDMA) were produced via composition-controlled photo-polymerization. Their composites contained 67.5wt% of micro and 7.5wt% of nano-sized filler. The performances of both copolymers and composites were evaluated by a battery of clinically-relevant assessments: degree of vinyl conversion (DC: FTIR and NIR spectroscopy); refractive index (n: optical microscopy); elastic modulus (E), flexural strength (F) and fracture toughness (K IC ) (universal mechanical testing); Knoop hardness (HK; indentation); water sorption (W sp ) and solubility (W su ) (gravimetry); polymerization shrinkage (S v ; mercury dilatometry) and polymerization stress (tensometer). The experimental UDMA/TEG-DVBE composites were compared with the Bis-GMA/TEGDMA composites containing the identical filler contents, and with the commercial micro hybrid flowable composite. UDMA/TEG-DBVE composites exhibited n, E, W sp , W su and S v equivalent to the controls. They outperformed the controls with respect to F (up to 26.8% increase), K IC (up to 27.7% increase), modulus recovery upon water sorption (full recovery vs. 91.9% recovery), and stress formation (up to 52.7% reduction). In addition, new composites showed up to 27.7% increase in attainable DC compared to the traditional composites. Bis-GMA/TEGDMA controls exceeded the experimental composites with respect to only one property, the composite hardness. Significantly, up to 18.1% lower HK values in

  4. Polymerization of Polar Monomers from a Theoretical Perspective

    KAUST Repository

    Alghamdi, Miasser

    2016-10-11

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

  5. Graft copolimerization of hydrophilic monomers onto irradiated polypropylene fibers

    International Nuclear Information System (INIS)

    Sundardi, F.

    1978-01-01

    A method of graft copolymerization of hydrophilic monomers, such as 1-vinyl-2-pyrrolidone, acrylonitrile, acrylic acid, and acrylamide, onto irradiated polypropylene fibers has been studied. γ ray as well as electron beam were employed for the irradiation processes. Graft-copolymerization kinetics and the properties of grafted fibers have been investigated. Moisture regain, dyes absorption, and melting point of the grafted fibers were found to increase with the increasing of the degree of grafting. Polypropylene for 1-vinyl-2-pyrrolidone grafted fibers showed excellent dye absorption for almost all kinds of dyes such as direct, basic, acid, reactive, disper, and naphthol dyes. However, for polypropylene acrylic acid grafted fibers, the colorfastness to washing was found to be unsatisfactory. The colorfastness to washing for polypropylene 1-vinyl-2-pyrrolidone grafted fibers was found to be fairly good for certain types of dyes such as vat and naphthol dyes. (author)

  6. Biobased Epoxy Nanocomposites Derived from Lignin-Based Monomers.

    Science.gov (United States)

    Zhao, Shou; Abu-Omar, Mahdi M

    2015-07-13

    Biobased epoxy nanocomposites were synthesized based on 2-methoxy-4-propylphenol (dihydroeugenol, DHE), a molecule that has been obtained from the lignin component of biomass. To increase the content of hydroxyl groups, DHE was o-demethylated using aqueous HBr to yield propylcatechol (DHEO), which was subsequently glycidylated to epoxy monomer. Optimal conditions in terms of yield and epoxy equivalent weight were found to be 60 °C with equal NaOH/phenolic hydroxyl molar ratio. The structural evolution from DHE to cured epoxy was followed by (1)H NMR and Fourier transform infrared spectroscopy. The nano-montmorillonite modified DHEO epoxy exhibited improved storage modulus and thermal stability as determined from dynamic mechanical analysis and thermogravimetric analysis. This study widens the synthesis routes of biobased epoxy thermosets from lignin-based molecules.

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

    International Nuclear Information System (INIS)

    Wang Meng; Zhou Yang; Chen Dongzhong; Duan Junfei

    2016-01-01

    In this work, azobenzene mesogen-containing tin thiolates have been synthesized, which possess ordered lamellar structures persistent to higher temperature and serve as liquid crystalline precursors. Based on the preorganized tin thiolate precursors, SnS nanocrystals encapsulated with in-situ N-doped carbon layer have been achieved through a simple solventless pyrolysis process with the azobenzene mesogenic thiolate precursor served as Sn, S, N, and C sources simultaneously. Thus prepared nanocomposite materials as anode of lithium ion batteries present a large specific capacity of 604.6 mAh·g −1 at a current density of 100 mA·g −1 , keeping a high capacity retention up to 96% after 80 cycles, and display high rate capability due to the synergistic effect of well-dispersed SnS nanocrystals and N-doped carbon layer. Such encouraging results shed a light on the controlled preparation of advanced nanocomposites based on liquid crystalline metallomesogen precursors and may boost their novel intriguing applications. (special topic)

  8. On-line measurement of residual monomer during polymerisation of acrylamide using ultrasonics

    International Nuclear Information System (INIS)

    Ponraju, D.; Sebastian, Letha; Viswanathan, S.; Natarajan, A.; Palanichamy, P.; Jayakumar, T.; Baldev Raj

    1996-01-01

    An ultrasonic technique for the estimation of residual acrylamide monomer during the polymerization of aqueous acrylamide solution has been investigated. Polyacrylamide gel medium serves as a sensitive medium for detection and dosimetry of fast and thermal neutrons. This technique is based on the fact that the velocity of ultrasonic wave increases with the increase in elasticity due to polymerization. The percentage of residual acrylamide monomer is estimated using ultraviolet spectrophotometric analysis. The ultrasonic velocity is correlated with the residual monomer concentration

  9. Influence of template/functional monomer/cross‐linking monomer ratio on particle size and binding properties of molecularly imprinted nanoparticles

    DEFF Research Database (Denmark)

    Yoshimatsu, Keiichi; Yamazaki, Tomohiko; Chronakis, Ioannis S.

    2012-01-01

    A series of molecularly imprinted polymer nanoparticles have been synthesized employing various template/functional monomer/crosslinking monomer ratio and characterized in detail to elucidate the correlation between the synthetic conditions used and the properties (e.g., particle size and templat...... tuning of particle size and binding properties are required to fit practical applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012...

  10. Stripe and line textures in the B2 phase of bent-shape molecules in samples with polar surface anchoring

    Czech Academy of Sciences Publication Activity Database

    Lejček, Lubor; Novotná, Vladimíra; Glogarová, Milada

    2011-01-01

    Roč. 84, č. 6 (2011), 061701/1-061701/12 ISSN 1539-3755 R&D Projects: GA ČR(CZ) GAP204/11/0723 Institutional research plan: CEZ:AV0Z10100520 Keywords : liquid crystals Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.255, year: 2011

  11. 46 CFR 151.50-34 - Vinyl chloride (vinyl chloride monomer).

    Science.gov (United States)

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Vinyl chloride (vinyl chloride monomer). 151.50-34... chloride (vinyl chloride monomer). (a) Copper, aluminum, magnesium, mercury, silver, and their alloys shall... equipment that may come in contact with vinyl chloride liquid or vapor. (b) Valves, flanges, and pipe...

  12. Oligodeoxynucleotides containing 2'-amino-LNA nucleotides as constrained morpholino phosphoramidate and phosphorodiamidate monomers

    DEFF Research Database (Denmark)

    Kristensen, Kim Vejlegaard; Paul, Sibasish; Kosbar, Tamer

    2017-01-01

    Incorporation in a 2'→5' direction of a phosphorodiamidite 2'-amino-LNA-T nucleotide as the morpholino phosphoramidate and N,N-dimethylamino phosphorodiamidate monomers into six oligonucleotides is reported. Thermal denaturation studies showed that the novel 2'-amino-LNA-based morpholino monomers...

  13. Modulation of i-motif thermodynamic stability by the introduction of UNA (unlocked nucleic acid) monomers

    DEFF Research Database (Denmark)

    Pasternak, Anna; Wengel, Jesper

    2011-01-01

    The influence of acyclic RNA derivatives, UNA (unlocked nucleic acid) monomers, on i-DNA thermodynamic stability has been investigated. The 22 nt human telomeric fragment was chosen as the model sequence for stability studies. UNA monomers modulate i-motif stability in a position-depending manner...

  14. Triptycene-based ladder monomers and polymers, methods of making each, and methods of use

    KAUST Repository

    Pinnau, Ingo; Ghanem, Bader; Swaidan, Raja

    2015-01-01

    Embodiments of the present disclosure provide for a triptycene-based A-B monomer, a method of making a triptycene-based A-B monomer, a triptycene-based ladder polymer, a method of making a triptycene-based ladder polymers, a method of using

  15. Sulfonated copolyimide membranes derived from a novel diamine monomer with pendant benzimidazole groups for fuel cells

    DEFF Research Database (Denmark)

    Li, Wei; Guo, Xiaoxia; Aili, David

    2015-01-01

    . A series of sulfonated copolyimides (SPI) are prepared via random copolymerizatio of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) with a new diamine monomer with pendant benzimidazole groups, 2,2'-bis(4-(1H-benzo[d]imidazol-2-yl)phenoxy)benzidine (BIPOB), and a sulfonated diamine monomer 4,4'-bis...

  16. Ligustrazine monomer against cerebral ischemia-reperfusion injury

    Directory of Open Access Journals (Sweden)

    Hai-jun Gao

    2015-01-01

    Full Text Available Ligustrazine (2,3,5,6-tetramethylpyrazine is a major active ingredient of the Szechwan lovage rhizome and is extensively used in treatment of ischemic cerebrovascular disease. The mechanism of action of ligustrazine use against ischemic cerebrovascular diseases remains unclear at present. This study summarizes its protective effect, the optimum time window of administration, and the most effective mode of administration for clinical treatment of cerebral ischemia/reperfusion injury. We examine the effects of ligustrazine on suppressing excitatory amino acid release, promoting migration, differentiation and proliferation of endogenous neural stem cells. We also looked at its effects on angiogenesis and how it inhibits thrombosis, the inflammatory response, and apoptosis after cerebral ischemia. We consider that ligustrazine gives noticeable protection from cerebral ischemia/reperfusion injury. The time window of ligustrazine administration is limited. The protective effect and time window of a series of derivative monomers of ligustrazine such as 2-[(1,1-dimethylethyloxidoimino]methyl]-3,5,6-trimethylpyrazine, CXC137 and CXC195 after cerebral ischemia were better than ligustrazine.

  17. Adjuvant activity of peptidoglycan monomer and its metabolic products.

    Science.gov (United States)

    Halassy, Beata; Krstanović, Marina; Frkanec, Ruza; Tomasić, Jelka

    2003-02-14

    Peptidoglycan monomer (PGM) is a natural compound of bacterial origin. It is a non-toxic, non-pyrogenic, water-soluble immunostimulator potentiating humoral immune response to ovalbumin (OVA) in mice. It is fast degraded and its metabolic products-the pentapeptide (PP) and the disaccharide (DS)-are excreted from the mammalian organism upon parenteral administration. The present study investigates: (a). whether PGM could influence the long-living memory generation; (b). whether metabolic products retain adjuvant properties of the parent compound and contribute to its adjuvanticity. We report now that mice immunised twice with OVA+PGM had significantly higher anti-OVA IgG levels upon challenge with antigen alone 6 months later in comparison to control group immunised with OVA only. PP and DS were prepared enzymatically in vitro as apyrogenic and chemically pure compounds. When mice were immunised with OVA plus PP and DS, respectively, the level of anti-OVA IgGs in sera was not higher than in mice immunised with OVA alone, while PGM raised the level of specific antibodies. Results implicate that the adjuvant active molecule, capable of enhancing long-living memory generation, is PGM itself, and none of its metabolic products.

  18. Use of Monomer Fraction Data in the Parametrization of Association Theories

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios; Tsivintzelis, Ioannis; von Solms, Nicolas

    2010-01-01

    the monomer fraction of hydrogen bonding compounds and their mixtures. Monomer fraction data are obtained from spectroscopic measurements and they are available for a few compounds such as pure water and alcohols as well as for some alcohol–alkane and similar mixtures. These data are useful...... “improved” model parameters can be obtained if monomer fraction data are included in the parameter estimation together with vapor pressures and liquid densities. The expression “improved” implies parameters which can represent several pure compound properties as well as monomer fraction data for pure......, liquid densities and monomer fractions of water and alcohols. The 4C scheme is the best choice for water, while for methanol there is small difference between the 2B and 3B association schemes....

  19. Polyfunctional monomers as additives for enhancing the radiation copolymerization of styrene with polyethylene, polypropylene, and PVC

    International Nuclear Information System (INIS)

    Ang, C.H.; Garnett, J.L.; Levot, R.; Long, M.A.

    1982-01-01

    Additives which can increase the yield in the radiation grafting of monomers to polymers are useful. The use of polyfunctional monomers as additives (approx. = 1% v/v) are shown to enhance significantly the copolymerization yields of styrene in methanol to films of polyethylene and polypropylene under certain radiation conditions. The results obtained when the polyolefins are replaced by PVC as backbone polymer in these accelerated grafting reactions are reported. Divinylbenzene (DVB) and trimethylolpropane triacrylate (TMPTA) were used as representative polyfunctional monomers for the enhancement effect. When polypropylene was used as backbone polymer, the inclusion of DVB significantly enhanced the radiation grafting of styrene in methanol at all monomer concentrations studied above 35%. At certain monomer concentrations (50% , 60%), the yield of graft copolymer was almost doubled by the addition of DVB. 3 tables. (DP)

  20. Effect of molecular structure and thermal treatment on photooptical properties of photochromic azobenzene-containing polymers films

    Czech Academy of Sciences Publication Activity Database

    Bobrovsky, A.; Shibaev, V.; Bubnov, Alexej; Hamplová, Věra; Kašpar, Miroslav; Pociecha, D.; Glogarová, Milada

    2011-01-01

    Roč. 212, č. 4 (2011), s. 342-352 ISSN 1022-1352 R&D Projects: GA AV ČR IAA100100911; GA AV ČR(CZ) GA202/09/0047; GA MŠk(CZ) OC10006 Grant - others:Federal Agency for Science and Innovation , Russian Federation(RU) RFASI No 02.740.11.5166 Institutional research plan: CEZ:AV0Z10100520 Keywords : calorimetry * liquid-crystalline polymers (LCP) * monomers phase behavior * polysiloxanes Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.361, year: 2011 http://onlinelibrary.wiley.com/doi/10.1002/macp.201000534/pdf

  1. Investigation on physical behavior of styrene wood-polymer in different concentrations of monomer

    Directory of Open Access Journals (Sweden)

    maryam ghorbani

    2016-09-01

    Full Text Available This research was conducted to study the effect of different concentrations of styrene lumen monomer on the physical properties of beech wood. Physical test samples were prepared according to ASTM-D1037 standard and treated with vacuum-pressure method at five concentration levels; 0, 40, 60, 80 and 100 percent of soluble monomer. For polymerization, treated samples were heated in oven for two 24-hour period at 90 and 103ºC respectively. Monomer and polymer absorption, density variation, water absorption, swelling and anti-swelling efficiency (ASE were determined. According to the results, Monomer and polymer absorption were increment by monomer concentration increase, and they were reported 38.2% and 26% in highest level. With polymer absorption enhancement, density of wood increased from 0/63g/cm³ in control to 0/91g/cm³ in the highest monomer concentration level that reduces pores in wood-polymer structure. Absorbed polymer enhancement decreased hydrophilicity and dimensional changes of treated samples, so that water absorption and swelling volume of the samples saturated with 100% concentration of monomer were decreased 64% and 45.3% after the longest immersion time. Highest Anti-swelling efficiency of Styrene-saturated samples was determined 56.15% in the maximum concentration level of treatment.

  2. Solubility of mixed monomers of tetrafluoroethylene and propylene in water and latex

    International Nuclear Information System (INIS)

    Watanabe, Hiromasa; Okamoto, Jiro

    1978-03-01

    For kinetical analysis of the emulsion copolymerization of tetrafluoroethylene with propylene and selection of the optimum reaction conditions, the monomer concentrations and composition of the polymer particle were measured and the relations with reaction conditions were determined. Solubilities of tetrafluoroethylene and propylene in water increase with pressure. solubility of propylene is larger than that of tetrafluoroethylene. Solubility of the mixed monomers in water and latex increases with pressure and propylene concentration and decreases with temperature. Propylene concentration in the dissolved monomers is dependent on its concentration in the gas phase and independent of pressure and temperature. The monomer concentrations and the composition were estimated from measurements. Under propylene concentration in the gas phase of 0 to 40 wt % at 30 Kg/cm 2 G and 40 0 C, the monomer concentration and propylene fraction of the polymer particle are 17 -- 27% and 0 -- 62% respectively. The amount of propylene in the particle increases with its fraction in the gas phase, but the amount of tetrafluoroethylene is independent of its fraction in the gas phase. Monomer composition of the polymer particle is dependent on monomer composition of the gas phase and independent of temperature and pressure. The concentration in the polymer particle is 17% at propylene concentration 10 mole % in the gas phase. (auth.)

  3. Vogel-Fulcher dependence of relaxation rates in a nematic monomer and elastomer

    Science.gov (United States)

    Shenoy, D.; Filippov, S.; Aliev, F.; Keller, P.; Thomsen, D.; Ratna, B.

    2000-12-01

    Dielectric relaxation spectroscopy is used to study the relaxation processes in a nematic monomer and the corresponding cross-linked polymer nematic liquid crystal (elastomer). In the frequency window 10 mHz to 2 GHz the monomer liquid crystal shows a single relaxation whereas the polymer exhibits three relaxation processes, two of which are quantitatively analyzed. The temperature dependence of relaxation times in both the monomer and polymer follows a Vogel-Fulcher behavior. The relaxation processes are identified with specific molecular motions and activation energies are calculated in a linear approximation for comparison with literature data.

  4. Synthesis and characterization of novel organotin carboxylate maleimide monomers and copolymers

    Directory of Open Access Journals (Sweden)

    2009-06-01

    Full Text Available Two novel tributyltin carboxylate maleimide monomers, tributyltin(maleimidoacetate and tributyltin(4-maleimidobenzoate, were synthesized by condensation reaction of maleimidoacetic acid or 4-maleimidobenzoic acid with bis(tributyltin oxide. Copolymerization of these monomers with styrene was carried in dioxane at 70°C using asobisisobutyronitrile as free radical initiator. The structures of monomers and copolymers were confirmed by FT-IR (Fourier Transform Infrared, 1H and 13C NMR (nuclear magnetic resonance spectroscopy and elemental analysis. The copolymers were characterized by solubility and thermal analysis.

  5. Radiation curing of mixtures of diallylphthalate prepolymer and vinyl monomer, 9

    International Nuclear Information System (INIS)

    Gotoda, Masao; Kitada, Yoshinori.

    1975-01-01

    Radiation curing, mainly by electron beams was studied with mixtures of low molecular weight diallylphthalate prepolymer (DAPsub(p).L) and vinyl monomers with special reference to their workability. Among the vinyl monomers, acrylonitrile gave a solution of low viscosity and methyl acrylate gave a solution of low dose curing. Radiation curing of DAPsub(p).L/vinyl monomer mixtures impregnated in wood was also tried. To obtain uniform wood-polymer composites, γ-irradiation after impregnation at 10 kg/cm 2 was found to be required for thick plate (110 mm), while electron beam irradiation after impregnation at normal pressure was sufficient for thin plate. (author)

  6. Effect of monomer composition on the properties of high temperature polymer concretes

    Energy Technology Data Exchange (ETDEWEB)

    Zeldin, A.; Kukacka, L.E.; Carciello, N.

    1980-01-01

    The effects of organic monomer composition on the thermomechanical properties of polymer concrete (PC) containing sand-cement mixtures as an agregate filler were investigated. The effects of various monomer mixtures on compressive strength and hydrolytic stability are discussed. Composites were fabricated in the same way as ordinary concrete, with monomer solutions of various compositions and concentrations used to bind the sand-cement mixture. The compressive strengths of th composites before and after exposure to air and to brine solutions at 240/sup 0/C are discussed.

  7. Self-assembly of actin monomers into long filaments: Brownian Dynamics simulations

    DEFF Research Database (Denmark)

    Shillcock, Julian C.

    2009-01-01

    Brownian dynamics simulations are used to study the dynamical process of self-assembly of actin monomers into long filaments containing up to 1000 actin protomers. In order to overcome the large separation of time scales between the diffusive motion of the freemonomers and the relatively slow....../detachment events. When a single filament is allowed to grow in a bath of constant concentration of free ADP-actin monomers, its growth rate increases linearly with the free monomer concentration in quantitative agreement with in vitro experiments. Theresults also show that the waiting time is governed by...

  8. Dynamic conformations of nucleophosmin (NPM1 at a key monomer-monomer interface affect oligomer stability and interactions with granzyme B.

    Directory of Open Access Journals (Sweden)

    Wei D Duan-Porter

    Full Text Available Nucleophosmin (NPM1 is an abundant, nucleolar tumor antigen with important roles in cell proliferation and putative contributions to oncogenesis. Wild-type NPM1 forms pentameric oligomers through interactions at the amino-terminal core domain. A truncated form of NPM1 found in some hepatocellular carcinoma tissue formed an unusually stable oligomer and showed increased susceptibility to cleavage by granzyme B. Initiation of translation at the seventh methionine generated a protein (M7-NPM that shared all these properties. We used deuterium exchange mass spectrometry (DXMS to perform a detailed structural analysis of wild-type NPM1 and M7-NPM, and found dynamic conformational shifts or local "unfolding" at a specific monomer-monomer interface which included the β-hairpin "latch." We tested the importance of interactions at the β-hairpin "latch" by replacing a conserved tyrosine in the middle of the β-hairpin loop with glutamic acid, generating Y67E-NPM. Y67E-NPM did not form stable oligomers and further, prevented wild-type NPM1 oligomerization in a dominant-negative fashion, supporting the critical role of the β-hairpin "latch" in monomer-monomer interactions. Also, we show preferential cleavage by granzyme B at one of two available aspartates (either D161 or D122 in M7-NPM and Y67E-NPM, whereas wild-type NPM1 was cleaved at both sites. Thus, we observed a correlation between the propensity to form oligomers and granzyme B cleavage site selection in nucleophosmin proteins, suggesting that a small change at an important monomer-monomer interface can affect conformational shifts and impact protein-protein interactions.

  9. Guidelines To Select the N-Heterocyclic Carbene for the Organopolymerization of Monomers with a Polar Group

    KAUST Repository

    Falivene, Laura; Cavallo, Luigi

    2017-01-01

    be tuned by the hindrance of the NHC and the nature of the monomer. In addition to rationalize existing systems, the 45 NHC/monomer combinations we examined can be used as a guideline to predict the behavior of a new NHC/monomer combination.

  10. A approximate non-isothermal method to study kinetic processes controlled by a distribution of rate constants: the case of a photochromic azobenzene derivative dissolved in a polymer matrix

    Czech Academy of Sciences Publication Activity Database

    Janus, K.; Koshets, I. A.; Sworakowski, J.; Nešpůrek, Stanislav

    2002-01-01

    Roč. 12, č. 6 (2002), s. 1657-1663 ISSN 0959-9428 R&D Projects: GA AV ČR IAA1050901; GA ČR GA202/01/0518 Institutional research plan: CEZ:AV0Z4050913 Keywords : photochromism * bleaching kinetics * azobenzene Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 2.683, year: 2002

  11. Study on grafting of different types of acrylic monomers onto natural rubber by γ-rays

    International Nuclear Information System (INIS)

    Dafader, N.C.; Haque, M.E.; Akhtar, F.; Ahmad, M.U.

    2006-01-01

    A comparative study of various acrylic monomers for grafting onto natural rubber was done. The stability of natural rubber latex (NRL) against coagulum with monomer, mechanical properties of grafted rubbers and percent of grafting were investigated. The NRL with monomers, methylacrylate (MA), ethylacrylate (EA) and n-butylacrylate (n-BA), is unstable but it is stable with methyl methacrylate (MMA), n-butyl methacrylate (BMA) and cyclohexyl methacrylate (CHMA). The mechanical properties and degree of grafting attained a maximum at a total radiation dose of 4 kGy. The values of tensile properties of MMA and CHMA grafted rubbers are almost similar, and higher than those of BMA grafted rubbers. On the other hand, the degree of grafting for CHMA is higher than those of MMA and BMA grafted rubbers. The infrared (IR) spectra of monomer grafted natural rubber were also studied

  12. Determination of unreacted monomers in restorative dental resins based on dimethacrylate by NMR hydrogen

    International Nuclear Information System (INIS)

    Correa, Ivo Carlos; Miranda Junior, Walter G.; Tavares, Maria Ines B.

    2001-01-01

    The presence of unreacted monomers after photo-activation of dental composites causes mechanical and biological properties to decrease and could be detected by NMR analysis. The aim of this study was to evaluate the percentage of leachable monomers of light-cured composites under the effect of variations of exposure time of photo activation by nuclear magnetic resonance of hydrogen in solution (NMR 1 H). The composite resins tested Z250 and Fill Magic obtained similar values of unreacted monomers (%) at photo curing time suggested by the manufacturer and values were also lower than Durafill and A110 concentrations. From the NMR results, one day extractable time was efficient to quantify the amount of residual monomers in the dental composites tested, unless for Durafill composite. (author)

  13. Chimeric polymers formed from a monomer capable of free radical, oxidative and electrochemical polymerisation.

    Science.gov (United States)

    Lakshmi, Dhana; Whitcombe, Michael J; Davis, Frank; Chianella, Iva; Piletska, Elena V; Guerreiro, Antonio; Subrahmanyam, Sreenath; Brito, Paula S; Fowler, Steven A; Piletsky, Sergey A

    2009-05-21

    A new monomer, which incorporates both aniline and methacrylamide functional groups, was shown to possess orthogonal polymerisation behaviour to produce conjugated polyaniline suitable for a wide range of applications.

  14. Radical copolymerization in homogenous medium and emulsion system monomers acrylonitrile/styrene

    Directory of Open Access Journals (Sweden)

    Boussehel H.

    2013-09-01

    Full Text Available This study examines the radical copolymerization in homogeneous and emulsion of the monomer system acrylonitrile/styrene. These copolymers are of great interest to the plastics industry, because they combine the good mechanical properties and implementation provided by the styrene units in the very high solvent resistance and extreme gas impermeability provided by the acrylonitrile units. The properties of a copolymer are directly related to its composition and distribution of monomer units in its macromolecular chains. Based on the reports of the couple reactivity's of monomers (AN/S found in the literature, the objective of the work is to provide theoretical simulation (by analytical and numerical integration of the equation of copolymerization: The kinetics of the reaction copolymerization of AN/S in a homogeneous medium and emulsion (drift composition, azeotropic and the microstructure (distribution of monomer sequences and the glass transition property of the macromolecular chains instant formed throughout the copolymerization reaction.

  15. A comment on water’s structure using monomer fraction data and theories

    DEFF Research Database (Denmark)

    Liang, Xiaodong; Maribo-Mogensen, Bjørn; Tsivintzelis, Ioannis

    2016-01-01

    Monomer fraction data for water (and other compounds) can provide useful information about their structure and can be used in “advanced” equations of state, which account explicitly for association phenomena. Recent findings about the performance of association theories in representing the monomer...... fraction of water are reviewed. Three such theories are considered and all of them perform qualitatively similar. They can all represent phase equilibria for water solutions qualitatively well but with parameters which are not in good agreement with Luck’s famous monomer fraction data. While this could set...... the theoretical basis of these theories in doubt, we also show in this work that the findings with these association models are in agreement with a recently presented theory which links monomer fraction to dielectric constants. This new theory, like the three thermodynamic models, predicts more hydrogen bonding...

  16. Vinyl Monomers Double as UV Stabilizers: 179th ACS Meeting Houston.

    Science.gov (United States)

    Chemical and Engineering News, 1980

    1980-01-01

    Synthesis and polymerization of vinyl monomers that double as stabilizers against degradation of plastics by ultraviolet light has been accomplished. Potential applications include protection of photovoltaic cells in solar power plants. (Author/RE)

  17. Triptycene-based ladder monomers and polymers, methods of making each, and methods of use

    KAUST Repository

    Pinnau, Ingo

    2015-02-05

    Embodiments of the present disclosure provide for a triptycene-based A-B monomer, a method of making a triptycene-based A-B monomer, a triptycene-based ladder polymer, a method of making a triptycene-based ladder polymers, a method of using triptycene-based ladder polymers, a structure incorporating triptycene-based ladder polymers, a method of gas separation, and the like.

  18. The mutual diffusion coefficient for (meth)acrylate monomers as determined with a nuclear microprobe

    International Nuclear Information System (INIS)

    Leewis, Christian M.; Mutsaers, Peter H.A.; Jong, Arthur M. de; Ijzendoorn, Leo J. van; Voigt, Martien J.A. de; Ren, Min Q.; Watt, Frank; Broer, Dirk J.

    2004-01-01

    The value of the mutual diffusion coefficient D V of two acrylic monomers is determined with nuclear microprobe measurements on a set of polymer films. These films have been prepared by allowing the monomers to diffuse into each other for a certain time and subsequently applying fast ultraviolet photo-polymerization, which freezes the concentration profile. The monomer diffusion profiles are studied with a scanning 2.1 MeV proton microprobe. Each monomer contains a marker element, e.g., Cl and Si, which are easily detected with proton induced x-ray emission. From the diffusion profiles, it is possible to determine the mutual diffusion coefficient. The mutual diffusion coefficient is dependent of concentration, which is concluded from the asymmetry in the Cl- and Si-profiles. A linear dependence of the mutual diffusion coefficient on the composition is used as a first order approximation. The best fits are obtained for a value of b=(0.38±0.15), which is the ratio of the diffusion coefficient of 1,3-bis(3-methacryloxypropyl)-1, 1,3,3-tetramethyldisiloxane in pure 2-chloroethyl acrylate and the diffusion coefficient of 2-chloroethyl acrylate in pure 1,3-bis(3-methacryloxypropyl)-1,1,3,3-tetramethyldisiloxane. Under the assumption of a linear dependence of the mutual diffusion coefficient D V on monomer composition, it follows that D V =(2.9±0.6)·10 -10 m 2 /s at a 1:1 monomer ratio. With Flory-Huggins expressions for the monomer chemical potentials, one can derive approximate values for the individual monomer diffusion coefficients

  19. Radiation Induced Crosslinking of Polyethylene in the Presence of Bifunctional Vinyl Monomers

    DEFF Research Database (Denmark)

    Joshi, M. S.; Singer, Klaus Albert Julius; Silverman, J.

    1977-01-01

    Several reports have been published showing that the radiation induced grafting of bifunctional vinyl monomers to low density polyethylene results in a product with an unusually high density of crosslinks. The same grafting reactions are shown to reduce the incipient gel dose by more than a factor...... of fifty. This paper is concerned with the apparent crosslinking produced by the radiation grafting of two monomers to polyethylene: acrylic acid and acrylonitrile....

  20. Effect of food simulating liquids on release of monomers from two dental resin composites

    Directory of Open Access Journals (Sweden)

    Ghavam M

    2010-06-01

    Full Text Available "nBackground and Aims: The elution of residual monomers from cured dental composites to oral cavity has a harmful effect on human health and can affect their clinical durability. The purpose of this study was to evaluate the amount of eluted monomers (Bis-GMA, TEGDMA, UDMA from two types of composites (Gradia and P60 after exposure to food simulating liquids such as ethanol (25, 50, 75 % and heptane 50 % for 24 hours and 7 days. "nMaterials and Methods: Forty specimens of each composite were prepared. Equal numbers of each composite were immersed in tubes containing 2cc volumes of 25, 50, 75 % ethanole and 50 % heptane. The amount of eluted monomers in standard condition such as Bis-GMA, TEGDMA and UDMA was measured by GC/MS (Gas Chromatography/Mass Spectroscopy and results were statistically analysed by three way and one way ANOVA. P<0.05 was considered as the level of significancy. "nResults: The results showed that Gradia released more TEGDMA than P60. In assessing the effect of environment, the result showed that ethanol caused releasing monomers more than heptane and the concentration rate of 75 % ethanole resulted in most releasing of monomers. In assessing the effect of time, the observation showed that more monomers were released 7 days compared to 24 hours. Bis-GMA and UDMA were not detected in any solutions in these conditions. "nConclusion: Ethanole caused more release of monomers than heptane and 75 % ethanole released the most amount of monomers. Gradia released more amount of TEGDMA than P60.

  1. Inhibition of odontogenic differentiation of human dental pulp cells by dental resin monomers

    OpenAIRE

    Kwon, Ji Hyun; Park, Hee Chul; Zhu, Tingting; Yang, Hyeong-Cheol

    2015-01-01

    Background Dental resin monomers that are leached from the resin matrix due to incomplete polymerization can affect the viability and various functions of oral tissues and cells. In this study, the effects of triethylene glycol dimethacrylate (TEGDMA) and 2-hydroxyethyl methacrylate (HEMA) on odontogenic differentiation of human dental pulp cells (HDPCs) were examined. To mimic clinical situations, dental pulp cells were treated with resin monomers for 24?h prior to the analysis of alkaline p...

  2. Residual monomer content determination in some acrylic denture base materials and possibilities of its reduction

    Directory of Open Access Journals (Sweden)

    Kostić Milena

    2009-01-01

    Full Text Available Background/Aim. Polymethyl methacrylate is used for producing a denture basis. It is a material made by the polymerization process of methyl methacrylate. Despite of the polymerization type, there is a certain amount of free methyl methacrylate (residual monomer incorporated in the denture, which can cause irritation of the oral mucosa. The aim of this study was to determine the amount of residual monomer in four different denture base acrylic resins by liquid chromatography and the possibility of its reduction. Methods. After the polymerization, a postpolymerization treatment was performed in three different ways: in boiling water for thirty minutes, with 500 W microwaves for three minutes and in steam bath at 22º C for one to thirty days. Results. The obtained results showed that the amount of residual monomer is significantly higher in cold polymerizing acrylates (9.1-11%. The amount of residual monomer after hot polymerization was in the tolerance range (0.59- 0.86%. Conclusion. The obtained results denote a low content of residual monomer in the samples which have undergone postpolymerization treatment. A lower percent of residual monomer is established in samples undergone a hot polymerization.

  3. Kinetics of the monomer-dimer reaction of yeast hexokinase PI.

    Science.gov (United States)

    Hoggett, J G; Kellett, G L

    1992-10-15

    Kinetic studies of the glucose-dependent monomer-dimer reaction of yeast hexokinase PI at pH 8.0 in the presence of 0.1 M-KCl have been carried out using the fluorescence temperature-jump technique. A slow-relaxation effect was observed which was attributed from its dependence on enzyme concentration to the monomer-dimer reaction; the reciprocal relaxation times tau-1 varied from 3 s-1 at low concentrations of glucose to 42 s-1 at saturating concentrations. Rate constants for association (kass.) and dissociation (kdiss.) were determined as a function of glucose concentration using values of the equilibrium association constant of the monomer-dimer reaction derived from sedimentation ultracentrifugation studies under similar conditions, and also from the dependence of tau-2 on enzyme concentration. kass. was almost independent of glucose concentration and its value (2 x 10(5) M-1.s-1) was close to that expected for a diffusion-controlled process. The influence of glucose on the monomer-dimer reaction is entirely due to effects on kdiss., which increases from 0.21 s-1 in the absence of glucose to 25 s-1 at saturating concentrations. The monomer and dimer forms of hexokinase have different affinities and Km values for glucose, and the results reported here imply that there may be a significant lag in the response of the monomer-dimer reaction to changes in glucose concentrations in vivo with consequent hysteretic effects on the hexokinase activity.

  4. Synthesis and evaluation of novel siloxane-methacrylate monomers used as dentin adhesives.

    Science.gov (United States)

    Ge, Xueping; Ye, Qiang; Song, Linyong; Misra, Anil; Spencer, Paulette

    2014-09-01

    The objectives of this study were to synthesize two new siloxane-methacrylate (SM) monomers for application in dentin adhesives and to investigate the influence of different functionality of the siloxane-containing monomers on the adhesive photopolymerization, water sorption, and mechanical properties. Two siloxane-methacrylate monomers (SM1 and SM2) with four and eight methacrylate groups were synthesized. Dentin adhesives containing BisGMA, HEMA and the siloxane-methacrylate monomers were photo-polymerized. The experimental adhesives were compared with the control adhesive (HEMA/BisGMA, 45/55, w/w) and characterized with regard to degree of conversion (DC), water miscibility of the liquid resin, water sorption and dynamic mechanical analysis (DMA). The experimental adhesives exhibited improved water miscibility as compared to the control. When cured in the presence of 12 wt% water to simulate the wet environment of the mouth, the SM-containing adhesives showed DC comparable to the control. The experimental adhesives showed higher rubbery modulus than the control under dry conditions. Under wet conditions, the mechanical properties of the formulations containing SM monomer with increased functionality were comparable with the control, even with more water sorption. The concentration and functionality of the newly synthesized siloxane-methacrylate monomers affected the water miscibility, water sorption and mechanical properties of the adhesives. The experimental adhesives show improved water compatibility compared with the control. The mechanical properties were enhanced with an increase of the functionality of the siloxane-containing monomers. The results provide critical structure/property relationships and important information for future development of durable, versatile siloxane-containing dentin adhesives. Published by Elsevier Ltd.

  5. Thermodynamically stable amyloid-β monomers have much lower membrane affinity than the small oligomers

    Directory of Open Access Journals (Sweden)

    Bidyut eSarkar

    2013-04-01

    Full Text Available Amyloid beta (Aβ is an extracellular 39-43 residue long peptide present in the mammalian cerebrospinal fluid, whose aggregation is associated with Alzheimer’s disease. Small oligomers of Aβ are currently thought to be the key to toxicity. However, it is not clear why the monomers of Aβ are non-toxic, and at what stage of aggregation toxicity emerges. Interactions of Aβ with cell membranes is thought to be the initiator of toxicity, but membrane-binding studies with different preparations of monomers and oligomers have not settled this issue. We have earlier found that thermodynamically stable Aβ monomers emerge spontaneously from oligomeric mixtures upon long term incubation in physiological solutions (Nag et al, JBC, 2011. Here we show that the membrane-affinity of these stable Aβ monomers is much lower than that of a mixture of small oligomers (containing dimers to decamers, providing a clue to the emergence of toxicity. Fluorescently labeled Aβ40 monomers show negligible binding to cell membranes of a neuronal cell line (RN46A at physiological concentrations (250 nM, while oligomers at the same concentrations show strong binding within 30 minutes of incubation. The increased affinity most likely does not require any specific neuronal receptor, since this difference in membrane-affinity was also observed in a somatic cell-line (HEK 293T. Similar results are also obtained for Aβ42 monomers and oligomers. Minimal amount of cell death is observed at these concentrations even after 36 hours of incubation. It is likely that membrane binding precedes subsequent slower toxic events induced by Aβ. Our results a provide an explanation for the non-toxic nature of Aβ monomers, b suggest that Aβ toxicity emerges at the initial oligomeric phase, and c provide a quick assay for monitoring the benign-to-toxic transformation of Aβ.

  6. Anisotropy of the monomer random walk in a polymer melt: local-order and connectivity effects

    International Nuclear Information System (INIS)

    Bernini, S; Leporini, D

    2016-01-01

    The random walk of a bonded monomer in a polymer melt is anisotropic due to local order and bond connectivity. We investigate both effects by molecular-dynamics simulations on melts of fully-flexible linear chains ranging from dimers (M  =  2) up to entangled polymers (M  =  200). The corresponding atomic liquid is also considered a reference system. To disentangle the influence of the local geometry and the bond arrangements, and to reveal their interplay, we define suitable measures of the anisotropy emphasising either the former or the latter aspect. Connectivity anisotropy, as measured by the correlation between the initial bond orientation and the direction of the subsequent monomer displacement, shows a slight enhancement due to the local order at times shorter than the structural relaxation time. At intermediate times—when the monomer displacement is comparable to the bond length—a pronounced peak and then decays slowly as t −1/2 , becoming negligible when the displacement is as large as about five bond lengths, i.e. about four monomer diameters or three Kuhn lengths. Local-geometry anisotropy, as measured by the correlation between the initial orientation of a characteristic axis of the Voronoi cell and the subsequent monomer dynamics, is affected at shorter times than the structural relaxation time by the cage shape with antagonistic disturbance by the connectivity. Differently, at longer times, the connectivity favours the persistence of the local-geometry anisotropy, which vanishes when the monomer displacement exceeds the bond length. Our results strongly suggest that the sole consideration of the local order is not enough to understand the microscopic origin of the rattling amplitude of the trapped monomer in the cage of the neighbours. (paper)

  7. Net expansion of dried demineralized dentin matrix produced by monomer/alcohol saturation and solvent evaporation.

    Science.gov (United States)

    Agee, Kelli A; Becker, Thomas D; Joyce, Anthony P; Rueggeberg, Frederick A; Borke, James L; Waller, Jennifer L; Tay, Franklin R; Pashley, David H

    2006-11-01

    The purpose of this work was to determine if nonaqueous methacrylate monomer/alcohol mixtures could expand dried collapsed demineralized dentin matrix. Thin disks (ca. 200 microm) of human dentin were demineralized and placed in wells beneath contact probes of linear variable differential transformers. The probes were placed on water-saturated expanded matrices to record the shrinkage associated with drying. Monomer mixtures containing hydroxyethyl methacrylate, 2,2-bis[4-(2-hydroxy-3 methacryloyloxy)propoxyphenyl] propane, or triethyleneglycol dimethacrylate were mixed with methanol or ethanol at alcohol/monomer mass fraction % of 90/10, 70/30, 50/50, or 30/70. They were randomly applied to the dried matrices to determine the rate and magnitude of expansion; then shrinkage was recorded during evaporation of the alcohols. The results indicated that matrix expansion was positively correlated with the Hoy's solubility parameters for hydrogen bonding forces (delta(h)) of the monomer/solvent mixtures (p methanol-containing than with ethanol-containing monomer mixtures. For the test solutions, triethyleneglycol dimethacrylate-containing mixtures produced the slowest rate of matrix expansion and hydroxyethyl methacrylate-containing mixtures the most rapid expansion. When the solvents were evaporated, the matrix shrank in proportion to the solvent content and the delta(h) of the monomer-solvent mixtures. The results indicate that expansion of dried, collapsed dentin matrices requires that the delta(h) of the mixtures be larger than 17 (J/cm(3))(1/2). The greater the delta(h) of the monomer solutions, the greater the rate and extent of expansion.

  8. Synthesis of phosphate monomers and bonding to dentin: esterification methods and use of phosphorus pentoxide.

    Science.gov (United States)

    Ogliari, Fabrício Aulo; da Silva, Eduardo de Oliveira; Lima, Giana da Silveira; Madruga, Francine Cardozo; Henn, Sandrina; Bueno, Márcia; Ceschi, Marco Antônio; Petzhold, Cesar Liberato; Piva, Evandro

    2008-03-01

    The aim of this study was to synthesize an acidic monomer using an alternative synthetic pathway and to evaluate the influence of the acidic monomer concentration on the microtensile bond strength to dentin. The intermediary 5-hydroxypentyl methacrylate (HPMA) was synthesized through methacrylic acid esterification with 1,5-pentanediol, catalyzed by p-toluenesulfonic acid. To displace the reaction balance, the water generated by esterification was removed by three different methods: anhydrous sodium sulfate; molecular sieves or azeotropic distillation. In the next step, a phosphorus pentoxide (4.82 mmol) slurry was formed in cold acetone and 29 mmol of HPMA was slowly added by funnel addition. After the reaction ended, solvent was evaporated and the product was characterized by 1HNMR and FTIR. The phosphate monomer was introduced in a self-etch primer at concentrations of 0, 15, 30, 50, 70 and 100 wt%. Clearfil SE Bond was used as commercial reference. Microtensile bond strength to dentin was evaluated 24h after the bonding procedures, followed by fracture analysis (n=20). Data was submitted to ANOVA and Tukey's post hoc test. The highest yield was obtained (62%) when azeotropic distillation was used, while the reaction with molecular sieves was not feasible. The phosphoric moiety attachment to the monomer was successfully performed with a quantitative yield that reached around 100%. The acidic monomer concentration significantly affected the bond strength and the highest mean (55.1+/-12.8 MPa) was obtained when 50% of acidic monomer was used. The synthesis pathways described in the present study appear to be a viable alternative for developing phosphate monomers.

  9. Photoresponsive layer-by-layer ultrathin films prepared from a hyperbranched azobenzene-containing polymeric diazonium salt

    International Nuclear Information System (INIS)

    Li Xinyang; Fan Pengwei; Tuo Xinlin; He Yaning; Wang Xiaogong

    2009-01-01

    In this work, a hyperbranched diazonium salt (HB-DAS), prepared through azo-coupling reaction of an AB 2 monomer (N, N-bis[2-(4-aminobenzoyloxy)ethyl]aniline), was used to prepare self-assembled multilayers and ultrathin films. Multilayer films were fabricated by dipping substrates in HB-DAS and other polyelectrolyte solutions alternately in a layer-by-layer (LBL) manner. It was somewhat surprising to observe that HB-DAS forms multilayer films with either a polyanion (poly(styrenesulfonate sodium salt), PSS) or a polycation (poly(diallyldimethylammonium chloride), PDAC) through alternate deposition in the solutions. Ultrathin films were formed in a sequential growth manner by dipping the substrates in the HB-DAS solution, washing with deionized water and drying repeatedly. In all the processes, the absorbance and thickness of the thin films linearly increase as the number of the dipping cycle increases. HB-DAS/PSS multilayer possesses an obviously larger bilayer thickness and lower density compared with the other two counterparts. The drying step after each deposition is necessary for the HB-DAS ultrathin film growth through the repeated dip-coating of HB-DAS. The multilayer and ultrathin films prepared by the above methods all show high resistance to erosion by organic solvents. The multilayers and ultrathin films exhibit photoinduced dichroism upon the irradiation of a polarized Ar + laser beam

  10. Photoresponsive layer-by-layer ultrathin films prepared from a hyperbranched azobenzene-containing polymeric diazonium salt

    Energy Technology Data Exchange (ETDEWEB)

    Li Xinyang; Fan Pengwei; Tuo Xinlin; He Yaning [Department of Chemical Engineering, Laboratory for Advanced Materials, Tsinghua University, Beijing, 100084 (China); Wang Xiaogong [Department of Chemical Engineering, Laboratory for Advanced Materials, Tsinghua University, Beijing, 100084 (China)], E-mail: wxg-dce@mail.tsinghua.edu.cn

    2009-01-30

    In this work, a hyperbranched diazonium salt (HB-DAS), prepared through azo-coupling reaction of an AB{sub 2} monomer (N, N-bis[2-(4-aminobenzoyloxy)ethyl]aniline), was used to prepare self-assembled multilayers and ultrathin films. Multilayer films were fabricated by dipping substrates in HB-DAS and other polyelectrolyte solutions alternately in a layer-by-layer (LBL) manner. It was somewhat surprising to observe that HB-DAS forms multilayer films with either a polyanion (poly(styrenesulfonate sodium salt), PSS) or a polycation (poly(diallyldimethylammonium chloride), PDAC) through alternate deposition in the solutions. Ultrathin films were formed in a sequential growth manner by dipping the substrates in the HB-DAS solution, washing with deionized water and drying repeatedly. In all the processes, the absorbance and thickness of the thin films linearly increase as the number of the dipping cycle increases. HB-DAS/PSS multilayer possesses an obviously larger bilayer thickness and lower density compared with the other two counterparts. The drying step after each deposition is necessary for the HB-DAS ultrathin film growth through the repeated dip-coating of HB-DAS. The multilayer and ultrathin films prepared by the above methods all show high resistance to erosion by organic solvents. The multilayers and ultrathin films exhibit photoinduced dichroism upon the irradiation of a polarized Ar{sup +} laser beam.

  11. Photopolymerizable phosphate acrylates as comonomers in dental adhesives with or without triclosan monomer units

    International Nuclear Information System (INIS)

    Melinte, Violeta; Buruiana, Tinca; Aldea, Horia; Matiut, Simona; Silion, Mihaela; Buruiana, Emil C.

    2014-01-01

    Phosphate diacrylates (CO-DAP, TMP-DAP) based on castor oil or trimethylolpropane were synthesized and evaluated in dental adhesive formulations in comparison with 3-acryloyloxy-2-hydroxypropyl methacrylate phosphate (AMP-P). In an attempt to promote antibacterial activity, another photopolymerizable monomer (TCS-UMA) containing 5-chloro-2-(2,4-dichlorophenoxy)phenol moiety (triclosan) was prepared and incorporated in adhesive resins. Each of these monomers had a molecular structure confirmed by spectral methods. The photopolymerization rates for monomers (0.063–0.088 s −1 ) were lower than those determined in the monomer combinations (0.116–0.158 s −1 ) incorporating phosphate diacrylate (11 wt.%), BisGMA (33 wt.%), TEGDMA (10 wt.%), UDMA (10 wt.%) and HEMA (15 wt.%), the degree of conversion varying between 63.4 and 74.5%. The formed copolymers showed high values for water sorption (18.65–57.02 μg/mm 3 ) and water solubility (3.51–13.38 μg/mm 3 ), and the contact angle was dependent on the presence of CO-DAP (θ F1 : 66.67°), TMP-DAP (θ F2 : 55.05°) or AMP-P (θ F3 : 52.90°) in the photocrosslinked specimens compared to the sample without phosphate monomer (θ F4 : 82.14°). The scanning electron microscopy image of the dentin–resin composite interface after applying our F1 formulation (pH: 4.1) and its light-curing for 20 s supports the evidence of the formation of the hybrid layer with the tooth structure created by self-etching approach, with no gaps or cracks in the adhesive. A comparative analysis of the adhesion achieved with commercial adhesive systems (Single Bond Universal, C-Bond) rather indicates similarities than differences between them. The addition of triclosan methacrylate (1 wt.%) into the formulation inhibited the bacterial growth of the Streptococcus mutans and Escherichia coli in the direct contact area due to the covalently linked antibacterial monomer. - Highlights: • Synthesis of photopolymerizable phosphate acrylate

  12. Photopolymerizable phosphate acrylates as comonomers in dental adhesives with or without triclosan monomer units

    Energy Technology Data Exchange (ETDEWEB)

    Melinte, Violeta [Petru Poni Institute of Macromolecular Chemistry, 41 A Gr. Ghica Voda Alley, 700487 Iasi (Romania); Buruiana, Tinca, E-mail: tbur@icmpp.ro [Petru Poni Institute of Macromolecular Chemistry, 41 A Gr. Ghica Voda Alley, 700487 Iasi (Romania); Aldea, Horia [Gr. T. Popa University of Medicine and Pharmacy, Faculty of Dentistry, Iasi (Romania); Matiut, Simona [Praxis Medical Investigations, 33 Independence, 700102 Iasi (Romania); Silion, Mihaela; Buruiana, Emil C. [Petru Poni Institute of Macromolecular Chemistry, 41 A Gr. Ghica Voda Alley, 700487 Iasi (Romania)

    2014-01-01

    Phosphate diacrylates (CO-DAP, TMP-DAP) based on castor oil or trimethylolpropane were synthesized and evaluated in dental adhesive formulations in comparison with 3-acryloyloxy-2-hydroxypropyl methacrylate phosphate (AMP-P). In an attempt to promote antibacterial activity, another photopolymerizable monomer (TCS-UMA) containing 5-chloro-2-(2,4-dichlorophenoxy)phenol moiety (triclosan) was prepared and incorporated in adhesive resins. Each of these monomers had a molecular structure confirmed by spectral methods. The photopolymerization rates for monomers (0.063–0.088 s{sup −1}) were lower than those determined in the monomer combinations (0.116–0.158 s{sup −1}) incorporating phosphate diacrylate (11 wt.%), BisGMA (33 wt.%), TEGDMA (10 wt.%), UDMA (10 wt.%) and HEMA (15 wt.%), the degree of conversion varying between 63.4 and 74.5%. The formed copolymers showed high values for water sorption (18.65–57.02 μg/mm{sup 3}) and water solubility (3.51–13.38 μg/mm{sup 3}), and the contact angle was dependent on the presence of CO-DAP (θ{sub F1}: 66.67°), TMP-DAP (θ{sub F2}: 55.05°) or AMP-P (θ{sub F3}: 52.90°) in the photocrosslinked specimens compared to the sample without phosphate monomer (θ{sub F4}: 82.14°). The scanning electron microscopy image of the dentin–resin composite interface after applying our F1 formulation (pH: 4.1) and its light-curing for 20 s supports the evidence of the formation of the hybrid layer with the tooth structure created by self-etching approach, with no gaps or cracks in the adhesive. A comparative analysis of the adhesion achieved with commercial adhesive systems (Single Bond Universal, C-Bond) rather indicates similarities than differences between them. The addition of triclosan methacrylate (1 wt.%) into the formulation inhibited the bacterial growth of the Streptococcus mutans and Escherichia coli in the direct contact area due to the covalently linked antibacterial monomer. - Highlights: • Synthesis of

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-08-15

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

  14. Effect of solubility parameter of monomers on electron beam induced graft-polymerization onto polyethylene films

    International Nuclear Information System (INIS)

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

    1991-01-01

    Electron beam induced graft-polymerization by the mutual irradiation technique of monomers with different solubility parameters δ onto low density polyethylene films (LDPE) and high density polyethylene films (HDPE) were investigated at high dose rates (25 Mrad per second). Graft-polymerization mechanisms were discussed on the basis of grafting rates, surface tensions, atomic ratios of surface by XPS, and SEM images of the grafted films. Grafting rates decreased with increasing δ of monomers, and grafting rates onto LDPE were larger than those onto HDPE. Graft chain contents on surface, which were evaluated in terms of surface tensions and atomic ratios of the surface, increased with increasing δ of monomers, and graft chain contents on surface of HDPE were higher than those of LDPE. It is assumed that mutual solubility of PE and monomers, i.e., infiltration of monomers into PE during graft-polymerization influence grafting rates and graft sites in films. In case of high mutual solubility, grafting rates were large and graft sites spread from the surface into bulk. On the other hand, in case of low mutual solubility, grafting rates were small and graft sites localized on the surface of films. (author)

  15. Do CAD/CAM dentures really release less monomer than conventional dentures?

    Science.gov (United States)

    Steinmassl, Patricia-Anca; Wiedemair, Verena; Huck, Christian; Klaunzer, Florian; Steinmassl, Otto; Grunert, Ingrid; Dumfahrt, Herbert

    2017-06-01

    Computer-aided design (CAD)/computer-aided manufacturing (CAM) dentures are assumed to have more favourable material properties than conventionally fabricated dentures, among them a lower methacrylate monomer release. The aim of this study was to test this hypothesis. CAD/CAM dentures were generated from ten different master casts by using four different CAD/CAM systems. Conventional, heat-polymerised dentures served as control group. Denture weight and volume were measured; the density was calculated, and the denture surface area was assessed digitally. The monomer release after 7 days of water storage was measured by high-performance liquid chromatography. Whole You Nexteeth and Wieland Digital Dentures had significantly lower mean volume and weight than conventional dentures. Baltic Denture System and Whole You Nexteeth had a significantly increased density. Baltic Denture System had a significantly smaller surface area. None of the CAD/CAM dentures released significantly less monomer than the control group. All tested dentures released very low amounts of methacrylate monomer, but not significantly less than conventional dentures. A statistically significant difference might nevertheless exist in comparison to other, less recommendable denture base materials, such as the frequently used autopolymerising resins. CAD/CAM denture fabrication has numerous advantages. It enables the fabrication of dentures with lower resin volume and lower denture weight. Both could increase the patient comfort. Dentures with higher density might exhibit more favourable mechanical properties. The hypothesis that CAD/CAM dentures release less monomer than conventional dentures could, however, not be verified.

  16. Using monomer vibrational wavefunctions to compute numerically exact (12D) rovibrational levels of water dimer

    Science.gov (United States)

    Wang, Xiao-Gang; Carrington, Tucker

    2018-02-01

    We compute numerically exact rovibrational levels of water dimer, with 12 vibrational coordinates, on the accurate CCpol-8sf ab initio flexible monomer potential energy surface [C. Leforestier et al., J. Chem. Phys. 137, 014305 (2012)]. It does not have a sum-of-products or multimode form and therefore quadrature in some form must be used. To do the calculation, it is necessary to use an efficient basis set and to develop computational tools, for evaluating the matrix-vector products required to calculate the spectrum, that obviate the need to store the potential on a 12D quadrature grid. The basis functions we use are products of monomer vibrational wavefunctions and standard rigid-monomer basis functions (which involve products of three Wigner functions). Potential matrix-vector products are evaluated using the F matrix idea previously used to compute rovibrational levels of 5-atom and 6-atom molecules. When the coupling between inter- and intra-monomer coordinates is weak, this crude adiabatic type basis is efficient (only a few monomer vibrational wavefunctions are necessary), although the calculation of matrix elements is straightforward. It is much easier to use than an adiabatic basis. The product structure of the basis is compatible with the product structure of the kinetic energy operator and this facilitates computation of matrix-vector products. Compared with the results obtained using a [6 + 6]D adiabatic approach, we find good agreement for the inter-molecular levels and larger differences for the intra-molecular water bend levels.

  17. The binding of glucose to yeast hexokinase monomers is independent of ionic strength.

    Science.gov (United States)

    Mayes, E L; Hoggett, J G; Kellett, G L

    1982-05-01

    Hoggett & Kellett [Eur. J. Biochem. 66, 65-77 (1976)] have reported that the binding of glucose to the monomer of hexokinase PII isoenzyme is independent of ionic strength, in contrast to the subsequent claim of Feldman & Kramp [Biochemistry 17, 1541-1547 (1978)] that the binding is strongly dependent on ionic strength. Since measurements with native hexokinase P forms are complicated by the fact that the enzyme exists in a monomer-dimer association-dissociation equilibrium, we have now studied the binding of glucose to the proteolytically-modified S forms which are monomeric. At pH 8.5, the affinity of glucose for both SI and SII monomers is independent of salt concentration over the range of KCl concentrations 0-1.0 mol . dm-3 and is in good agreement with that of the corresponding P forms in both low and high salt. These observations confirm that the binding of glucose to hexokinase P monomers is independent of ionic strength and that the affinity of glucose for the hexokinase PII monomer is about an order of magnitude greater than that for the dimer.

  18. Growth of monodisperse mesoscopic metal-oxide colloids under constant monomer supply

    Science.gov (United States)

    Nozawa, Koh; Delville, Marie-Hélène; Ushiki, Hideharu; Panizza, Pascal; Delville, Jean-Pierre

    2005-07-01

    In closed systems, control over the size of monodisperse metal-oxide colloids is generally limited to submicrometric dimensions. To overcome this difficulty, we explore the formation and growth of silica particles under constant monomer supply. The monomer source is externally driven by the progressive addition into the system of one of the precursors. Monodisperse spherical particles are produced up to a mesoscopic size. We analyze their growth versus the monomer addition rate at different temperatures. Our results show that in the presence of a continuous monomer addition, growth is limited by diffusion over the investigated temporal window. Using the temperature variation of the growth rate, we prove that rescaling leads to a data reduction onto a single master curve. Contrary to the growth process, the final particle’s size reached after the end of the reagent supply strongly depends on the addition rate. The variation of the final particle size versus addition rate can be deduced from an analogy with crystal formation in jet precipitation. Within this framework, and using the temperature dependences of both the particle growth law and the final size, we determine the value of the molecular heat of dissolution associated to the silica solubility. These observations support the fact that classical theories of phase-ordering dynamics can be extended to the synthesis of inorganic particles. The emergence of a master behavior in the presence of continuous monomer addition also suggests the extension of these theories to open systems.

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

    Science.gov (United States)

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

    2018-03-20

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

  20. Design and Applications of Biodegradable Polyester Tissue Scaffolds Based on Endogenous Monomers Found in Human Metabolism

    Directory of Open Access Journals (Sweden)

    Devin G. Barrett

    2009-10-01

    Full Text Available Synthetic polyesters have deeply impacted various biomedical and engineering fields, such as tissue scaffolding and therapeutic delivery. Currently, many applications involving polyesters are being explored with polymers derived from monomers that are endogenous to the human metabolism. Examples of these monomers include glycerol, xylitol, sorbitol, and lactic, sebacic, citric, succinic, α-ketoglutaric, and fumaric acids. In terms of mechanical versatility, crystallinity, hydrophobicity, and biocompatibility, polyesters synthesized partially or completely from these monomers can display a wide range of properties. The flexibility in these macromolecular properties allows for materials to be tailored according to the needs of a particular application. Along with the presence of natural monomers that allows for a high probability of biocompatibility, there is also an added benefit that this class of polyesters is more environmentally friendly than many other materials used in biomedical engineering. While the selection of monomers may be limited by nature, these polymers have produced or have the potential to produce an enormous number of successes in vitro and in vivo.

  1. The influence of monomer concentration on the optical properties of electrochemically synthesized polypyrrole thin films

    International Nuclear Information System (INIS)

    Thombare, J. V.; Fulari, V. J.; Rath, M. C.; Han, S. H.

    2013-01-01

    Polypyrrole (PPy) thin films were deposited on stainless steel and ITO coated glass substrate at a constant deposition potential of 0.8 V versus saturated calomel electrode (SCE) by using the electrochemical polymerization method. The PPy thin films were deposited at room temperature at various monomer concentrations ranging from 0.1 M to 0.3 M pyrrole. The structural and optical properties of the polypyrrole thin films were investigated using an X-ray diffractometer (XRD), FTIR spectroscopy, scanning electron microscopy (SEM), and ultraviolet—visible (UV—vis) spectroscopy. The XRD results show that polypyrrole thin films have a semi crystalline structure. Higher monomer concentration results in a slight increase of crystallinity. The polypyrrole thin films deposited at higher monomer concentration exhibit high visible absorbance. The refractive indexes of the polypyrrole thin films are found to be in the range of 1 to 1.3 and vary with monomer concentration as well as wavelength. The extinction coefficient decreases slightly with monomer concentration. The electrochemically synthesized polypyrrole thin film shows optical band gap energy of 2.14 eV. (semiconductor materials)

  2. Controlled grafting of vinylic monomers on polyolefins: a robust mathematical modeling approach.

    Science.gov (United States)

    Saeb, Mohammad Reza; Rezaee, Babak; Shadman, Alireza; Formela, Krzysztof; Ahmadi, Zahed; Hemmati, Farkhondeh; Kermaniyan, Tayebeh Sadat; Mohammadi, Yousef

    2017-01-01

    Experimental and mathematical modeling analyses were used for controlling melt free-radical grafting of vinylic monomers on polyolefins and, thereby, reducing the disturbance of undesired cross-linking of polyolefins. Response surface, desirability function, and artificial intelligence methodologies were blended to modeling/optimization of grafting reaction in terms of vinylic monomer content, peroxide initiator concentration, and melt-processing time. An in-house code was developed based on artificial neural network that learns and mimics processing torque and grafting of glycidyl methacrylate (GMA) typical vinylic monomer on high-density polyethylene (HDPE). Application of response surface and desirability function enabled concurrent optimization of processing torque and GMA grafting on HDPE, through which we quantified for the first time competition between parallel reactions taking place during melt processing: (i) desirable grafting of GMA on HDPE; (ii) undesirable cross-linking of HDPE. The proposed robust mathematical modeling approach can precisely learn the behavior of grafting reaction of vinylic monomers on polyolefins and be placed into practice in finding exact operating condition needed for efficient grafting of reactive monomers on polyolefins.

  3. Radiation-initiated emulsion copolymerization of styrene and carboxylic acid monomers

    International Nuclear Information System (INIS)

    Egusa, S.; Makuuchi, K.

    1982-01-01

    The emulsion copolymerization of styrene and carboxylic acid monomers such as acrylic, methacrylic, and itaconic acids (AAc, MAAc, IAc) was studied by using 60 Co γ-rays as initiator and sodium dodecylsulfate as emulsifier. The polymerization behavior of these acid monomers was followed by simultaneous conductometric and potentiometric titrations for a latex sample taken in polymerization. The polymerization rate of these acid monomers increases in the following order of hydrophobicity: IAc < AAc < MAAc; this suggests that their polymerization sites are mainly the surface and/or subsurface regions of latex particles. The copolymerization rate of styrene and acid monomer increases with an increase in the acid monomer content for AAc and MAAc, whereas for IAc the rate decreases. The particle sizes determined by the stopped-flow method reveal that this variation of copolymerization rate cannot be explained by the number of growing particles and should be attributed to another factor; for instance, the transfer rate of styrene molecules from oil droplets to growing particles

  4. Inhibition of odontogenic differentiation of human dental pulp cells by dental resin monomers.

    Science.gov (United States)

    Kwon, Ji Hyun; Park, Hee Chul; Zhu, Tingting; Yang, Hyeong-Cheol

    2015-01-01

    Dental resin monomers that are leached from the resin matrix due to incomplete polymerization can affect the viability and various functions of oral tissues and cells. In this study, the effects of triethylene glycol dimethacrylate (TEGDMA) and 2-hydroxyethyl methacrylate (HEMA) on odontogenic differentiation of human dental pulp cells (HDPCs) were examined. To mimic clinical situations, dental pulp cells were treated with resin monomers for 24 h prior to the analysis of alkaline phosphatase (ALP) activity and mRNA expression of genes related to pulp cell differentiation. To elucidate the underlying signaling pathways, regulation of mitogen-activated protein (MAP) kinases by resin monomers was also investigated. The ALP activity of HDPCs was reduced by TEGDMA and HEMA at noncytotoxic concentrations. The mRNA expression of dentin sialophosphoprotein (DSPP), osteocalcin (OCN), and osteopontin (OPN) was also downregulated by resin monomers. However, DSPP expression was not affected by hydrogen peroxide (H2O2). Among the MAP kinases examined, ERK activation (ERK phosphorylation) was not affected by either resin monomers or H2O2, whereas JNK was phosphorylated by TEGDMA and HEMA. Phospho-p38 was upregulated by HEMA, while TEGDMA and H2O2 suppressed p38 phosphorylation. Exposure to TEGDMA and HEMA for a limited period suppresses differentiation of HDPCs via different signaling pathways.

  5. A light-driven modulation of electric conductance through the adsorption of azobenzene onto silicon-doped- and pyridine-like N3-vacancy graphene.

    Science.gov (United States)

    Zhao, Jun; Liu, Chunyan; Ma, Jing

    2017-12-14

    The ability to modulate the conductance of an electronic device under light irradiation is crucial to the practical applications of nanoscale electronics. Density functional theory calculations predict that the conductance of the photo-responsive graphene-based nanocomposites can be tuned through the noncovalent adsorption of an azobenzene (AB) derivative onto pristine, Si-doped, and pyridine-like N 3 -vacancy graphene. AB@graphene systems were found to exhibit a visible-light response within the low-frequency region, rendering the trans-to-cis isomerizations of these nanocomposites under the irradiation of solar light. The excellent solar light absorption performances of these hybrids can then be used to modulate the conductance of both N 3 -vacancy- and Si-doped-graphene AB hybrids effectively through the reversible change of the effective conjugate length of the AB molecule in the photoisomerization. In addition, the solar thermal energy up to 1.53 eV per AB molecule can be stored in the designed nanocomposites with the doped graphene. These findings provide clues for making multifunctional materials with potential applications as both optically controlled nanoelectronics and solar energy storage devices.

  6. Photoionization and trans-to-cis isomerization of β-cyclodextrin-encapsulated azobenzene induced by two-color two-laser-pulse excitation.

    Science.gov (United States)

    Takeshita, Tatsuya; Hara, Michihiro

    2018-03-15

    Azobenzene (1) and the complex resulting from the incorporation of 1 with cyclodextrin (1/CD) are attractive for light-driven applications such as micromachining and chemical biology tools. The highly sensitive photoresponse of 1 is crucial for light-driven applications containing both 1 and 1/CD to reach their full potential. In this study, we investigated the photoionization and trans-to-cis isomerization of 1/CD induced by one- and two-color two-laser pulse excitation. Photoionization of 1/CD, which was induced by stepwise two-photon absorption, was observed using laser pulse excitation at 266nm. Additionally, simultaneous irradiation with 266 and 532nm laser pulses increased the trans-to-cis isomerization yield (Υ t→c ) by 27%. It was concluded that the increase in Υ t→c was caused by the occurrence of trans-to-cis isomerization in the higher-energy singlet state (S n ), which was reached by S 1 →S n transition induced by laser pulse excitation at 532nm. The results of this study are potentially applicable in light-driven applications such as micromachining and chemical biology tools. Copyright © 2018 Elsevier B.V. All rights reserved.

  7. Testing of residual monomer content reduction possibility on acrilic resins quality

    Directory of Open Access Journals (Sweden)

    Kostić Milena

    2011-01-01

    Full Text Available Poly (methyl methacrylate (PMMA is material widely used in dentistry. Despite the various methods used to initiate the polymerization of acrylic resins, the conversion of monomer to polymer is not complete thus leaving some unreacted methyl methacrylate (MMA, known as residual monomer (RM, in denture structure. RM in dental acrylic resins has deleterious effects on their mechanical properties and their biocompatibility. The objective of the work was to test the residual monomer reduction possibility by applying the appropriate postpolymerization treatment as well as to determine the effects of this reduction on pressure yields stress and surface structure characteristics of the acrylic resins. Postpolymerization treatments and water storage induced reduction of RM amount in cold-polymerized acrylic resins improved their mechanical properties and the homogenized surface structure. After the polymerization of heat-polymerized acrylic resins the post-polymerization treatments for improving the quality of this material type are not necessary.

  8. Polymeric reaction of polymer-monomer system for pressure sensitive adhesives by low energy electron beam

    International Nuclear Information System (INIS)

    Takiguchi, R.; Uryu, T.

    1985-01-01

    Application of low-energy electron beam to non-solvent type pressure sensitive adhesives is investigated. The adhesive properties such as peel strength and holding time (dead-load strength) were closely related to the reaction of acrylate polymer-monomer systems. The reaction behavior is elucidated by combining the measurement of gel fraction, infrared spectrum of gel, and the molecular weight distribution detected by gel permeation chromatography. It was important for the production of pressure sensitive adhesives by electron beam that the adhesive with high peel strength and long holding time is composed of a proper combination of three factors, that is, about 35% gel fraction, 25% monomer units in gel, and 15% graft efficiency by irradiating the polymer-monomer system containing low molecular weight poly (butyl acrylate). (author)

  9. Dynamic mechanical properties of photopolymerizable poly(vinyl alcohol)-acrylate monomer blends

    International Nuclear Information System (INIS)

    Koshiba, M.; Yamaoka, T.; Tsunoda, T.

    1983-01-01

    Dynamic mechanical properties of photopolymerizable poly(vinyl alcohol) (PVA)-monoacrylate blends were investigated by measuring dynamic shear modulus G' and loss tangent, tan delta. The dynamic mechanical properties of the blends before being exposed to UV irradiation were governed by the weight percent of the monomers which act as plasticizers. On the other hand, the UV-irradiated blends seemed to be typical two-phase materials since they revealed two tan delta maxima whose positions were independent of the monomer content. Those two maxima were assigned to PVA and photopolymerized acrylates with reference to the dynamic mechanical data of PVA and a PVA-polyacrylamide polyblend. Those dynamic mechanical data suggested that insolubilization of the blend type photopolymers should be caused by a decrease in solubility due to graft polymerization of acrylate monomers onto PVA. 9 figures, 3 tables

  10. A study on radiation-induced graft copolymerization of monomer onto natural silk fabric

    International Nuclear Information System (INIS)

    Xiang Zhengyu; Wan Dairong; He Qian

    1995-02-01

    In order to improve the properties of natural silk fabric, the mechanism and method of the radiation induced graft copolymerization of monomers onto natural silk fabric were studied. Three monomers, acrylamide, methylacrylamide and hydroxymethyl acrylamide, were selected for grafting test according to requirements of graft processing. The processing conditions of monomer infusion were studied. The properties of grafted samples were measured. The results are as follows: the rate of weight increasing is 10%∼29%; the rate of thickness increasing is 5%∼20%; the abrupt elasticity rose by 30%; the retarded elasticity rose by 12%; wet elasticity rose by 40%; and the brightness of colour and lustre were improved. It is concluded that while the radiation grafted silk kept its natural characteristics, other properties were improved. It became even chubby and thicker. (4 refs., 3 figs., 3 tabs.)

  11. Improved thrombin binding aptamer by incorporation of a single unlocked nucleic acid monomer

    DEFF Research Database (Denmark)

    Pasternak, Anna; Hernandez, Frank J; Rasmussen, Lars Melholt

    2011-01-01

    A 15-mer DNA aptamer (named TBA) adopts a G-quadruplex structure that strongly inhibits fibrin-clot formation by binding to thrombin. We have performed thermodynamic analysis, binding affinity and biological activity studies of TBA variants modified by unlocked nucleic acid (UNA) monomers. UNA...... that a UNA monomer is allowed in many positions of the aptamer without significantly changing the thrombin-binding properties. The biological effect of a selection of the modified aptamers was tested by a thrombin time assay and showed that most of the UNA-modified TBAs possess anticoagulant properties......, and that the construct with a UNA-U monomer in position 7 is a highly potent inhibitor of fibrin-clot formation....

  12. Considerably Unfolded Transthyretin Monomers Preceed and Exchange with Dynamically Structured Amyloid Protofibrils

    DEFF Research Database (Denmark)

    Groenning, Minna; Campos, Raul I; Hirschberg, Daniel

    2015-01-01

    describe an unexpectedly dynamic TTR protofibril structure which exchanges protomers with highly unfolded monomers in solution. The protofibrils only grow to an approximate final size of 2,900 kDa and a length of 70 nm and a comparative HXMS analysis of native and aggregated samples revealed a much higher...... average solvent exposure of TTR upon fibrillation. With SAXS, we reveal the continuous presence of a considerably unfolded TTR monomer throughout the fibrillation process, and show that a considerable fraction of the fibrillating protein remains in solution even at a late maturation state. Together......, these data reveal that the fibrillar state interchanges with the solution state. Accordingly, we suggest that TTR fibrillation proceeds via addition of considerably unfolded monomers, and the continuous presence of amyloidogenic structures near the protofibril surface offers a plausible explanation...

  13. Precision design of ethylene- and polar-monomer-based copolymers by organometallic-mediated radical polymerization

    Science.gov (United States)

    Kermagoret, Anthony; Debuigne, Antoine; Jérôme, Christine; Detrembleur, Christophe

    2014-03-01

    The copolymerization of ethylene with polar monomers is a major challenge when it comes to the manufacture of materials with potential for a wide range of commercial applications. In the chemical industry, free-radical polymerization is used to make a large proportion of such copolymers, but the forcing conditions result in a lack of fine control over the architecture of the products. Herein we introduce a synthetic tool, effective under mild experimental conditions, for the precision design of unprecedented ethylene- and polar-monomer-based copolymers. We demonstrate how an organocobalt species can control the growth of the copolymer chains, their composition and the monomer distribution throughout the chain. By fine tuning the ethylene pressure during polymerization and by exploiting a unique reactive mode of the end of the organometallic chain, novel block-like copolymer structures can be prepared. This highly versatile synthetic platform provides access to a diverse range of polymer materials.

  14. Sustainable Poly(Ionic Liquids) for CO2 Capture Based on Deep Eutectic Monomers

    KAUST Repository

    Isik, Mehmet; Zulfiqar, Sonia; Edhaim, Fatimah; Ruiperez, Fernando; Rothenberger, Alexander; Mecerreyes, David

    2016-01-01

    The design of high performance solid sorbent materials for CO2 capture is a technology which has been employed to mitigate global warming. However, the covalent incorporation of functionalities into polymeric supports usually involves multistep energy-intensive chemical processes. This fact makes the net CO2 balance of the materials negative even though they possess good properties as CO2 sorbents. Here we show a new family of polymers which are based on amines, amidoximes, and natural carboxylic acids and can be obtained using sustainable low energy processes. Thus, deep eutectic monomers based on natural carboxylic acids, amidoximes, and amines have been prepared by just mixing with cholinium type methacrylic ammonium monomer. The formation of deep eutectic monomers was confirmed by differential scanning calorimetry measurements. In all cases, the monomers displayed glass transition temperatures well below room temperature. Computational studies revealed that the formation of eutectic complexes lengthens the distance between the cation and the anion causing charge delocalization. The liquid nature of the resulting deep eutectic monomers (DEMs) made it possible to conduct a fast photopolymerization process to obtain the corresponding poly(ionic liquids). Materials were characterized by means of nuclear magnetic resonance, differential scanning calorimetry, thermogravimetric analysis, and X-ray diffraction to evaluate the properties of the polymers. The polymers were then used as solid sorbents for CO2 capture. It has been shown that the polymers prepared with citric acid displayed better performance both experimentally and computationally. The current endeavor showed that sustainable poly(ionic liquids) based on deep eutectic monomers can be easily prepared to produce low-energy-cost alternatives to the materials currently being researched for CO2 capture. © 2016 American Chemical Society.

  15. High-speed atomic force microscopy reveals structural dynamics of α -synuclein monomers and dimers

    Science.gov (United States)

    Zhang, Yuliang; Hashemi, Mohtadin; Lv, Zhengjian; Williams, Benfeard; Popov, Konstantin I.; Dokholyan, Nikolay V.; Lyubchenko, Yuri L.

    2018-03-01

    α-Synuclein (α-syn) is the major component of the intraneuronal inclusions called Lewy bodies, which are the pathological hallmark of Parkinson's disease. α-Syn is capable of self-assembly into many different species, such as soluble oligomers and fibrils. Even though attempts to resolve the structures of the protein have been made, detailed understanding about the structures and their relationship with the different aggregation steps is lacking, which is of interest to provide insights into the pathogenic mechanism of Parkinson's disease. Here we report the structural flexibility of α-syn monomers and dimers in an aqueous solution environment as probed by single-molecule time-lapse high-speed AFM. In addition, we present the molecular basis for the structural transitions using discrete molecular dynamics (DMD) simulations. α-Syn monomers assume a globular conformation, which is capable of forming tail-like protrusions over dozens of seconds. Importantly, a globular monomer can adopt fully extended conformations. Dimers, on the other hand, are less dynamic and show a dumbbell conformation that experiences morphological changes over time. DMD simulations revealed that the α-syn monomer consists of several tightly packed small helices. The tail-like protrusions are also helical with a small β-sheet, acting as a "hinge". Monomers within dimers have a large interfacial interaction area and are stabilized by interactions in the non-amyloid central (NAC) regions. Furthermore, the dimer NAC-region of each α-syn monomer forms a β-rich segment. Moreover, NAC-regions are located in the hydrophobic core of the dimer.

  16. Sustainable Poly(Ionic Liquids) for CO2 Capture Based on Deep Eutectic Monomers

    KAUST Repository

    Isik, Mehmet

    2016-10-05

    The design of high performance solid sorbent materials for CO2 capture is a technology which has been employed to mitigate global warming. However, the covalent incorporation of functionalities into polymeric supports usually involves multistep energy-intensive chemical processes. This fact makes the net CO2 balance of the materials negative even though they possess good properties as CO2 sorbents. Here we show a new family of polymers which are based on amines, amidoximes, and natural carboxylic acids and can be obtained using sustainable low energy processes. Thus, deep eutectic monomers based on natural carboxylic acids, amidoximes, and amines have been prepared by just mixing with cholinium type methacrylic ammonium monomer. The formation of deep eutectic monomers was confirmed by differential scanning calorimetry measurements. In all cases, the monomers displayed glass transition temperatures well below room temperature. Computational studies revealed that the formation of eutectic complexes lengthens the distance between the cation and the anion causing charge delocalization. The liquid nature of the resulting deep eutectic monomers (DEMs) made it possible to conduct a fast photopolymerization process to obtain the corresponding poly(ionic liquids). Materials were characterized by means of nuclear magnetic resonance, differential scanning calorimetry, thermogravimetric analysis, and X-ray diffraction to evaluate the properties of the polymers. The polymers were then used as solid sorbents for CO2 capture. It has been shown that the polymers prepared with citric acid displayed better performance both experimentally and computationally. The current endeavor showed that sustainable poly(ionic liquids) based on deep eutectic monomers can be easily prepared to produce low-energy-cost alternatives to the materials currently being researched for CO2 capture. © 2016 American Chemical Society.

  17. Distinct Internalization Pathways of Human Amylin Monomers and Its Cytotoxic Oligomers in Pancreatic Cells

    Science.gov (United States)

    Trikha, Saurabh; Jeremic, Aleksandar M.

    2013-01-01

    Toxic human amylin oligomers and aggregates are implicated in the pathogenesis of type 2 diabetes mellitus (TTDM). Although recent studies have shown that pancreatic cells can recycle amylin monomers and toxic oligomers, the exact uptake mechanism and trafficking routes of these molecular forms and their significance for amylin toxicity are yet to be determined. Using pancreatic rat insulinoma (RIN-m5F) beta (β)-cells and human islets as model systems we show that monomers and oligomers cross the plasma membrane (PM) through both endocytotic and non-endocytotic (translocation) mechanisms, the predominance of which is dependent on amylin concentrations and incubation times. At low (≤100 nM) concentrations, internalization of amylin monomers in pancreatic cells is completely blocked by the selective amylin-receptor (AM-R) antagonist, AC-187, indicating an AM-R dependent mechanism. In contrast at cytotoxic (µM) concentrations monomers initially (1 hour) enter pancreatic cells by two distinct mechanisms: translocation and macropinocytosis. However, during the late stage (24 hours) monomers internalize by a clathrin-dependent but AM-R and macropinocytotic independent pathway. Like monomers a small fraction of the oligomers initially enter cells by a non-endocytotic mechanism. In contrast a majority of the oligomers at both early (1 hour) and late times (24 hours) traffic with a fluid-phase marker, dextran, to the same endocytotic compartments, the uptake of which is blocked by potent macropinocytotic inhibitors. This led to a significant increase in extra-cellular PM accumulation, in turn potentiating amylin toxicity in pancreatic cells. Our studies suggest that macropinocytosis is a major but not the only clearance mechanism for both amylin’s molecular forms, thereby serving a cyto-protective role in these cells. PMID:24019897

  18. Graft copolymerization of water soluble mixed monomers onto polyethylene by the pre-irradiation method

    International Nuclear Information System (INIS)

    Long Fu; Tang Liming; Zhao Jin; Gao Zhenyong

    1993-01-01

    Grafting of water soluble mixed monomers of acrylic acid (AA)/acrylamide (Am) and acrylic acid/methacrylic acid (MA) onto polyethylene film by the pre-irradiation grafting method was investigated. The results showed that the grafting proceeded successfully with the adding of ferric salt in the solution. In the case of AA/Am system, a synergistic effect was noticed. In the case of AA/MA system, the graft percent increased with the increase in the concentration of MA in the feed ratio. Furthermore, the effects of monomer concentration, radiation dose and temperature on the grafting were also studied

  19. Synthesis and ATRP of novel fluorinated aromatic monomer with pendant sulfonate group

    DEFF Research Database (Denmark)

    Dimitrov, Ivaylo; Jankova Atanasova, Katja; Hvilsted, Søren

    2013-01-01

    Novel, fluorinated monomer with pendant sulfonate group was synthesized utilizing a two-step derivatization of 2,3,4,5,6-pentafluorostyrene (FS). The first step was a nucleophilic substitution of the fluorine atom in para position by hydroxyl group followed by sulfopropylation. The monomer...... was polymerized under aqueous ATRP conditions to yield phenyl-fluorinated aromatic homopolymer bearing pendant sulfonates on each repeating unit. Furthermore, this polymer was used as macroinitiator for the ATRP of poly(ethylene glycol) methacrylate. The polymers were characterized by 1H NMR, SEC and FTIR...

  20. Cyclic 3-alkyl pyridinium alkaloid monomers from a New Zealand Haliclona sp. marine sponge.

    Science.gov (United States)

    Damodaran, Vidhiya; Ryan, Jason L; Keyzers, Robert A

    2013-10-25

    Bioassay and NMR approaches have been used to guide the isolation of one known and two new cyclic 3-alkyl pyridinium alkaloid (3-APA) monomers from the New Zealand marine sponge Haliclona sp. The new compounds, dehydrohaliclocyclins C (3) and F (4), are the first reported examples of cyclic 3-APA monomers with unsaturation in the alkyl chain. The known compound haliclocyclin C (2) was also isolated from a mixture with 4. The structures of compounds 2-4 were elucidated using NMR spectroscopy, mass spectrometry, and chemical degradation.

  1. Preparation of poly (vinyl alcohol) membranes grafted with n-vinyl pyridine/ acrylic acid binary monomers

    International Nuclear Information System (INIS)

    Ajji, A.; Ali, A.

    2014-03-01

    Poly(vinyl alcohol) films were grafted with two monomers using gamma radiation, acrylic acid and N-vinyl pyridine. The influence of different parameters on the grafting yield was investigated as: the comonomer concentration and composition, and irradiation dose. The suitable conditions of the process had been determined to prepare PVA membranes have both properties of the two monomers, acrylic acid and vinyl pyridine as comonomer concentration and composition, and irradiation dose. Some properties of the membranes had been investigated as maximum swelling and grafting. Also the ability of the grafted films to adsorb some heavy metals and dyes was elaborated and discussed.(author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-05-15

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

  3. PMR Polyimide prepreg with improved tack characteristics. [Polymerization of Monomer Reactants applications to fiber reinforced plastics

    Science.gov (United States)

    Serafini, T. T.; Delvigs, P.

    1978-01-01

    Current PMR Polyimide prepreg technology utilizes methanol or ethanol solvents for preparation of the PMR prepreg solutions. The volatility of these solvents limits the tack and drape retention characteristics of unprotected prepreg exposed to ambient conditions. Studies conducted to achieve PMR 15 Polyimide prepreg with improved tack and drape characteristics are described. Improved tack and drape retention were obtained by incorporation of an additional monomer. The effects of various levels of the added monomer on the thermo-oxidative stability and mechanical properties of graphite fiber reinforced PMR 15 composites exposed and tested at 316 C (600 F) are discussed.

  4. In situ polymerization of monomers for polyphenylquinoxaline/graphite fiber composites

    Science.gov (United States)

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

    1974-01-01

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

  5. New aromatic activated dihalides and bisphenol monomers for the preparation of novel poly(arylene ethers)

    Science.gov (United States)

    Wolfe, James F.

    1993-01-01

    The goal of this research program was to synthesize a series of unique monomers of type I to be utilized at NASA-Langley in the preparation of new poly(arylene ether ketones), poly(arylene ether ketosulfones), and poly(arylene ether ketophosphine oxides). These A-A and A-B monomer systems, which possess activated aryl halide and/or phenolic end groups, are accessible via condensation reactions of appropriately substituted aryl acetonitrile carbanions with activated aryl dihalides followed by oxidative decyanation.

  6. Photoligation of self-assembled DNA constructs containing anthracene-functionalized 2'-amino-LNA monomers

    DEFF Research Database (Denmark)

    Pasternak, Karol; Pasternak, Anna; Gupta, Pankaj

    2011-01-01

    Efficient synthesis of a novel anthracene-functionalized 2'-amino-LNA phosphoramidite derivative is described together with its incorporation into oligodeoxynucleotides. Two DNA strands with the novel 2'-N-anthracenylmethyl-2'-amino-LNA monomers can be effectively cross-linked by photoligation...... at 366nm in various types of DNA constructs. Successful application of three differently functionalized 2'-amino-LNA monomers in self-assembled higher ordered structures for simultaneous cross-linking and monitoring of assembly formation is furthermore demonstrated....

  7. Effect of mineral acid on polymer produced during radiation-induced grafting of styrene monomer

    International Nuclear Information System (INIS)

    Garnett, J.L.; Jankiewicz, S.V.; Sangster, D.F.

    1982-01-01

    The inclusion of mineral acid in a solution of styrene in methanol subjected to 60 Co γ irradiation markedly enhances the yield of monomer grafted to cellulose and other radiation grafting systems. Results were reported from a preliminary investigation into the mechanism of this acid effect through a study of the action of acid during the solution polymerization process. It was found that the presence of acid in a monomer solution such as styrene in 1, 4-dioxan led to an enhancement in the homopolymer yield of styrene; and it was showed that the acid also effected the number-average molecular weight of this homopolymer. 1 figure, 4 tables

  8. Penelitian penggunaan monomer n-butil akrilat untuk peningkatan mutu kulit secara iradiasi

    OpenAIRE

    Dwi Wahini Nurhajati; Suliestiyah Wiryodiningrat; Kadarijah Kadarijah; Penny Setyowati

    1996-01-01

    Research on the utilization of n-butyl acrylate monomer for quality improvement leather by irradiation cobalt-60 gamma-rays is carried out as follows: Javanese crust hide was impregnated with water emulsions of n-butyl acrylate monomer for 2 hours, packed in to poly ethylene bags, sealed, then irradiated by cobalt-60 gamma rays (doses : 5 to 25 kGy). The irradiated leather was washed by water, dried and then physical tested. The results of physical test of leather modified with n-butyl acryl...

  9. Do the monomers release from the composite resins after artificial aging?

    Science.gov (United States)

    Tokay, Ugur; Koyuturk, Alp Erdin; Aksoy, Abdurrahman; Ozmen, Bilal

    2015-04-01

    The aim of this study is to measure the effect of thermal cycling on the amount of monomer released from three different composite materials by HPLC analysis method. Three different composite materials, inlay composite, posterior composite and micro-hybrid composite were used. Sixty cylinder specimens each with a dimension of approximately 1 cm width and 3 mm depth, were prepared before experiments were carried out. Inlay composite material was polymerized according to manufacturers' instructions. Thermal cycling device was used to simulate thermal differences which occur in the mouth media. Monomers were analyzed using HPLC technic after thermal cycling process. The amount of ethoxylated Bis-GMA and urethane dimethacrylate (UDMA) in inlay composite material, the amount of ethoxylated Bis-GMA in posterior composite material, the amount of ethoxylated Bis-GMA and triethyleneglycol dimethacrylate (TEGDMA) in micro-hybrid composite material were investigated. Monomer release of thermal cycles levels showed a linear increase in UDMA and TEGDMA (P < 0.05). In terms of thermal cycles levels, Bis-EMA released from posterior composite showed a cubic change (P < 0.001). It was observed that use of additional polymerization processes might have positive effect on the decrease of residual monomer. In the light of the results, we suggest that indirect composite resins have more outstanding features than direct composite resins in terms of biocompatibility. © 2015 Wiley Periodicals, Inc.

  10. Pseudomonas syringae evades host immunity by degrading flagellin monomers with alkaline protease AprA

    NARCIS (Netherlands)

    Pel, Michiel J C; van Dijken, Anja J H; Bardoel, Bart W; Seidl, Michael F; van der Ent, Sjoerd; van Strijp, Jos A G; Pieterse, Corné M J

    Bacterial flagellin molecules are strong inducers of innate immune responses in both mammals and plants. The opportunistic pathogen Pseudomonas aeruginosa secretes an alkaline protease called AprA that degrades flagellin monomers. Here, we show that AprA is widespread among a wide variety of

  11. Pseudomonas syringae evades host Immunity by degrading flagellin monomers with alkaline protease AprA

    NARCIS (Netherlands)

    Pel, M.J.C.; Van Dijken, A.J.H.; Bardoel, B.W.; Seidl, M.F; Van der Ent, S.; Van Strijp, J.A.G.

    2014-01-01

    Bacterial flagellin molecules are strong inducers of innate immune responses in both mammals and plants. The opportunistic pathogen Pseudomonas aeruginosa secretes an alkaline protease called AprA that degrades flagellin monomers. Here, we show that AprA is widespread among a wide variety of

  12. Reduction of residual monomer in latex products by enhanced polymerization and extraction in supercritical carbon dioxide

    NARCIS (Netherlands)

    Kemmere, M.F.; Schilt, van M.A.; Cleven, M.H.W.; Herk, van A.M.; Keurentjes, J.T.F.

    2002-01-01

    The redn. of Me methacrylate (MMA) in a PMMA latex was chosen as a representative model system. Pulsed electron beam expts. were performed to study the effect of supercrit. carbon dioxide (scCO2) on the monomer concn. inside the polymer particles during the polymn. reaction. The partitioning

  13. Polyimide, dianhydride monomers, and polymers, methods of making and uses thereof

    KAUST Repository

    Pinnau, Ingo; Ghanem, Bader Saleh; Abdulhamid, Mahmoud Atef

    2017-01-01

    Embodiments of the present disclosure include, a dianhydride monomer, a polyimide, a method of making a dianhydride, a method of making a polyimide, and the like. Embodiments of the present disclosure can be used in membrane-based gas separation applications.

  14. Titanium, zirconium- and hafnium containing initiators in the polymerization of acrylic monomers to ''living'' polymers

    International Nuclear Information System (INIS)

    Farnham, W.B.; Hertler, W.R.

    1988-01-01

    This patent describes a process for preparing ''living'' polymer. The process comprises contacting one or more acrylic monomers under polymerizing conditions with a polymerization-initiating amount of a tetra-coordinate organotitanium, organozirconium or organo-hafnium polymerization initiator, and ''living'' polymers produced thereby

  15. Microwave-assisted cationic ring-opening polymerization of a soy-based 2-oxazoline monomer

    NARCIS (Netherlands)

    Hoogenboom, R.; Wiesbrock, F.D.; Schubert, U.S.

    2005-01-01

    The microwave-assisted cationic ring-opening polymn. of a soy based 2-oxazoline monomer (SoyOx) is described. The microwave irradn. provides more efficient heating when compared to conventional heating and, in addn., the SoyOx was prepd. starting from a sustainable resource (soy beans). The

  16. The Off-rate of Monomers Dissociating from Amyloid-β Protofibrils*

    Science.gov (United States)

    Grüning, Clara S. R.; Klinker, Stefan; Wolff, Martin; Schneider, Mario; Toksöz, Küpra; Klein, Antonia N.; Nagel-Steger, Luitgard; Willbold, Dieter; Hoyer, Wolfgang

    2013-01-01

    The interconversion of monomers, oligomers, and amyloid fibrils of the amyloid-β peptide (Aβ) has been implicated in the pathogenesis of Alzheimer disease. The determination of the kinetics of the individual association and dissociation reactions is hampered by the fact that forward and reverse reactions to/from different aggregation states occur simultaneously. Here, we report the kinetics of dissociation of Aβ monomers from protofibrils, prefibrillar high molecular weight oligomers previously shown to possess pronounced neurotoxicity. An engineered binding protein sequestering specifically monomeric Aβ was employed to follow protofibril dissociation by tryptophan fluorescence, precluding confounding effects of reverse or competing reactions. Aβ protofibril dissociation into monomers follows exponential decay kinetics with a time constant of ∼2 h at 25 °C and an activation energy of 80 kJ/mol, values typical for high affinity biomolecular interactions. This study demonstrates the high kinetic stability of Aβ protofibrils toward dissociation into monomers and supports the delineation of the Aβ folding and assembly energy landscape. PMID:24247242

  17. Polyimide, dianhydride monomers, and polymers, methods of making and uses thereof

    KAUST Repository

    Pinnau, Ingo

    2017-11-16

    Embodiments of the present disclosure include, a dianhydride monomer, a polyimide, a method of making a dianhydride, a method of making a polyimide, and the like. Embodiments of the present disclosure can be used in membrane-based gas separation applications.

  18. Visualization of monomer and polymer inside porous stones by using X-ray tomography

    International Nuclear Information System (INIS)

    Brunetti, Antonio; Princi, Elisabetta; Vicini, Silvia; Pincin, Silvia; Bidali, Simone; Mariani, Alberto

    2004-01-01

    Estimate of sorption of liquid materials inside porous stones is an important parameter in industrial material testing and cultural heritage conservation. In the latter case, a suitable polymer can be used for both consolidation and conservation, it being applied either in the final form or as its parent monomer, which is subsequently allowed to polymerize in situ by the classical method or by frontal polymerization. However, the sorption of such materials through the stone is often difficult because of their viscosity and/or stone porosity. For this reason, the amount of monomer (or polymer) is a parameter of great interest in order to determine the extent of protection reachable by the treatment. In this paper a new methodology based on X-ray tomography is presented. The methodology makes use of a contrast agent added to the monomer that does not interact with its propagation inside the stone and allows to increase the absorption coefficient and so to observe the monomer inside the sample, which is finally frontally polymerized

  19. Syntheses of monomers in the reaction of hexamethylolmelamine with 2-hydroxyethyl acrylate and their photocuring

    International Nuclear Information System (INIS)

    Huhui Houlianbo Hufei

    1999-01-01

    A process has been developed for the syntheses of monomers from 2-hydroxyethyl acrylate and hexamethylolmelamine. Their structure were identified by IR and sub 1H-NMR. The photocuring characteristics of these compound and properties of the UV-cured films have been studied

  20. Regulation of the PI3K pathway through a p85a monomer-homodimer equilibrium

    KAUST Repository

    Aljedani, Safia Salim Eid

    2017-01-08

    The phosphatidylinositol-3-kinase a (PI3Ka) is heterodimeric enzyme that is composed of p85a regulatory subunit and a p110a catalytic subunit. PI3Ka plays a key role in cell survival, growth and differentation. Owing to its role as a key regulator, the PI3Ka pathway is the most frequently mutated pathway in human cancers, and is targeted by many viruses to insure their survival and successful reproduction. Previous studies have shown that the equilibrium of p85 monomers and dimers regulates the PI3K pathway, suggesting that interrupting this equilibrium could lead to disease development. Moreover, studies suggest that the p85a monomers and dimers have opposing effects on PI3Ka signaling as only the p85a dimers bind to the PTEN phosphatase, whereas p85a monomers bind to the catalytic p110 subunit. However, the mechanism for dimerisation is controversial, and it is unknown why PTEN or p110a bind only dimer or monomer. Therefore, we combine molecular biology, biophsical, computational and structural methods to investigate the suprosingly complex p85 dimerisation mechanism and its control by ligands. Results may inspire novel theraputic approaches.

  1. High-resolution structure of a retroviral protease folded as a monomer

    Czech Academy of Sciences Publication Activity Database

    Gilski, M.; Kazmierczyk, M.; Krzywda, S.; Zábranská, Helena; Cooper, S.; Popovic, Z.; Khatíb, F.; Dímaio, F.; Thompson, J.; Baker, D.; Pichová, Iva; Jaskolski, M.

    D67, č. 11 (2011), s. 907-914 ISSN 0907-4449 R&D Projects: GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z40550506 Keywords : M-PMV protease * crystal structure * monomer * dimerization inhibitors Subject RIV: CE - Biochemistry Impact factor: 12.619, year: 2011

  2. Environmental effects on the lignin model monomer, vanillyl alcohol, studied by raman spectroscopy

    DEFF Research Database (Denmark)

    Larsen, Kiki Lyster; Barsberg, Søren Talbro

    2011-01-01

    model monomer, vanillyl alcohol (G type), dissolved in different solvents were compared to investigate such effects on the Raman band shapes and positions. Density functional theory combined with the polarizable continuum model were applied to assign the observed bands and tested for prediction accuracy...

  3. Enzymatic polymerization of bio-based monomers for applications in hydrogels and coatings

    DEFF Research Database (Denmark)

    Hoffmann, Christian; Nguyen, Hiep Dinh; Storgaard, Thomas

    of the enzymatic catalysts that can provide control over polymer structure in functional polymers. Lipase catalyzed polymerizations (specifically CALB) has been applied to prepare functional polyesters and to evaluate the possibilities of using less stable bio-based monomers such as itaconic acid or its...

  4. Effect of reactive monomer on PS-b-P2VP film with UV irradiation

    Science.gov (United States)

    Kim, H. J.; Shin, D. M.

    2012-03-01

    Poly(styrene-b-2-vinyl pyridine) (PS-b-P2VP) lamellar film which is hydrophobic block hydrophilic polyelectrolyte block polymer of 52 kg/mol -b- 57 kg/mol and PS-b-P2VP film with reactive monomer (RM257) were prepared for photonic gel films. The lamellar stacks, which is alternating layer of hydrophilic and hydrophobic part of PS-b-P2VP. We reported about the influence of reactive monomer on those photonic gel films. Added reactive monomer photonic gel film had higher absorbance than pure photonic gel films. And band gaps of the lamellar films shifted by the time of UV light irradiation. That Photonic gel films were measured with the UV spectrophotometer. As a result the photonic gel film with reactive monomer had more clear color. The lamellar films were swollen by DI water, Ethyl alcohol (aq) and calcium carbonate solution. Since the domain spacing of dried photonic gel films were not showing any color in visible wavelength. The band gap of the lamellar films were drastically shifted to longer wavelength swollen by calcium carbonate solution (absorbance peak 565nm-->617nm). And the lamellar films were shifted to shorter wave length swollen by ethanol (absorbance peak 565nm-->497nm). So each Photonic gel film showed different color.

  5. Monitoring of originated polymer in pure monomer with gradient polymer elution chromatography (GPEC)

    NARCIS (Netherlands)

    Staal, W.J.; Cools, P.J.C.H.; Herk, van A.M.; German, A.L.

    1994-01-01

    The anal. of the amt. of polymer in pure monomer with cloudpoint measurements gives only a qual. answer. Now by use of a liq. chromatograph and gradient elution a fully automated detn. the amt. of polymer can be measured and an impression of the molar mass can be achieved

  6. Residual monomer reduction in polymer latex products by extraction with supercritical carbon dioxide

    NARCIS (Netherlands)

    Aerts, M.; Meuldijk, J.; Kemmere, M.F.; Keurentjes, J.T.F.

    2011-01-01

    Extraction of residual monomer from a latex product with supercritical carbon dioxide ((sc)CO2) in a column was studied. Operating conditions were chosen at 35¿°C and 100 bar. For reducing the residual styrene level in a polystyrene latex from 104 ppm to 100¿ppm and from 104 ppm to 10¿ppm, a

  7. Stark effect measurements on monomers and trimers of reconstituted light-harvesting complex II of plants

    NARCIS (Netherlands)

    Palacios, M.A.; Caffarri, S.; Bassi, R.; Grondelle, van R.; Amerongen, van H.

    2004-01-01

    The electric-field induced absorption changes (Stark effect) of reconstituted light-harvesting complex II (LHCII) in different oligomerisation states - monomers and trimers - with different xanthophyll content have been probed at 77 K. The Stark spectra of the reconstituted control samples,

  8. Fatty Acid-Based Monomers as Styrene Replacements for Liquid Molding Resins

    Science.gov (United States)

    2005-05-01

    fatty acid length and unsaturation level on resin and polymer properties. Fig. 2. The addition of fatty acids ( oleic acid ) to glycidyl methacylate to...the synthetic route used to form the methacrylated fatty acids (MFA). The carboxylic acid of fatty acids undergoes a simple addition reaction with... form methacrylated fatty acid monomer

  9. The difference of acrylic resin residual monomer levels with various polymerization method

    Directory of Open Access Journals (Sweden)

    Sherman Salim

    2011-12-01

    Full Text Available Background: After polymerization process, heat cured acrylic resin denture base actually still contains residual monomers that can become potential irritants later in oral cavity. Polymerization process is essential to obtain acrylic resin which can meet the requirements of the biocompatible and good physical properties. To meet the requirements, there are several methods of polymerization process used. Purpose: The purpose of this study was to determine the differences of the residual monomer levels of acrylic resin processed by various polymerization methods. Methods: Acrylic resin powder and liquid were mixed based on the rules of factory, and sample was made with size of 30 mm × 50 mm × 3 mm and then polymerized by using microwave at 70° C for 24 hours based on the methods of Japan Industrial Standard (JIS. Each group of samples was cut with weight of ± 0.2 g, dissolved in 5 ml of methyl ethyl ketone in test tubes, and then stored at ± 5° C for four days. Residual monomer level was conducted by using gas chromatograph mass spectrometer. Data obtained were then analyzed by using One-Way ANOVA test with p < 0.05. Results: After the level of polymerizing residual monomer with JIS method was compared to that at 70° C for 24 hours using microwave, it is known that there were significant differences (p < 0.05. Conclusion: The highest level of residual monomer of acrylic resin was that polymerized at 70° C for 24 hours.Latar belakang: Basis gigi tiruan yang berbahan dasar resin akrilik jenis heat cured setelah proses polimerisasi selesai masih mengandung monomer sisa yang berpotensi sebagai bahan iritan dalam rongga mulut. Proses polimerisasi sangat penting untuk mendapatkan resin akrilik yang memenuhi persyaratan biokompatibilitas dan fisik yang baik. Untuk persyaratan tersebut digunakan berbagai macam proses polimerisasi. Tujuan: Penelitian ini bertujuan untuk menentukan kadar monomer sisa resin akrilik yang diproses dengan metode

  10. Concomitant sensitization to glutaraldehyde and methacrylic monomers among dentists and their patients

    Directory of Open Access Journals (Sweden)

    Maya Grigorievna Lyapina

    2016-06-01

    Full Text Available Background: A multitude of methacrylic monomers is used in dentistry. Glutaraldehyde (G is used in dental practice and consumer products as a broad-spectrum antimicrobial agent. The purpose of our study is to evaluate the frequency and the risk of concomitant sensitization to some methacrylic monomers (methyl methacrylate (MMA, triethyleneglycol dimethacrylate (TEGDMA, ethyleneglycol dimethacrylate (EGDMA, 2,2-bis-[4-(2-hydroxy-3-methacrylo-xypropoxyphenyl]-propane (Bis-GMA, 2-hydroxy-ethyl methacrylate (2-HEMA and tetrahydrofurfuryl methacrylate (THFMA and glutaraldehyde in students of dentistry, students from the dental technician school, dental professionals and dental patients. Material and Methods: A total of 262 participants were included in the study: students of dentistry, students from the dental technician school, dental professionals, and dental patients as a control group. All were patch-tested with methacrylic monomers and glutaraldehyde. The results were subject to the statistical analysis (p < 0.05. Results: Among the group of dental students, the highest frequency of concomitant sensitization was to TEGDMA and G (15.5%. In the group of patients the highest frequency of concomitant sensitization was to EGDMA and G (16.4%. The frequency of concomitant sensitization among dental professionals was much lower, with the highest rate to TEGDMA and G (7.7%, too. We consider the students from the dental technician school, where the exposure to glutaraldehyde is less likely, to be the group at a lesser risk of concomitant sensitization. Conclusions: Dental students and dental patients could be outlined as groups at the risk of concomitant sensitization to glutaraldehyde and methacrylic monomers. For dental professionals, we assumed an increased risk for concomitant sensitization to TEGDMA and aldehydes that are commonly used in dentistry. We consider the students from the dental technician school to be the group at a lesser risk of

  11. Coupling of g proteins to reconstituted monomers and tetramers of the M2 muscarinic receptor.

    Science.gov (United States)

    Redka, Dar'ya S; Morizumi, Takefumi; Elmslie, Gwendolynne; Paranthaman, Pranavan; Shivnaraine, Rabindra V; Ellis, John; Ernst, Oliver P; Wells, James W

    2014-08-29

    G protein-coupled receptors can be reconstituted as monomers in nanodiscs and as tetramers in liposomes. When reconstituted with G proteins, both forms enable an allosteric interaction between agonists and guanylyl nucleotides. Both forms, therefore, are candidates for the complex that controls signaling at the level of the receptor. To identify the biologically relevant form, reconstituted monomers and tetramers of the purified M2 muscarinic receptor were compared with muscarinic receptors in sarcolemmal membranes for the effect of guanosine 5'-[β,γ-imido]triphosphate (GMP-PNP) on the inhibition of N-[(3)H]methylscopolamine by the agonist oxotremorine-M. With monomers, a stepwise increase in the concentration of GMP-PNP effected a lateral, rightward shift in the semilogarithmic binding profile (i.e. a progressive decrease in the apparent affinity of oxotremorine-M). With tetramers and receptors in sarcolemmal membranes, GMP-PNP effected a vertical, upward shift (i.e. an apparent redistribution of sites from a state of high affinity to one of low affinity with no change in affinity per se). The data were analyzed in terms of a mechanistic scheme based on a ligand-regulated equilibrium between uncoupled and G protein-coupled receptors (the "ternary complex model"). The model predicts a rightward shift in the presence of GMP-PNP and could not account for the effects at tetramers in vesicles or receptors in sarcolemmal membranes. Monomers present a special case of the model in which agonists and guanylyl nucleotides interact within a complex that is both constitutive and stable. The results favor oligomers of the M2 receptor over monomers as the biologically relevant state for coupling to G proteins. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

  12. Poly(amic acid)s and their poly(amide imide) counterparts containing azobenzene moieties: Characterization, imidization kinetics and photochromic properties

    Energy Technology Data Exchange (ETDEWEB)

    Konieczkowska, Jolanta [Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34 M. Curie-Sklodowska Str., 41-819 Zabrze (Poland); Institute of Chemistry, University of Silesia, 9 Szkolna Str., 40-006 Katowice (Poland); Janeczek, Henryk [Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34 M. Curie-Sklodowska Str., 41-819 Zabrze (Poland); Kozanecka-Szmigiel, Anna, E-mail: annak@if.pw.edu.pl [Faculty of Physics, Warsaw University of Technology, 75 Koszykowa Str., 00-662 Warszawa (Poland); Schab-Balcerzak, Ewa, E-mail: eschab-balcerzak@cmpw-pan.edu.pl [Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34 M. Curie-Sklodowska Str., 41-819 Zabrze (Poland)

    2016-09-01

    We report on a series of novel photochromic poly(amide imide)s and their poly(amic acid) precursors bearing azobenzene chromophores as the side groups. The chemical structures of the polymers were designed so that they exhibited an enhanced thermal stability combined with a large and stable birefringence photogenerated by light of the wavelengths belonging to a wide spectral range. The polymers possessed rigidly attached azochromophores in the content of either one or two per a repeating unit, which in the latter case differed in their structures. The imidization kinetics of the poly(amic acid)s was investigated by differential scanning calorimetry and the kinetic parameters were estimated using Ozawa and Kissinger methods. Measurements of the selected physical properties of the polymers, such as solubility, supramolecular structure, linear absorption, thermal stability, glass transition and photochromic response were performed and used for determination of the structure-property relations. The measurements of photochromic properties showed a very efficient generation of optical anisotropy upon blue and violet irradiation, for both the poly(amide imide)s containing two different chromophores in the repeating unit and for their precursors. For these poly(amide imide)s and for their precursors an exceptionally slow decrease in the photoinduced optical anisotropy in the dark was also observed. - Highlights: • Three azopoly(amide imide)s were obtained from azopoly(amic acid)s. • Chosen physicochemical properties and photochromic responses were measured. • Desired optical response was found for polymers with two azo-dyes in repeating unit. • Structure-property relations were shown.

  13. Guidelines To Select the N-Heterocyclic Carbene for the Organopolymerization of Monomers with a Polar Group

    KAUST Repository

    Falivene, Laura

    2017-02-13

    We report on the DFT stability of zwitterion and spirocycle adducts of five polar monomers with nine N-heterocyclic carbenes (NHC), covering the most typical classes of monomers and NHCs used in organopolymerization. Results indicate that the relative stability of the two adducts is dominated by the singlet-triplet energy gap of the free NHC, with low energy gaps favoring the spirocycle adduct, while high energy gaps favor the zwitterionic adduct. This basic structure/property relationship can be tuned by the hindrance of the NHC and the nature of the monomer. In addition to rationalize existing systems, the 45 NHC/monomer combinations we examined can be used as a guideline to predict the behavior of a new NHC/monomer combination.

  14. Reactivity of vinyl ethers and vinyl ribosides in UV-initiated free radical copolymerization with acceptor monomers.

    Science.gov (United States)

    Pichavant, Loic; Guillermain, Céline; Coqueret, Xavier

    2010-09-13

    The reactivity of various vinyl ethers and vinyloxy derivatives of ribose in the presence of diethyl fumarate or diethyl maleate was investigated for evaluating the potential of donor-acceptor-type copolymerization applied to unsaturated monomers derived from renewable feedstock. The photochemically induced polymerization of model monomer blends in the bulk state was monitored by infrared spectroscopy. The method allowed us to examine the influence of monomer pair structure on the kinetic profiles. The simultaneous consumption of both monomers was observed, supporting an alternating copolymerization mechanism. A lower reactivity of the blends containing maleates compared with fumarates was confirmed. The obtained kinetic data revealed a general correlation between the initial polymerization rate and the Hansen parameter δ(H) associated with the H-bonding aptitude of the donor monomer.

  15. Luminal and parenteral TFF2 and TFF3 dimer and monomer in two models of experimental colitis in the rat

    DEFF Research Database (Denmark)

    Poulsen, Steen Seier; Kissow, Hannelouise; Hare, Kristine

    2005-01-01

    % dextran sodium sulphate in the drinking water or by one intraperitoneal injection of mitomycin C, 3.75 mg/kg. TFF peptides were administered as subcutaneous injections or directly into the lumen via a catheter placed in the proximal colon. Treatments were saline, TFF2, TFF3 monomer or TFF3 dimer 5 mg......2 had positive effect only in DSS-induced colitis. The TFF3 monomer was without any effects in both models. Treatment effect was most pronounced in the middle part of the colon, closest to the tip of the catheter. Injected TFF peptides, especially the TFF3 monomer, aggravated the colitis score...... in both colitis models. CONCLUSIONS: Intracolonic administration of TFF3 dimer and TFF2 improves experimentally induced colitis in rats. The TFF3 monomer has no effect. Parenteral administration of TFF peptides aggravates the colitis especially the TFF3 monomer....

  16. Inverse opal pH sensors with various protic monomers copolymerized with polyhydroxyethylmethacrylate hydrogel

    International Nuclear Information System (INIS)

    Shin, Jinsub; Han, Sung Gu; Lee, Wonmok

    2012-01-01

    Highlights: ► We polymerized four different inverse opal pH sensors by using vinyl monomers containing acidic or basic substituents. ► Stepwise swelling response from polyprotic acid sensor was investigated. ► Opposite color changing responses were obtained for acidic and basic sensors. ► Composite pH sensor with wide pH sensing range was fabricated by mixing different monomers. ► Both acid and base sensors show the response time as fast as ∼10 s. - Abstract: pH sensitive inverse opal sensors were synthesized using various vinyl monomers containing acidic or basic substituents. Acrylic acid (AA), vinylphosphonic acid (VPA), vinylimidazole (VI), and dimethylaminoethylmethacrylic acid (DMAEMA) were respectively copolymerized with hydroxyethylmethacrylate (HEMA), the building block monomer of the hydrogel via UV-initiated photopolymerization. Opal templating and subsequent template removal enabled the fabrication of four inverse opal (IO) hydrogel colorimetric sensors, which responded to pH in different fashions. pH-dependent swelling of the IO hydrogel induced the red-shift of the diffracted color. The sensors containing AA or VPA, the proton donating monomers showed the color shifts from green to red with pH increase due to the increased concentration of carboxylate anions bound to the hydrogel. Diprotic VPA sensor exhibited two-step increases of diffracted wavelengths at its pK a1 and pK a2 respectively. The sensors containing proton acceptors, VI and DMAEMA showed the pH-dependent color changes in an opposite way to the AA sensor and the VPA sensor since their ionizations take place by lowering pH due to the protonation at the amino groups. The shapes of pH response curves of VI and DMAEMA sensors were similar but pK b s were different from each other. Optical diffraction responses of four sensors were compared with the calculated concentration ratios of the ionized species to the total monomer with pH variation, and a deswelling effect in the

  17. Mangrove tannins and their flavanoid monomers as alternative steel corrosion inhibitors in acidic medium

    International Nuclear Information System (INIS)

    Rahim, Afidah A.; Rocca, E.; Steinmetz, J.; Kassim, M.J.; Adnan, R.; Sani Ibrahim, M.

    2007-01-01

    The inhibitive behaviour on steel of flavanoid monomers that constitute mangrove tannins namely catechin, epicatechin, epigallocatechin and epicatechingallate was investigated in an aerated HCl solution via electrochemical methods. The monomers were found to be mainly cathodic inhibitors and the inhibition efficiency was dependent on concentration. To explain the adsorptive behaviour of the molecules on the steel surface, a semiempirical approach involving quantum chemical calculations using HyperChem 6.0 was undertaken. The HOMO electronic density of the molecule was used to explain the inhibiting mechanism. The most probable adsorption centers were found in the vicinity of the phenolic groups. In a second part, the use of mangrove tannin, extracted from the mangrove barks as steel corrosion inhibitors in acidic media was investigated and its inhibitive efficiency was compared with that of commercial mimosa, quebracho and chestnut tannins. The inhibitive performance of mangrove tannins was comparable to the other tannins investigated, indicating their potential in corrosion protection

  18. Radiation initiated grafting of hydrophilic and reactive monomers on polyetherurethane for biomedical application

    International Nuclear Information System (INIS)

    Jansen, B.; Ellinghorst, G.

    1981-01-01

    Hydrogels such poly(hydroxyethylmethacrylate), poly (acrylamide) and poly(2,3-dihydroxypropylmethacrylate) are a class of well-known materials with good to excellent biomedical properties. Unfortunately the mechanical behaviour of the water-swollen gels is poor, and thus their application in pure state is limited. Much work has been done, especially by the grafting technique, on supporting the hydrogels by several techniques in order to improve their mechanical properties. In this work grafting of hydrogel forming or reactive monomers (which can be made hydrophilic by a following chemical process) onto a polyetherurethane was performed by a technique in which the trunk polymer is swollen in the graft monomer before irradiation. (author)

  19. Preparation of unsaturated acrylic prepolymer and electron beam curing of its mixture with vinyl monomers

    International Nuclear Information System (INIS)

    Pyun, H.C.; Park, W.B.; Kim, K.Y.; Sung, K.Y.

    1980-01-01

    Electron beam curable prepolymers were prepared by the addition reaction of methyl methacrylate-glycidyl methacrylate copolymer with methacrylic acid, and electron beam curing was studied for the prepolymer and their mixtures of several kind of vinyl monomers. When the reaction was carried out in the presence of triethylbenzyl ammonium chloride in N,N-dimethyl formamide solution, the rate of addition reaction obeyed first-order kinetics. In the electron beam curing, the rate of gel formation of the prepolymer was slower than that of the mixtures of prepolymer and monomers. In the curing of mixtures of prepolymer with polyethyleneglycol dimethacrylates, the rate of gel formation increased with the increase in the degree of polymerization of polyethylene oxide fraction of polyethyleneglycol dimethacrylate, and decreased with the increase the polyethyleneglycol dimethacrylate content. The properties of cured coatings were also examined. (author)

  20. Dip-pen nanopatterning of photosensitive conducting polymer using a monomer ink

    Science.gov (United States)

    Su, Ming; Aslam, Mohammed; Fu, Lei; Wu, Nianqiang; Dravid, Vinayak P.

    2004-05-01

    Controlled patterning of conducting polymers at a micro- or nanoscale is the first step towards the fabrication of miniaturized functional devices. Here, we introduce an approach for the nanopatterning of conducting polymers using an improved monomer "ink" in dip-pen nanolithography (DPN). The nominal monomer "ink" is converted, in situ, to its conducting solid-state polymeric form after patterned. Proof-of-concept experiments have been performed with acid-promoted polymerization of pyrrole in a less reactive environment (tetrahydrofuran). The ratios of reactants are optimized to give an appropriate rate to match the operation of DPN. A similar synthesis process for the same polymer in its bulk form shows a high conductance and crystalline structure. The miniaturized conducting polymer sensors with light detection ability are fabricated by DPN using the improved ink formula, and exhibit excellent response, recovery, and sensitivity parameters.

  1. Dip-pen nanopatterning of photosensitive conducting polymer using a monomer ink

    International Nuclear Information System (INIS)

    Su Ming; Aslam, Mohammed; Fu Lei; Wu Nianqiang; Dravid, Vinayak P.

    2004-01-01

    Controlled patterning of conducting polymers at a micro- or nanoscale is the first step towards the fabrication of miniaturized functional devices. Here, we introduce an approach for the nanopatterning of conducting polymers using an improved monomer 'ink' in dip-pen nanolithography (DPN). The nominal monomer 'ink' is converted, in situ, to its conducting solid-state polymeric form after patterned. Proof-of-concept experiments have been performed with acid-promoted polymerization of pyrrole in a less reactive environment (tetrahydrofuran). The ratios of reactants are optimized to give an appropriate rate to match the operation of DPN. A similar synthesis process for the same polymer in its bulk form shows a high conductance and crystalline structure. The miniaturized conducting polymer sensors with light detection ability are fabricated by DPN using the improved ink formula, and exhibit excellent response, recovery, and sensitivity parameters

  2. Mangrove tannins and their flavanoid monomers as alternative steel corrosion inhibitors in acidic medium

    Energy Technology Data Exchange (ETDEWEB)

    Rahim, Afidah A. [School of Chemical Sciences, University Sains Malaysia, 11800 Penang (Malaysia)]. E-mail: afidah@usm.my; Rocca, E. [Laboratoire de Chimie du Solide Mineral, Universite Henri Poincare, Nancy I BP 239, 54506 Vandoeuvre Les Nancy (France); Steinmetz, J. [Laboratoire de Chimie du Solide Mineral, Universite Henri Poincare, Nancy I BP 239, 54506 Vandoeuvre Les Nancy (France); Kassim, M.J. [School of Chemical Sciences, University Sains Malaysia, 11800 Penang (Malaysia); Adnan, R. [School of Chemical Sciences, University Sains Malaysia, 11800 Penang (Malaysia); Sani Ibrahim, M. [School of Chemical Sciences, University Sains Malaysia, 11800 Penang (Malaysia)

    2007-02-15

    The inhibitive behaviour on steel of flavanoid monomers that constitute mangrove tannins namely catechin, epicatechin, epigallocatechin and epicatechingallate was investigated in an aerated HCl solution via electrochemical methods. The monomers were found to be mainly cathodic inhibitors and the inhibition efficiency was dependent on concentration. To explain the adsorptive behaviour of the molecules on the steel surface, a semiempirical approach involving quantum chemical calculations using HyperChem 6.0 was undertaken. The HOMO electronic density of the molecule was used to explain the inhibiting mechanism. The most probable adsorption centers were found in the vicinity of the phenolic groups. In a second part, the use of mangrove tannin, extracted from the mangrove barks as steel corrosion inhibitors in acidic media was investigated and its inhibitive efficiency was compared with that of commercial mimosa, quebracho and chestnut tannins. The inhibitive performance of mangrove tannins was comparable to the other tannins investigated, indicating their potential in corrosion protection.

  3. Penelitian penggunaan monomer n-butil akrilat untuk peningkatan mutu kulit secara iradiasi

    Directory of Open Access Journals (Sweden)

    Dwi Wahini Nurhajati

    1996-06-01

    Full Text Available Research on the utilization of n-butyl acrylate monomer for quality improvement leather by irradiation cobalt-60 gamma-rays is carried out as follows: Javanese crust hide was impregnated with water emulsions of n-butyl acrylate monomer for 2 hours, packed in to poly ethylene bags, sealed, then irradiated by cobalt-60 gamma rays (doses : 5 to 25 kGy. The irradiated leather was washed by water, dried and then physical tested. The results of physical test of leather modified with n-butyl acrylate showed the increasing of tensile strength and elongation, decreasing of water absorption, resistance against the flexing test of 20,000 times, and PH was constant. Organoleptic test showed that the softly of the modified leather was no different with unmodified leather.

  4. GPCR homomers and heteromers: a better choice as targets for drug development than GPCR monomers?

    Science.gov (United States)

    Casadó, Vicent; Cortés, Antoni; Mallol, Josefa; Pérez-Capote, Kamil; Ferré, Sergi; Lluis, Carmen; Franco, Rafael; Canela, Enric I

    2009-11-01

    G protein-coupled receptors (GPCR) are targeted by many therapeutic drugs marketed to fight against a variety of diseases. Selection of novel lead compounds are based on pharmacological parameters obtained assuming that GPCR are monomers. However, many GPCR are expressed as dimers/oligomers. Therefore, drug development may consider GPCR as homo- and hetero-oligomers. A two-state dimer receptor model is now available to understand GPCR operation and to interpret data obtained from drugs interacting with dimers, and even from mixtures of monomers and dimers. Heteromers are distinct entities and therefore a given drug is expected to have different affinities and different efficacies depending on the heteromer. All these concepts would lead to broaden the therapeutic potential of drugs targeting GPCRs, including receptor heteromer-selective drugs with a lower incidence of side effects, or to identify novel pharmacological profiles using cell models expressing receptor heteromers.

  5. Synthesis and Characterization of Oligodeoxyribonucleotides Modified with 2'-Amino-α-l-LNA Adenine Monomers

    DEFF Research Database (Denmark)

    Andersen, Nicolai K; Anderson, Brooke A; Wengel, Jesper

    2013-01-01

    The development of conformationally restricted nucleotide building blocks continues to attract considerable interest because of their successful use within antisense, antigene, and other gene-targeting strategies. Locked nucleic acid (LNA) and its diastereomer α-l-LNA are two interesting examples...... (ONs) modified with 2'-amino-α-l-LNA adenine monomers W-Z. The synthesis of the target phosphoramidites 1-4 is initiated from pentafuranose 5, which upon Vorbrüggen glycosylation, O2'-deacylation, O2'-activation and C2'-azide introduction yields nucleoside 8. A one-pot tandem Staudinger....... ONs modified with pyrene-functionalized 2'-amino-α-l-LNA adenine monomers X-Z display greatly increased affinity toward DNA targets (ΔTm/modification up to +14 °C). Results from absorption and fluorescence spectroscopy suggest that the duplex stabilization is a result of pyrene intercalation...

  6. Effect of Monomer Dosing Rate in the Preparation of Mesoporous Polystyrene Nanoparticles by Semicontinuous Heterophase Polymerization

    Directory of Open Access Journals (Sweden)

    Dalia Y. Sosa

    2014-12-01

    Full Text Available The semicontinuous heterophase polymerization of styrene in the presence of cross-linking and porogen agents was carried out. Latexes with close to 20% solid content, which contained mesoporous nanoparticles with 28 nm in average diameters, up to 0.5 cm3/g in porosity and 6–8 nm in pore diameters were obtained. By varying the monomer dosing rate over the micellar solution, an unexpected direct dependence of instantaneous conversion on the monomer dosing rate was found. This was ascribed to the higher average number of radicals per particle attained in the polymerization at the higher dosing rate, which in turn would arise from the higher gel percentage in the polymer. It is believed that the cross-linked chains prevent encounters between radicals, delaying the bimolecular termination reactions and allowing the existence of more than one radical inside the particles, which in turn increases the propagation rate.

  7. Immobilization of enzymes by radiation-induced polymerization of glass-forming monomers

    International Nuclear Information System (INIS)

    Yoshida, M.; Kumakura, M.; Kaetsu, I.

    1979-01-01

    The effect of cooling rate of a monomeric system on the porosity and activity of an immobilized enzyme prepared by radiation-induced polymerization of 2-hydroxyethyl methacrylate at low temperatures has been studied. Slow cooling gave the same effect on porosity of the polymer as decreasing the monomer concentration. A glass-forming solvent such as diethylene glycol was added to water to study the effect of the supercooling tendency of the solvent. Addition of diethylene glycol decreased porosity and also enzymic activity. Water was replaced by the miscible solvent p-dioxane and the immiscible solvent n-decane in order to clarify the effect of solvent. p-Dioxane had a similar effect to water on the relation between the monomer concentration, porosity and activity. On the other hand, polymer prepared from the system containing n-decane showed different immobilization properties owing to the presence of independent pores in the matrix. (author)

  8. Modeling the structure and vibrational spectra for oxouranium dichloride monomer and dimer

    Science.gov (United States)

    Umreiko, D. S.; Shundalau, M. B.; Trubina, O. V.

    2010-11-01

    Structural models are designed and spectral characteristics are computed for the monomer and dimer of the oxouranium dichloride (UOCl2) molecule based on ab initio calculations. The calculations were carried out in the LANL2DZ effective core potential approximation for the uranium atom and all-electron basis sets using DFT methods for oxygen and chlorine atoms (B3LYP/cc-pVDZ). A close-to-planar Y-shaped equilibrium configuration with Cs symmetry is obtained for the UOCl2 monomer. The formation of the dimer is accompanied by both significant changes in the structure of the monomeric fragments and the actual loss of their identities. The obtained spectral characteristics are analyzed and compared with experimental data. The adequacy of the proposed models and qualitative agreement between calculation and experiment are demonstrated.

  9. An ionic force-field study of monomers, dimers and higher polymers in pentafluoride vapors

    Energy Technology Data Exchange (ETDEWEB)

    Cicek Onem, Z. [Department of Physics, Istanbul University, Istanbul (Turkey); Akdeniz, Z. [Department of Physics, Istanbul University, Istanbul (Turkey); Classe di Scienze, Scuola Normale Superiore, I-56126 Pisa (Italy)], E-mail: zakdeniz@istanbul.edu.tr; Tosi, M.P. [Classe di Scienze, Scuola Normale Superiore, I-56126 Pisa (Italy)], E-mail: tosim@sns.it

    2008-08-01

    Pentafluoride compounds such as NbF{sub 5} and TaF{sub 5} have been reported in the literature to admit various states of polymerization coexisting with monomers in their vapor phase, in relative concentrations that vary with temperature and pressure. We construct a microscopic interionic force-field model for the molecular monomer of these compounds (including VF{sub 5}, SbF{sub 5} and MoF{sub 5} in addition to NbF{sub 5} and TaF{sub 5}), the stable form of the monomer being in the shape of a D{sub 3h} trigonal bipyramid in all cases. The model emulates chemical bonds by allowing for electrical and short-range overlap polarizabilities of the fluorines, and is used to evaluate the structure and the stability of (MF{sub 5}){sub n} molecules with n running from 2 to 6. The dimer is formed by two distorted edge-sharing octahedral, while the trimer and the higher polymers can form rings of distorted corner-sharing octahedra. A chain-like configuration is also found for the trimer of NbF{sub 5}, which consists of a seven-fold coordinated Nb bonded to two distorted octahedra via edge sharing. Comparison of calculated vibrational frequencies and bond lengths with experimental data is made whenever possible. We find that there is a small net gain of energy in the formation of a dimer, while otherwise the static energy of the n-mer is very close to that of n separated monomers. High sensitivity of the state of molecular aggregation to the thermodynamic conditions of the vapor is clearly indicated by our calculations.

  10. Graft copolymers of polypropylene films. 1. radiation induced grafting of mixed monomers. Vol. 3

    International Nuclear Information System (INIS)

    El-Salmawi, K.M.; El-Naggar, A.M.; Said, H.M.; Zahran, A.H.

    1996-01-01

    Radiation graft copolymerization of co monomer mixtures of acrylic acid (AAC), and styrene (S) onto polypropylene (PP) film by mutual method has been investigated. The effects of different factors that may affect the grafting yield such as inhibitor concentration (Mohr's salt), solvent composition (MeOH and H 2 O), radiation dose and dose rate were considered. It was found that the role of Mohr's salt is very effective when the ratio of AAC in the co monomer mixtures was at lower values. However, the addition of 1.25 Wt% of Mohr's salt reduced the homo polymer formation and enhances the grafting process. Graft copolymerization in presence of solvent mixture composed of methanol and water was found to afford higher grafting than in pure methanol regardless of the composition of the co monomer mixture used. However, the highest degree of grafting was obtained at a solvent composition of 20% H 2 O:80%MeOH and a co monomer mixture of 20%AAC:80%sty. An attempt was made to determine each PAAC and PS fractions in the total graft yield obtained. Two methods of analysis based on using the reactivity ratios reported in literature, elemental analysis and IR spectroscopy. The determination of poly (acrylic acid) and polystyrene fractions by elemental analysis is believed more accurate than these by reactivity ratio. The precise results obtained by elemental analysis with respect to the chemical structure of known polymer prepared under identical conditions. The results obtained by IR measurements go well with that obtained with the reactivity ratio methods. 5 figs., 3 tabs

  11. Inclusion polymerization of vinyl chloride monomer in deoxycholic acid host via γ-ray irradiation

    International Nuclear Information System (INIS)

    Chirachanchai, S.; Kumkrong, A.; Ishida, Hatsuo

    2000-01-01

    Inclusion polymerization of vinyl chloride monomer (VCM) was studied in the system of 3α, 12α -dihydroxy-5β-cholan-24-oic acid (deoxycholic acid, DCA). DCA-VCM inclusion compound system was originally prepared by guest intercalation technique in DCA guest free crystal. The inclusion polymerization of DCA-VCM by γ-irradiation at total dose 2 Mrad, gives a syndiotactic rich polyvinyl chloride (PVC) as can be confirmed by FT-IR and FT-NMR. (author)

  12. Inclusion polymerization of vinyl chloride monomer in deoxycholic acid host via {gamma}-ray irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Chirachanchai, S.; Kumkrong, A. [The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok (Thailand); Ishida, Hatsuo [Department of Macromolecular Science, Case Western Reserve University, Cleveland, OH (United States)

    2000-03-01

    Inclusion polymerization of vinyl chloride monomer (VCM) was studied in the system of 3{alpha}, 12{alpha} -dihydroxy-5{beta}-cholan-24-oic acid (deoxycholic acid, DCA). DCA-VCM inclusion compound system was originally prepared by guest intercalation technique in DCA guest free crystal. The inclusion polymerization of DCA-VCM by {gamma}-irradiation at total dose 2 Mrad, gives a syndiotactic rich polyvinyl chloride (PVC) as can be confirmed by FT-IR and FT-NMR. (author)

  13. Polymerization of unsaturated monomers with radiation in the presence of salts

    International Nuclear Information System (INIS)

    Phalangas, C.J.; Restaino, A.J.; Yun, H.B.

    1977-01-01

    Improved process is claimed for the preparation of water-soluble, substantially linear, high molecular weight polymers, comprising irradiating an aqueous solution of an ethylenically unsaturated monomer and a water-soluble salt under controlled conditions of concentration, radiation intensity, conversion, and total radiation dose. The polymers may be obtained in aqueous gel form or recovered in the form of powder. The polymers are useful as flocculating, thickening, and mobility control agents

  14. Graft copolymers of polypropylene films. 1. radiation induced grafting of mixed monomers. Vol. 3

    Energy Technology Data Exchange (ETDEWEB)

    El-Salmawi, K M; El-Naggar, A M; Said, H M; Zahran, A H [Radiation Chemistry Department, National Center for Radiation Research and Technology, Atomic Energy Authority, Cairo, (Egypt)

    1996-03-01

    Radiation graft copolymerization of co monomer mixtures of acrylic acid (AAC), and styrene (S) onto polypropylene (PP) film by mutual method has been investigated. The effects of different factors that may affect the grafting yield such as inhibitor concentration (Mohr`s salt), solvent composition (MeOH and H{sub 2} O), radiation dose and dose rate were considered. It was found that the role of Mohr`s salt is very effective when the ratio of AAC in the co monomer mixtures was at lower values. However, the addition of 1.25 Wt% of Mohr`s salt reduced the homo polymer formation and enhances the grafting process. Graft copolymerization in presence of solvent mixture composed of methanol and water was found to afford higher grafting than in pure methanol regardless of the composition of the co monomer mixture used. However, the highest degree of grafting was obtained at a solvent composition of 20% H{sub 2} O:80%MeOH and a co monomer mixture of 20%AAC:80%sty. An attempt was made to determine each PAAC and PS fractions in the total graft yield obtained. Two methods of analysis based on using the reactivity ratios reported in literature, elemental analysis and IR spectroscopy. The determination of poly (acrylic acid) and polystyrene fractions by elemental analysis is believed more accurate than these by reactivity ratio. The precise results obtained by elemental analysis with respect to the chemical structure of known polymer prepared under identical conditions. The results obtained by IR measurements go well with that obtained with the reactivity ratio methods. 5 figs., 3 tabs.

  15. Effect of radiation combined with Chinese medicinal monomers on Me180 cells

    International Nuclear Information System (INIS)

    Geng Chuanying; Xu Bo; Li Hongyan; Chen Zhihua; Xia Qisheng; Xu Mei; Liu Xuan; Xiang Qing; Liu Yufeng

    2009-01-01

    Objective: To observe the effect of radiation treatment combined with Chinese medicinal monomers on the proliferation function, telomerase activity, expressions of apoptosis- and proliferation-related genes of Me180 cells. Methods: Me180 cells were cultured in the medium with oleanolic acid, curcumin and allicin. The survival rates of cells were detected by the methods of MTT, the telomerase activity by the method of telomeric repeat amplification protocol (TRAP) and the apoptosis -and proliferation-related genes by the method of reverse transeriptase-PCR. Me180 cells were cultured in the medium with Chinese medicinal monomers, and exposed to X-ray irradiation and the survival rates were detected. Results: The results of MTY showed that survival rates of tumor cells exposed to X rays in combination with oleanolic acid, curcumin and allicin were decreased significantly(t=2.81, 4.16, and 3.42, P<0.05). Chinese medicinal monomers inhibited the telomerase activity of MelS0 cells and the inhibiting function changed with time. At 16 h, the telomerase activities of MelS0 cells administered with oleanolic acid and allicin were reduced markedly (t=5.11 and 5.29, P<0.05). After 48 h, the telomerase activities returned to the normal level. The gene expressions of p21 and p16 in Me180 cells treated with oleanolic acid were 2.43 and 2.78 times higher than the control, respectively, while those of cyclin D1 and CDK4 were 56% and 41% of the control, respectively. Conclusions: Chinese medicinal monomers could effectively kill tumor cells, inhibit the telomerase activity and the expression of proliferation-related genes, and enhance the radiosensitivity of tumor cells. (authors)

  16. Solubility enhancement of dioxins and PCBs by surfactant monomers and micelles quantified with polymer depletion techniques.

    Science.gov (United States)

    Schacht, Veronika J; Grant, Sharon C; Escher, Beate I; Hawker, Darryl W; Gaus, Caroline

    2016-06-01

    Partitioning of super-hydrophobic organic contaminants (SHOCs) to dissolved or colloidal materials such as surfactants can alter their behaviour by enhancing apparent aqueous solubility. Relevant partition constants are, however, challenging to quantify with reasonable accuracy. Partition constants to colloidal surfactants can be measured by introducing a polymer (PDMS) as third phase with known PDMS-water partition constant in combination with the mass balance approach. We quantified partition constants of PCBs and PCDDs (log KOW 5.8-8.3) between water and sodium dodecyl sulphate monomers (KMO) and micelles (KMI). A refined, recently introduced swelling-based polymer loading technique allowed highly precise (4.5-10% RSD) and fast (KMO. SHOC losses to experimental surfaces were substantial (8-26%) in monomer solutions, but had a low impact on KMO (0.10-0.16 log units). Log KMO for PCDDs (4.0-5.2) were approximately 2.6 log units lower than respective log KMI, which ranged from 5.2 to 7.0 for PCDDs and 6.6-7.5 for PCBs. The linear relationship between log KMI and log KOW was consistent with more polar and moderately hydrophobic compounds. Apparent solubility increased with increasing hydrophobicity and was highest in micelle solutions. However, this solubility enhancement was also considerable in monomer solutions, up to 200 times for OCDD. Given the pervasive presence of surfactant monomers in typical field scenarios, these data suggest that low surfactant concentrations may be effective long-term facilitators for subsurface transport of SHOCs. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Enhanced lignin monomer production caused by cinnamic Acid and its hydroxylated derivatives inhibits soybean root growth.

    Directory of Open Access Journals (Sweden)

    Rogério Barbosa Lima

    Full Text Available Cinnamic acid and its hydroxylated derivatives (p-coumaric, caffeic, ferulic and sinapic acids are known allelochemicals that affect the seed germination and root growth of many plant species. Recent studies have indicated that the reduction of root growth by these allelochemicals is associated with premature cell wall lignification. We hypothesized that an influx of these compounds into the phenylpropanoid pathway increases the lignin monomer content and reduces the root growth. To confirm this hypothesis, we evaluated the effects of cinnamic, p-coumaric, caffeic, ferulic and sinapic acids on soybean root growth, lignin and the composition of p-hydroxyphenyl (H, guaiacyl (G and syringyl (S monomers. To this end, three-day-old seedlings were cultivated in nutrient solution with or without allelochemical (or selective enzymatic inhibitors of the phenylpropanoid pathway in a growth chamber for 24 h. In general, the results showed that 1 cinnamic, p-coumaric, caffeic and ferulic acids reduced root growth and increased lignin content; 2 cinnamic and p-coumaric acids increased p-hydroxyphenyl (H monomer content, whereas p-coumaric, caffeic and ferulic acids increased guaiacyl (G content, and sinapic acid increased sinapyl (S content; 3 when applied in conjunction with piperonylic acid (PIP, an inhibitor of the cinnamate 4-hydroxylase, C4H, cinnamic acid reduced H, G and S contents; and 4 when applied in conjunction with 3,4-(methylenedioxycinnamic acid (MDCA, an inhibitor of the 4-coumarate:CoA ligase, 4CL, p-coumaric acid reduced H, G and S contents, whereas caffeic, ferulic and sinapic acids reduced G and S contents. These results confirm our hypothesis that exogenously applied allelochemicals are channeled into the phenylpropanoid pathway causing excessive production of lignin and its main monomers. By consequence, an enhanced stiffening of the cell wall restricts soybean root growth.

  18. Interactions between resin monomers and commercial composite resins with human saliva derived esterases.

    Science.gov (United States)

    Jaffer, F; Finer, Y; Santerre, J P

    2002-04-01

    Cholesterol esterase (CE) and pseudocholinesterase (PCE) have been reported to degrade commercial and model composite resins containing bisphenylglycidyl dimethacrylate (BisGMA), triethylene glycol dimethacrylate (TEGDMA) or the latter in combination with urethane modified BisGMA monomer systems. In addition, human saliva has been shown to contain esterase like activities similar to CE and PCE. Hence, it was the aim of the current study to determine to what extent human saliva could degrade two common commercial composite resins (Z250 from 3M Inc. and Spectrum TPH from L.D. Caulk) which contain the above monomer systems. Saliva samples from different volunteers were collected, processed, pooled, and freeze-dried. TEGDMA and BisGMA monomers were incubated with human saliva derived esterase activity (HSDEA) and their respective hydrolysis was monitored using high performance liquid chromatography (HPLC). Both monomers were completely hydrolyzed within 25 h by HSDEA. Photopolymerized composites were incubated with buffer or human saliva (pH 7.0 and 37 C) for 2, 8 and 16 days. The incubation solutions were analyzed using HPLC and mass spectrometry. Surface morphology characterization was carried out using scanning electron microscopy. Upon biodegradation, the Z250 composite yielded higher amounts of BisGMA and TEGDMA related products relative to the TPH composite. However, there were higher amounts of ethoxylated bis-phenol A released from the TPH material. In terms of total mass of products released, human saliva demonstrated a greater ability to degrade Z250. In summary, HSDEA has been shown to contain esterase activities that can readily catalyze the biodegradation of current commercial composite resins.

  19. Solid-support Electron Paramagnetic Resonance (EPR) Studies of Aβ40 Monomers Reveal a Structured State with Three Ordered Segments*

    Science.gov (United States)

    Gu, Lei; Ngo, Sam; Guo, Zhefeng

    2012-01-01

    Alzheimer disease is associated with the pathological accumulation of amyloid-β peptide (Aβ) in the brain. Soluble Aβ oligomers formed during early aggregation process are believed to be neurotoxins and causative agents in Alzheimer disease. Aβ monomer is the building block for amyloid assemblies. A comprehensive understanding of the structural features of Aβ monomer is crucial for delineating the mechanism of Aβ oligomerization. Here we investigated the structures of Aβ40 monomer using a solid-support approach, in which Aβ40 monomers are tethered on the solid support via an N-terminal His tag to prevent further aggregation. EPR spectra of tethered Aβ40 with spin labels at 18 different positions show that Aβ40 monomers adopt a completely disordered structure under denaturing conditions. Under native conditions, however, EPR spectra suggest that Aβ40 monomers adopt both a disordered state and a structured state. The structured state of Aβ40 monomer has three more ordered segments at 14–18, 29–30, and 38–40. Interactions between these segments may stabilize the structured state, which likely plays an important role in Aβ aggregation. PMID:22277652

  20. Hydrophobic Coatings on Cotton Obtained by in Situ Plasma Polymerization of a Fluorinated Monomer in Ethanol Solutions.

    Science.gov (United States)

    Molina, Ricardo; Teixidó, Josep Maria; Kan, Chi-Wai; Jovančić, Petar

    2017-02-15

    Plasma polymerization using hydrophobic monomers in the gas phase is a well-known technology to generate hydrophobic coatings. However, synthesis of functional hydrophobic coatings using plasma technology in liquids has not yet been accomplished. This work is consequently focused on polymerization of a liquid fluorinated monomer on cotton fabric initiated by atmospheric plasma in a dielectric barrier discharge configuration. Functional hydrophobic coatings on cotton were successfully achieved using in situ atmospheric plasma-initiated polymerization of fluorinated monomer dissolved in ethanol. Gravimetric measurements reveal that the amount of polymer deposited on cotton substrates can be modulated with the concentration of monomer in ethanol solution, and cross-linking reactions occur during plasma polymerization of a fluorinated monomer even without the presence of a cross-linking agent. FTIR and XPS analysis were used to study the chemical composition of hydrophobic coatings and to get insights into the physicochemical processes involved in plasma treatment. SEM analysis reveals that at high monomer concentration, coatings possess a three-dimensional pattern with a characteristic interconnected porous network structure. EDX analysis reveals that plasma polymerization of fluorinated monomers takes place preferentially at the surface of cotton fabric and negligible polymerization takes place inside the cotton fabric. Wetting time measurements confirm the hydrophobicity of cotton coatings obtained although equilibrium moisture content was slightly decreased. Additionally, the abrasion behavior and resistance to washing of plasma-coated cotton has been evaluated.

  1. Selective extraction of bisphenol A from water by one-monomer molecularly imprinted magnetic nanoparticles.

    Science.gov (United States)

    Lin, Zhenkun; Zhang, Yanfang; Su, Yu; Qi, Jinxia; Jia, Yinhang; Huang, Changjiang; Dong, Qiaoxiang

    2018-01-15

    One-monomer molecularly imprinted magnetic nanoparticles were prepared as adsorbents for selective extraction of bisphenol A from water in this study. A single bi-functional monomer was adopted for preparation of the molecularly imprinted polymer, avoiding the tedious trial-and-error optimizations as traditional strategy. Moreover, bisphenol F was used as the dummy template for bisphenol A to avoid the interference from residual template molecules. These nanoparticles showed not only large adsorption capacity and good selectivity to the bisphenol A but also outstanding magnetic response performance. Furthermore, they were successfully used as magnetic solid-phase extraction adsorbents of bisphenol A from various water samples, including tap water, river water, and seawater. The developed method was found to be much more efficient, convenient, and economical for selective extraction of bisphenol A compared with the traditional solid-phase extraction. Separation of these nanoparticles can be easily achieved with an external magnetic field, and the optimized adsorption time was only 15 min. The recoveries of bisphenol A in different water samples ranged from 85.38 to 93.75%, with relative standard deviation lower than 7.47%. These results showed that one-monomer molecularly imprinted magnetic nanoparticles had the potential to be popular adsorbents for selective extraction of pollutants from water. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthesis and characterization of copolymers from hindered amines and vinyl monomers

    Directory of Open Access Journals (Sweden)

    Marcelo Aparecido Chinelatto

    2014-01-01

    Full Text Available New copolymers from hindered amines and vinyl monomers were synthesized by radical chain polymerization. To obtain polymeric HALS, acrylamide-(1ATP and acrylate-(4ATP monomers, derivatives from 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethyl-4-piperidinol were synthesized. The radical chain polymerization of 1ATP with styrene (Sty using 1-butanethiol (BTN resulted in a copolymer with 95 units of Sty and 15 units of 1ATP. The radical chain polymerization of 1ATP and vinyl acetate (VAc has produced only 1ATP homopolymer. In the chain polymerization of 4ATP with Sty or VAc, the hydrogen atom bonded to the nitrogen of 4ATP is labile enough to originate another radical at this site. The steric hindrance imposed by methyl groups on this bonding site hampers its reaction with other propagating species and the formation of a copolymer or network structure will be dependent on the size of the pendent group in the vinyl monomer.

  3. Enzyme-catalyzed hydrolysis of dentin adhesives containing a new urethane-based trimethacrylate monomer

    Science.gov (United States)

    Park, Jong-Gu; Ye, Qiang; Topp, Elizabeth M.; Spencer, Paulette

    2009-01-01

    A new trimethacrylate monomer with urethane-linked groups, 1,1,1-tri-[4-(methacryloxyethylamino-carbonyloxy)-phenyl]ethane (MPE), was synthesized, characterized, and used as a co-monomer in dentin adhesives. Dentin adhesives containing 2-hydroxyethyl methacrylate (HEMA, 45% w/w) and 2,2-bis[4(2-hydroxy-3-methacryloyloxy-propyloxy)-phenyl] propane (BisGMA, 30% w/w) in addition to MPE (25% w/w) were formulated with H2O at 0 (MPE0), 8 (MPE8) and 16 wt % water (MPE16) to simulate the wet demineralized dentin matrix and compared with controls [HEMA/BisGMA, 45/55 w/w, at 0 (C0), 8 (C8) and 16 wt% water (C16)]. The new adhesive showed a degree of double bond conversion and mechanical properties comparable with control, with good penetration into the dentin surface and a uniform adhesive/dentin interface. On exposure to porcine liver esterase, the net cumulative methacrylic acid (MAA) release from the new adhesives was dramatically (P < 0.05) decreased relative to the control, suggesting that the new monomer improves esterase resistance. PMID:19582843

  4. Jellium-model calculation for monomer and dimer decays of some potassium clusters

    International Nuclear Information System (INIS)

    Saito, Susumu; Cohen, M.L.; Lawrence Berkeley Lab., CA

    1989-01-01

    We have studied several decay processes of potassium clusters and found that a dimer-decay mechanism can explain the observed lowest abundance of K 10 in the K n mass spectra. Total-energy curves for decay processes are calculated using a jellium-background model for positive-ion cores and the local-spin-density-functional approximation for valence electrons. The energy-barrier height for a dimer decay of K 10 from the energy-minimum point is found to be 0.18 eV, which is a reasonable magnitude for the decay to take place thermally in the experiment. The monomer decay of K 9 and the dimer decay of K 11 , which are expected to be the most favorable decays of K 9 and K 11 , are found to have high barriers. Monomer and dimer decays of K 8 are also studied and the monomer decay is found to be more favorable, in accord with the high-nozzle-temperature mass spectrum. (orig.)

  5. Modification of polyethersulfone films by grafting hydrophilic monomers with 60Co γ-rays

    International Nuclear Information System (INIS)

    Hou Zhengchi; Deng Bo; Li Jing

    2006-01-01

    Polyethersulfone (PES), with its high strength, high temperature resistance, corrosion- resistance, oxidation resistance and applicability under wide pH range, is used extensively as ultrafiltration and nanofiltration membrane. However, PES membranes foul easily in such an application because of hydrophobic nature of PES raw materials. Improving the hydrophilicity of PES by grafting hydrophilic monomers onto it is of potential to solve the problem. At present, common approaches to improve hydrophilicity of PES membranes are UV grafting modification, plasma modification, and chemical modification, whereas grafting and modifying PES films by 60 Co γ-rays has rarely been reported. Studies have been carried out in our laboratory to graft hydrophilic monomers onto PES membranes directly or PES powders via simultaneous radiation grafting with the rays. Acrylic acid, methyl acrylic acid or acrylamide was used to study effects of the monomer concentration, irradiation dose and dose rate, solvent, inhibitor and pH of the grafting solution on the degree of grafting. The results showed that hydrophilicity of all the PES membranes could be improved, with the extent of improvement being dependent on the grafting conditions. (authors)

  6. NGAL (Lcn2) monomer is associated with tubulointerstitial damage in chronic kidney disease.

    Science.gov (United States)

    Nickolas, Thomas L; Forster, Catherine S; Sise, Meghan E; Barasch, Nicholas; Solá-Del Valle, David; Viltard, Melanie; Buchen, Charles; Kupferman, Shlomo; Carnevali, Maria Luisa; Bennett, Michael; Mattei, Silvia; Bovino, Achiropita; Argentiero, Lucia; Magnano, Andrea; Devarajan, Prasad; Mori, Kiyoshi; Erdjument-Bromage, Hediye; Tempst, Paul; Allegri, Landino; Barasch, Jonathan

    2012-09-01

    The type and the extent of tissue damage inform the prognosis of chronic kidney disease (CKD), but kidney biopsy is not a routine test. Urinary tests that correlate with specific histological findings might serve as surrogates for the kidney biopsy. We used immunoblots and ARCHITECT-NGAL assays to define the immunoreactivity of urinary neutrophil gelatinase-associated lipocalin (NGAL) in CKD, and we used mass spectroscopy to identify associated proteins. We analyzed kidney biopsies to determine whether specific pathological characteristics associated with the monomeric NGAL species. Advanced CKD urine contained the NGAL monomer as well as novel complexes of NGAL. When these species were separated, we found a significant correlation between the NGAL monomer and glomerular filtration rate (r=-0.53, P<0.001), interstitial fibrosis (mild vs. severe disease; mean 54 vs. 167 μg uNGAL/g Cr, P<0.01), and tubular atrophy (mild vs. severe disease; mean 54 vs. 164 μg uNGAL/g Cr, P<0.01). Monospecific assays of the NGAL monomer demonstrated a correlation with histology that typifies progressive, severe CKD.

  7. A new label dosimetry system based on pentacosa-diynoic acid monomer for low dose applications

    International Nuclear Information System (INIS)

    Abdel-Fattah, A.A.; Abdel-Rehim, F.; Soliman, Y.S.

    2012-01-01

    The dosimetric characteristics of γ-radiation sensitive labels based on polyvinyl butyral (PVB) and a conjugated diacetylene monomer, 10,12-pentacosa-diynoic acid (PCDA) have been investigated using reflectance colorimeter. Two types of labels (colourless and yellow) based on PCDA monomer were prepared using an Automatic Film Applicator System. Upon γ-ray exposure, the colourless label turns progressively blue, while the yellow colour label turns to green then to dark blue. The colour intensity of the labels is proportional to the radiation absorbed dose. The useful dose range was 15 Gy-2 kGy depending on PCDA monomer concentration. The expanded uncertainty of dose measurement of the colourless label was 6.06 (2σ). - Highlights: → Using 10,12-pentacosa-diynoic acid (PCDA) in preparation of label dosimeter. → PCDA polymerises upon γ-rays exposure producing a blue coloured polymer. → Useful dose range is 15 Gy to 2 kGy depending on concentration of PCDA. → Overall uncertainty of label dosimeter was 6.06 at 2σ.

  8. A new label dosimetry system based on pentacosa-diynoic acid monomer for low dose applications

    Energy Technology Data Exchange (ETDEWEB)

    Abdel-Fattah, A.A.; Abdel-Rehim, F. [National Center for Radiation Research and Technology, Atomic Energy Authority, P.O. Box 8029, Nasr City, Cairo (Egypt); Soliman, Y.S., E-mail: yasser_shabaan@hotmail.com [National Center for Radiation Research and Technology, Atomic Energy Authority, P.O. Box 8029, Nasr City, Cairo (Egypt)

    2012-01-15

    The dosimetric characteristics of {gamma}-radiation sensitive labels based on polyvinyl butyral (PVB) and a conjugated diacetylene monomer, 10,12-pentacosa-diynoic acid (PCDA) have been investigated using reflectance colorimeter. Two types of labels (colourless and yellow) based on PCDA monomer were prepared using an Automatic Film Applicator System. Upon {gamma}-ray exposure, the colourless label turns progressively blue, while the yellow colour label turns to green then to dark blue. The colour intensity of the labels is proportional to the radiation absorbed dose. The useful dose range was 15 Gy-2 kGy depending on PCDA monomer concentration. The expanded uncertainty of dose measurement of the colourless label was 6.06 (2{sigma}). - Highlights: > Using 10,12-pentacosa-diynoic acid (PCDA) in preparation of label dosimeter. > PCDA polymerises upon {gamma}-rays exposure producing a blue coloured polymer. > Useful dose range is 15 Gy to 2 kGy depending on concentration of PCDA. > Overall uncertainty of label dosimeter was 6.06 at 2{sigma}.

  9. Kinetic behaviour of graft copolymerisation of nitrogenous heterocyclic monomer onto EB-irradiated ETFE films

    International Nuclear Information System (INIS)

    Paveswari Sithambaranathan; Arshad Ahmad; Mohamed Mahmoud Nasef; Universiti Teknologi Malaysia Campus, Kuala Lumpur

    2015-01-01

    Kinetic behaviour of graft copolymerisation of a nitrogenous heterocyclic monomer, 4-vinylpyridine (4-VP), onto electron beam irradiated poly(ethylene-co-tetrafluoroethylene) (ETFE) films was investigated in correlation with reaction parameters (absorbed dose, monomer concentration and reaction temperature). This was established by determination of initial polymerisation rate (r p0 ), characteristic radical recombination rate (γ) and delay time (t 0 ). The orders of the dependence of the initial rate of grafting on the absorbed dose and monomer concentration were found to be 2.28 and 3.49, respectively. The effect of temperature was investigated in the range of 50-70 deg C and the activation energy was determined. The incorporation of poly(4-VP) grafts and the accompanied chemical changes in the grafted ETFE films were monitored using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, respectively. The results of the present study showed that a quantitative kinetic description for grafting of 4-VP onto ETFE can be established and the degree of grafting can be tuned by controlling the reaction parameters. (author)

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

    Science.gov (United States)

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

    2016-05-17

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

  11. Permeability of different types of medical protective gloves to acrylic monomers.

    Science.gov (United States)

    Lönnroth, Emma-Christin; Wellendorf, Hanne; Ruyter, Eystein

    2003-10-01

    Dental personnel and orthopedic surgeons are at risk when manually handling products containing methyl methacrylate (MMA). Dental products may also contain cross-linking agents such as ethylene glycol dimethacrylate (EGDMA) or 1,4-butanediol dimethacrylate (1,4-BDMA). Skin contact with monomers can cause hand eczema, and the protection given by gloves manufactured from different types of material is not well known. The aim of this study was to determine the breakthrough time (BTT, min) as a measure of protection (according to the EU standard EN-374-3) for a mixture consisting of MMA, EGDMA and 1,4-BDMA. Fifteen different gloves representing natural rubber latex material, synthetic rubber material (e.g. nitrile rubbers), and synthetic polymer material were tested. The smallest monomer MMA permeated within 3 min through all glove materials. A polyethylene examination glove provided the longest protection period to EGDMA and 1, 4-BDMA (> 120 min and 25.0 min), followed by the surgical glove Tactylon (6.0 min and 8.7 min) and the nitrile glove Nitra Touch (5.0 min and 8.7 min). This study showed that the breakthrough time (based on permeation rate) cannot be regarded as a 'safe limit'. When the permeation rate is low, monomers may have permeated before BTT can be determined. Using double gloves with a synthetic rubber inner glove and a natural rubber outer glove provided longer protection when the inner glove was rinsed in water before placing the outer glove on top.

  12. 1 / n Expansion for the Number of Matchings on Regular Graphs and Monomer-Dimer Entropy

    Science.gov (United States)

    Pernici, Mario

    2017-08-01

    Using a 1 / n expansion, that is an expansion in descending powers of n, for the number of matchings in regular graphs with 2 n vertices, we study the monomer-dimer entropy for two classes of graphs. We study the difference between the extensive monomer-dimer entropy of a random r-regular graph G (bipartite or not) with 2 n vertices and the average extensive entropy of r-regular graphs with 2 n vertices, in the limit n → ∞. We find a series expansion for it in the numbers of cycles; with probability 1 it converges for dimer density p diverges as |ln(1-p)| for p → 1. In the case of regular lattices, we similarly expand the difference between the specific monomer-dimer entropy on a lattice and the one on the Bethe lattice; we write down its Taylor expansion in powers of p through the order 10, expressed in terms of the number of totally reducible walks which are not tree-like. We prove through order 6 that its expansion coefficients in powers of p are non-negative.

  13. Improved i-motif thermal stability by insertion of anthraquinone monomers

    DEFF Research Database (Denmark)

    Gouda, Alaa S; Amine, Mahasen S.; Pedersen, Erik Bjerregaard

    2017-01-01

    In order to gain insight into how to improve thermal stability of i-motifs when used in the context of biomedical and nanotechnological applications, novel anthraquinone-modified i-motifs were synthesized by insertion of 1,8-, 1,4-, 1,5- and 2,6-disubstituted anthraquinone monomers into the TAA...... loops of a 22mer cytosine-rich human telomeric DNA sequence. The influence of the four anthraquinone linkers on the i-motif thermal stability was investigated at 295 nm and pH 5.5. Anthraquinone monomers modulate the i-motif stability in a position-depending manner and the modulation also depends...... unlocked nucleic acid monomers or twisted intercalating nucleic acid. The 2,6-disubstituted anthraquinone linker replacing T10 enabled a significant increase of i-motif thermal melting by 8.2 °C. A substantial increase of 5.0 °C in i-motif thermal melting was recorded when both A6 and T16 were modified...

  14. Effect of reactive monomer on PS-b-P2VP film.

    Science.gov (United States)

    Kim, H J; Shin, D M

    2014-08-01

    Poly(styrene-b-2-vinyl pyridine) (PS-b-P2VP) lamellar film which is hydrophobic block-hydrophilic polyelectrolyte block polymer of 52 kg/mol-b-57 kg/mol and PS-b-P2VP film with reactive monomer (RM257) were prepared for photonic gel films. The lamellar stacks, which is alternating layer of hydrophilic and hydrophobic moiety of PS-b-P2VP, were obtained by exposing the spin coated film under chloroform vapor. The lamellar films were quaternized with 5 wt% of iodomethane diluted by n-hexane. We reported about the influence of reactive monomer on those photonic gel films. Added reactive monomer photonic gel film had higher absorbance than pure photonic gel films. As a result the photonic gel film with RM had more clear color. The lamellar films were swollen by DI water, ethanol (aq) and calcium carbonate solution. The band gaps of the lamellar films were drastically shifted to longer wavelength swollen by calcium carbonate solution. And the lamellar films were shifted to shorter wave length swollen by ethanol. So each lamellar film showed different color.

  15. Copolymerization parameters of N-Methacryloyloxy tetrabromophthalimide with different vinyl monomers

    International Nuclear Information System (INIS)

    Mahmoud, A.A.

    2005-01-01

    N-Methacryloyloxytetrabromophthalimide (NMTP) was synthesized by the reaction of N-hydroxytetrabromophthalimide with either methacryloyl chloride or methacrylic acid in the presence of triethylamine or N, Ndicyclohexylcarbodiimide respectively. Binary copolymerization reactions of the prepared monomer with ethyl acrylate (EA), n-butyl methacrylate (n.BMA), tertiary butylacrylate (t.BA) and vinyl acetate (VA) were performed in methylene chloride at 65 degree C using 1 mol % azobisisobutylronitrile (AIBN) as initiator. The structure of the prepared monomer was investigated by IR and 1H NMR spectroscopy. The copolymer compositions were determined from bromine analysis. Copolymerization parameters for each system were calculated by the Fineman-Ross and Kelen-Tudos methods. The monomer reactivity ratios for the systems NMTP-EA, NMTP-n.BMA, NMTP-t.BA and NMTP-VA were found to be r1 0.180, r2 = 0.893, r1 = 0.025, r2 = 0.680, r1 0.014, r2 0.956 and r1 1.002, r2 1.004 respectively

  16. Two Functionally Distinct Sources of Actin Monomers Supply the Leading Edge of Lamellipodia

    Science.gov (United States)

    Vitriol, Eric A.; McMillen, Laura M.; Kapustina, Maryna; Gomez, Shawn M.; Vavylonis, Dimitrios; Zheng, James Q.

    2015-01-01

    Summary Lamellipodia, the sheet-like protrusions of motile cells, consist of networks of actin filaments (F-actin) regulated by the ordered assembly from and disassembly into actin monomers (G-actin). Traditionally, G-actin is thought to exist as a homogeneous pool. Here, we show that there are two functionally and molecularly distinct sources of G-actin that supply lamellipodial actin networks. G-actin originating from the cytosolic pool requires the monomer binding protein thymosin β4 (Tβ4) for optimal leading edge localization, is targeted to formins, and is responsible for creating an elevated G/F-actin ratio that promotes membrane protrusion. The second source of G-actin comes from recycled lamellipodia F-actin. Recycling occurs independently of Tβ4 and appears to regulate lamellipodia homeostasis. Tβ4-bound G-actin specifically localizes to the leading edge because it doesn’t interact with Arp2/3-mediated polymerization sites found throughout the lamellipodia. These findings demonstrate that actin networks can be constructed from multiple sources of monomers with discrete spatiotemporal functions. PMID:25865895

  17. Effect of polyfunctional monomers on properties of radiation crosslinked EPDM/waste tire dust blend

    International Nuclear Information System (INIS)

    Yasin, Tariq; Khan, Sajid; Nho, Young-Chang; Ahmad, Rashid

    2012-01-01

    In this study, waste tire dust is recycled as filler and blended with ethylene-propylene diene monomer (EPDM) rubber. Three different polyfuntional monomers (PFMs) are incorporated into the standard formulation and irradiated under electron beam at different doses up to maximum of 100 kGy. The combined effects of PFMs and absorbed dose on the physical properties of EPDM/WTD blend are measured and compared with sulfur crosslinked formulation. Thermogravimetric analysis showed that radiation developed better crosslinked network with higher thermal stability than sulfur crosslinked structure. The physical properties of radiation crosslinked blend are similar to the sulfur crosslinked blend. The absence of toxic chemicals/additives in radiation crosslinked blends made them an ideal candidate for many applications such as roof sealing sheets, water retention pond, playground mat, sealing profile for windows etc. - Highlights: ► We have recycled waste tire dust and blended it with EPDM. ► EB crosslinking is carried in the presence of polyfuntional monomers. ► Radiation gave better network with higher thermal stability than sulfur. ► The absence of toxic chemicals in EB blends will increase its acceptability.

  18. Bioaccumulation study of acrylate monomers in algae (Chlorella Kessleri) by PY-GC and PY-GC/MS

    International Nuclear Information System (INIS)

    Halas, L.; Orinak, A.; Adamova, M.; Ladomersky, J.

    2004-01-01

    Acrylate monomers methylmethacrylate (MMA) and cyclohexylmethacrylate (CHMA) bioaccumulation has been determined in aquatic organism, algae (Chlorella kessleri). Algae were collected in amount of 0.4 mg and directly injected to the paralytic cell. In algae bodies accumulated monomers were analysed by pyrolysis gas chromatography (Py-GC) and pyrolysis gas chromatography coupled with mass spectrometry (Py-GC/MS). Traces of the accumulated monomers in algae body can be determined after 1-, 2 -, 3-weeks of incubation. Maximum content of MMA was determined after 3-week of experiment, contrariwise in the case of CHMA after 2-week exposition. Relationship with pyrolysis temperature has also been studied. (authors)

  19. Simple introduction of sulfonic acid group onto polyethylene by radiation-induced cografting of sodium styrenesulfonate with hydrophilic monomers

    International Nuclear Information System (INIS)

    Tsuneda, Satoshi; Saito, Kyoichi; Furusaki, Shintaro; Sugo, Takanobu; Makuuchi, Keizo

    1993-01-01

    The sulfonic acid (SO 3 H) group was readily introduced into a polyethylene (PE) membrane by radiation-induced cografting of sodium styrenesulfonate (SSS) with hydrophilic monomers such as acrylic acid (AAc) and hydroxyethyl methacrylate (HEMA). The density of SSS grafted onto the PE membrane was determined as a function of molar ratio of hydrophilic monomer to SSS in the monomer mixture. Immersion of the electron-beam-irradiated PE membrane into the mixture of SSS and HEMA for 5 h at 323 K provided to the SO 3 H density of 2.5 mol/kg of the H-type product

  20. Synthesis and characterization of zinc-organic frameworks with 1,4-benzenedicarboxylic acid and azobenzene-4,4'-dicarboxylic acid

    Science.gov (United States)

    Nguyen, Van Hung; Phuong Thuy Nguyen, Ngoc; Tuyet Nhung Nguyen, Thi; Thanh Thuy Le, Thi; Nghiem Le, Van; Chinh Nguyen, Quoc; Quang Ton, That; Hoang Nguyen, Thai; Phuong Thoa Nguyen, Thi

    2011-06-01

    The solvothermal reactions of 1,4-bezenedicarboxylic acid (H2BDC) or azobenzene-4,4'-dicarboxylic acid (H2ABD) with zinc ions/clusters lead to the formation of four crystalline materials. All of these compounds were characterized by x-ray diffraction, optical microscopy, thermo-gravimetric analysis and nitrogen adsorption. Block-shaped crystals (BZ1) with various shapes and sizes were obtained at H2BDC:Zn mole ratio of 1:1 and H2BDC concentration of 0.1 M. At more dilute H2BDC concentration of 0.01 M and H2BDC:Zn mole ratio of 1 : 4, the reaction product was cubic crystals (BZ2) with a size of 250 μm. In the H2ABD system, flat-plate-like crystals (AZ1) were obtained at H2ABD:Zn mole ratio of 1 : 1 and H2ABD concentration of 0.01 M. Meanwhile, thick-block-like crystals (AZ2) were formed at the same H2ABD:Zn mole ratio but at 0.004 M H2ABD. The Langmuir surface area (SLang) of the materials was remarkable, enhanced by diluting the reaction solution. For the compounds synthesized in N,N'-dimethylformamide (DMF), SLang increased from 304.6 m2 g-1 for BZ1 to 2631 m2 g-1 for BZ2 and from 475.8 m2 g-1 for AZ1 to 3428 m2 g-1 for AZ2. Meanwhile, BZ2 synthesized in N,N'-diethylformamide (BZ2/DEF) got the highest SLang of 4330 m2 g-1. Both AZ2 and BZ2 materials were stable up to 400 °C.

  1. Effect of monomer concentration on the kinetics of emulsifier-free emulsion polymerization of Vinyl Acetate and Methyl Acrylate

    International Nuclear Information System (INIS)

    Mohammad Beigi, H. R.

    2001-01-01

    The effect of monomer concentration on the kinetics of the emulsifier-free emulsion polymerization of vinyl acetate and methyl acrylate were studied. The polymerizations were carried out using potassium persulfate as the initiator. Form the electron micrographs of the resulting lattices, monodisperse PVAc and PMA lattices with particle diameters varying between 149-443 mm and 112-497 nm, respectively were processed. Uniformity of particle size indicated that nucleation of stable particle occurs early in the polymerization process. The polymerization rate was found to be proportional to the 0.88 and 1.5 power of the initial monomer concentration of vinyl acetate and methyl acrylate, respectively. Higher monomer concentration results in fewer particles and larger final particle diameter. With increasing monomer solubility in water the size of particle decreases and its distribution broadens

  2. Influence of Monomer Concentration on the Morphologies and Electrochemical Properties of PEDOT, PANI, and PPy Prepared from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Shalini Kulandaivalu

    2016-01-01

    Full Text Available Poly(3,4-ethylenedioxyhiophene (PEDOT, polyaniline (PANI, and polypyrrole (PPy were prepared on indium tin oxide (ITO substrate via potentiostatic from aqueous solutions containing monomer and lithium perchlorate. The concentration of monomers was varied between 1 and 10 mM. The effects of monomer concentration on the polymers formation were investigated and compared by using Fourier transform infrared spectroscopy (FTIR, Raman spectroscopy, scanning electron microscopy (SEM, cyclic voltammetry (CV, and electrochemical impedance spectroscopy (EIS measurements. FTIR and Raman spectra showed no changes in the peaks upon the increment of the concentration. Based on the SEM images, the increment in monomer concentration gives significant effect on morphologies and eventually affects the electrochemical properties. PEDOT electrodeposited from 10 mM solution showed excellent electrochemical properties with the highest specific capacitance value of 12.8 mF/cm2.

  3. Fluorescent oligonucleotides containing a novel perylene 2′-amino-α-L-LNA monomer: Synthesis and analytical potential

    DEFF Research Database (Denmark)

    Astakhova, Irina; Kumar, Santhosh T.; Wengel, Jesper

    2011-01-01

    efficiency of the resulting perylene-2'-amino-alpha-L-LNA monomer (T*) into synthetic oligonucleotides was significantly improved by replacement of the typically used 1H-tetrazole activator with pyridine hydrochloride. Generally, oligonucleotides containing monomer T* showed high binding affinity towards...... incorporations of monomers T* was quenched (quantum yield Phi(F) = 0.21) relative to duplexes of this probe with complementary DNA and RNA (Phi(F) = 0.42 and 0.35, respectively). On the contrary, a strong fluorescence quenching upon target binding was demonstrated by two short oligonucleotides of analogues...... sequences containing monomers T* at 5'- and 3'-terminal positions. We explain the hybridization-induced light-up effect observed for double-labeled probe by a reduction of fluorescence quenching due to precise positioning of the fluorophores within the double-stranded complexes. Furthermore, we propose...

  4. Photo-induced isomerization of ethylene-bridged azobenzene explored by ab initio based non-adiabatic dynamics simulation: A comparative investigation of the isomerization in the gas and solution phases

    Energy Technology Data Exchange (ETDEWEB)

    Cao Jun; Liu Lihong; Fang Weihai [Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875 (China); Xie Zhizhong [Department of Chemistry, School of Science, Wuhan University of Technology, Wuhan 430070 (China); Zhang Yong [Department of Chemistry, Chemical Biology, and Biomedical Engineering, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, New Jersey 07030 (United States)

    2013-04-07

    Azobenzene is one of the most widely used photoactive units and recently an ethylene-bridged azobenzene (BAB) was reported to have greatly enhanced conversion efficiency, quantum yield, and other favorable properties. As the first step towards exploring its photo-switchable character in real systems, we report here a systematic study on the photoisomerization dynamics between trans (E) and cis (Z) isomers in the gas phase and the CH{sub 3}OH solution, using ab initio based surface hopping and molecular dynamics, which is the first report of dynamics simulation to reveal the environmental effects on BAB photoreactions. Results show that while the relatively faster S{sub 1} relaxation of the photo-induced E{yields}Z process is only mildly affected by the solvent effect, the relatively slower S{sub 1} relaxation of the reverse reaction becomes even slower in the solution compared to the gas phase. The subsequent S{sub 0} dynamics from the conical intersection between S{sub 1} and S{sub 0} (CI{sub E}) to Z is accelerated in solution compared to the gas phase because of avoided re-crossing to the S{sub 1} state, while the S{sub 0} dynamics from the conical intersection between S{sub 1} and S{sub 0} (CI{sub Z}) to E are basically the same in both phases. Overall, the solvent effect was found to enhance the back-and-forth photo-switch efficiency between the Z and E isomers compared to the gas phase, while the quantum yields are reduced. But the solution yields of both the forward and backward photoreactions are still around 0.4. Therefore, BAB may have good photo-responsive properties if used as a photoactive unit in real systems. These results will facilitate future experimental and theoretical studies in this area to help design new azobenzene derivatives as photoactive units in biological processes, nanoscale devices, and photo-responsive materials.

  5. Conformationally locked aryl C-nucleosides: synthesis of phosphoramidite monomers and incorporation into single-stranded DNA and LNA (locked nucleic acid)

    DEFF Research Database (Denmark)

    Babu, B. Ravindra; Prasad, Ashok K.; Trikha, Smriti

    2002-01-01

    . The phosphoramidite approach was used for automated incorporation of the LNA-type beta-configured C-aryl monomers 17a-17e into short DNA and 2'-OMe-RNA/LNA strands. It is shown that universal hybridization can be obtained with a conformationally restricted monomer as demonstrated most convincingly for the pyrene LNA...... monomer 17d, both in a DNA context and in an RNA-like context. Increased binding affinity of oligonucleotide probes for universal hybridization can be induced by combining the pyrene LNA monomer 17d with affinity-enhancing 2'-OMe-RNA/LNA monomers....

  6. Computational Modeling and Theoretical Calculations on the Interactions between Spermidine and Functional Monomer (Methacrylic Acid in a Molecularly Imprinted Polymer

    Directory of Open Access Journals (Sweden)

    Yujie Huang

    2015-01-01

    Full Text Available This paper theoretically investigates interactions between a template and functional monomer required for synthesizing an efficient molecularly imprinted polymer (MIP. We employed density functional theory (DFT to compute geometry, single-point energy, and binding energy (ΔE of an MIP system, where spermidine (SPD and methacrylic acid (MAA were selected as template and functional monomer, respectively. The geometry was calculated by using B3LYP method with 6-31+(d basis set. Furthermore, 6-311++(d, p basis set was used to compute the single-point energy of the above geometry. The optimized geometries at different template to functional monomer molar ratios, mode of bonding between template and functional monomer, changes in charge on natural bond orbital (NBO, and binding energy were analyzed. The simulation results show that SPD and MAA form a stable complex via hydrogen bonding. At 1 : 5 SPD to MAA ratio, the binding energy is minimum, while the amount of transferred charge between the molecules is maximum; SPD and MAA form a stable complex at 1 : 5 molar ratio through six hydrogen bonds. Optimizing structure of template-functional monomer complex, through computational modeling prior synthesis, significantly contributes towards choosing a suitable pair of template-functional monomer that yields an efficient MIP with high specificity and selectivity.

  7. Effect of Laser-assisted and Conventional In-office Bleaching on Monomer Release from Microhybrid and Nanohybrid Composite.

    Science.gov (United States)

    Omrani, Ladan Ranjbar; Farjadfar, Shayan; Pedram, Parham; Sadray, Sima; Kamangar, Sedighe Sadat Hashemi; Chiniforoush, Nasim

    2017-06-30

    Bleaching might affect structural properties of composite materials, and lead to monomer release. This study aimed to evaluate the effect of Laser-assisted and conventional in-office bleaching on the release of BIS-GMA, TEGDMA, and UDMA monomers from a nanohybrid and a microhybrid BIS-GMA based composite. 32 samples of each composite, were divided into 4 subgroups; subgroup 1: Conventional in-office bleaching (CIB) with the Opalescence Boost PF 38% gel, subgroup 2: Laser-assisted bleaching (LBO) with the Opalescence Boost PF 38% gel, subgroup 3: Laser-assisted bleaching (LBH) with the JW Power bleaching gel, subgroup 4: (CO) control without bleaching. All the samples were immersed in tubes of 2cc Ethanol 75% medium. The released monomers were analyzed using the high performance liquid chromatography (HPLC) method 24 h, 7, and 28 days. Data's were analyzed by Univariate Analysis of Variance test followed by Tukeys HSD. The amount of TEGDMA monomer released was not significant. However, nanohybrid composites showed significantly more monomer release than microhybrid composites (P Bleaching by laser with JW Power Bleaching gel led to more monomer release in nanohybrid composite.

  8. Graft copolymers of polyurethane with various vinyl monomers via radiation-induced miniemulsion polymerization: Influential factors to grafting efficiency and particle morphology

    Energy Technology Data Exchange (ETDEWEB)

    Wang Hua [CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China (USTC), Hefei, Anhui 230026 (China); Wang Mozhen [CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China (USTC), Hefei, Anhui 230026 (China)], E-mail: pstwmz@ustc.edu.cn; Ge Xuewu [CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China (USTC), Hefei, Anhui 230026 (China)], E-mail: xwge@ustc.edu.cn

    2009-02-15

    Graft copolymers of polyurethane (PU) with various vinyl monomers were synthesized through a one-pot but two-step miniemulsion polymerization process. Firstly, the polycondensation of isophorone diisocyanate (IPDI) with hydroxyl-terminated polybutadiene (HTPB) had been performed in aqueous miniemulsion at 40 deg. C in order to obtain PU dispersions. Consecutively, an in-situ graft copolymerization of the vinyl monomers with the synthesized PU was initiated by {gamma}-ray radiation at room temperature. The grafting efficiency of PU with vinyl monomer (G{sub PU/monomer}) was calculated from {sup 1}H NMR spectra and the particle morphology of the final hybrid latex was observed by transmission electron microscopy (TEM). As there was no monomer transferring in miniemulsion system, homogenous hybrid particles would be synthesized provided that the monomer was miscible with PU, such as styrene. With the increase of the polarity of the monomer, the compatibility of PU with monomer decreased. G{sub PU/monomer} varied as G{sub PU/styrene}(37%)>G{sub PU/butyl} {sub acrylate} {sub (BA)}(21%)>G{sub PU/methyl} {sub methacrylate} {sub (MMA)}(12%). The proportion of homogeneous nucleation would increase as the hydrophilicity of the monomer increased. High temperature would destabilize the miniemulsion so as to result in a less grafting efficiency. Compared to the phase separation during the seeded emulsion polymerization, the miniemulsion polymerization method facilitated the preparation of homogeneous materials owing to its monomer droplet nucleation mechanism.

  9. Fabrication of Surface Protein-Imprinted Nanoparticles Using a Metal Chelating Monomer via Aqueous Precipitation Polymerization.

    Science.gov (United States)

    Li, Wei; Sun, Yan; Yang, Chongchong; Yan, Xianming; Guo, Hao; Fu, Guoqi

    2015-12-16

    Molecular imprinting is a promising way for constructing artificial protein recognition materials, but it has been challenged by difficulties such as restricted biomacromolecule transfer in the cross-linked polymer networks, and reduced template-monomer interactions that are due to the required aqueous media. Herein, we propose a strategy for imprinting of histidine (His)-exposed proteins by combining previous approaches such as surface imprinting over nanostructures, utilization of metal coordination interactions, and adoption of aqueous precipitation polymerization capable of forming reversible physical crosslinks. With lysozyme as a model template bearing His residues, imprinted polymer nanoshells were grafted over vinyl-modified nanoparticles by aqueous precipitation copolymerization of a Cu(2+) chelating monomer with a temperature-responsive monomer carried out at 37 °C, above the volume phase-transition temperature (VPTT) of the final copolymer. The imprinted nanoshells showed significant temperature sensitivity and the template removal could be facilitated by swelling of the imprinted layers at 4 °C, below the VPTT. The resultant core-shell imprinted nanoparticles exhibited strikingly high rebinding selectivity against a variety of nontemplate proteins. An imprinting factor up to 22.7 was achieved, which is among the best values reported for protein imprinting, and a rather high specific binding capacity of 67.3 mg/g was obtained. Moreover, this approach was successfully extended to preliminary imprinting of hemoglobin, another protein with accessible His. Therefore, it may be a versatile method for fabrication of high-performance surface-imprinted nanoparticles toward His-exposed proteins.

  10. High-resolution structure of a retroviral protease folded as a monomer

    International Nuclear Information System (INIS)

    Gilski, Miroslaw; Kazmierczyk, Maciej; Krzywda, Szymon; Zábranská, Helena; Cooper, Seth; Popović, Zoran; Khatib, Firas; DiMaio, Frank; Thompson, James; Baker, David; Pichová, Iva; Jaskolski, Mariusz

    2011-01-01

    The crystal structure of Mason–Pfizer monkey virus protease folded as a monomer has been solved by molecular replacement using a model generated by players of the online game Foldit. The structure shows at high resolution the details of a retroviral protease folded as a monomer which can guide rational design of protease dimerization inhibitors as retroviral drugs. Mason–Pfizer monkey virus (M-PMV), a D-type retrovirus assembling in the cytoplasm, causes simian acquired immunodeficiency syndrome (SAIDS) in rhesus monkeys. Its pepsin-like aspartic protease (retropepsin) is an integral part of the expressed retroviral polyproteins. As in all retroviral life cycles, release and dimerization of the protease (PR) is strictly required for polyprotein processing and virion maturation. Biophysical and NMR studies have indicated that in the absence of substrates or inhibitors M-PMV PR should fold into a stable monomer, but the crystal structure of this protein could not be solved by molecular replacement despite countless attempts. Ultimately, a solution was obtained in mr-rosetta using a model constructed by players of the online protein-folding game Foldit. The structure indeed shows a monomeric protein, with the N- and C-termini completely disordered. On the other hand, the flap loop, which normally gates access to the active site of homodimeric retropepsins, is clearly traceable in the electron density. The flap has an unusual curled shape and a different orientation from both the open and closed states known from dimeric retropepsins. The overall fold of the protein follows the retropepsin canon, but the C α deviations are large and the active-site ‘DTG’ loop (here NTG) deviates up to 2.7 Å from the standard conformation. This structure of a monomeric retropepsin determined at high resolution (1.6 Å) provides important extra information for the design of dimerization inhibitors that might be developed as drugs for the treatment of retroviral infections

  11. Prediction of monomer isomery in Florine: a workflow dedicated to nonribosomal peptide discovery.

    Directory of Open Access Journals (Sweden)

    Thibault Caradec

    Full Text Available Nonribosomal peptides represent a large variety of natural active compounds produced by microorganisms. Due to their specific biosynthesis pathway through large assembly lines called NonRibosomal Peptide Synthetases (NRPSs, they often display complex structures with cycles and branches. Moreover they often contain non proteogenic or modified monomers, such as the D-monomers produced by epimerization. We investigate here some sequence specificities of the condensation (C and epimerization (E domains of NRPS that can be used to predict the possible isomeric state (D or L of each monomer in a putative peptide. We show that C- and E- domains can be divided into 2 sub-regions called Up-Seq and Down-Seq. The Up-Seq region corresponds to an InterPro domain (IPR001242 and is shared by C- and E-domains. The Down-Seq region is specific to the enzymatic activity of the domain. Amino-acid signatures (represented as sequence logos previously described for complete C-and E-domains have been restricted to the Down-Seq region and amplified thanks to additional sequences. Moreover a new Down-Seq signature has been found for Ct-domains found in fungi and responsible for terminal cyclization of the peptides. The identification of these signatures has been included in a workflow named Florine, aimed to predict nonribosomal peptides from NRPS sequence analyses. In some cases, the prediction of isomery is guided by genus-specific rules. Florine was used on a Pseudomonas genome to allow the determination of the type of pyoverdin produced, the update of syringafactin structure and the identification of novel putative products.

  12. A model study of aggregates composed of spherical soot monomers with an acentric carbon shell

    Science.gov (United States)

    Luo, Jie; Zhang, Yongming; Zhang, Qixing

    2018-01-01

    Influences of morphology on the optical properties of soot particles have gained increasing attentions. However, studies on the effect of the way primary particles are coated on the optical properties is few. Aimed to understand how the primary particles are coated affect the optical properties of soot particles, the coated soot particle was simulated using the acentric core-shell monomers model (ACM), which was generated by randomly moving the cores of concentric core-shell monomers (CCM) model. Single scattering properties of the CCM model with identical fractal parameters were calculated 50 times at first to evaluate the optical diversities of different realizations of fractal aggregates with identical parameters. The results show that optical diversities of different realizations for fractal aggregates with identical parameters cannot be eliminated by averaging over ten random realizations. To preserve the fractal characteristics, 10 realizations of each model were generated based on the identical 10 parent fractal aggregates, and then the results were averaged over each 10 realizations, respectively. The single scattering properties of all models were calculated using the numerically exact multiple-sphere T-matrix (MSTM) method. It is found that the single scattering properties of randomly coated soot particles calculated using the ACM model are extremely close to those using CCM model and homogeneous aggregate (HA) model using Maxwell-Garnett effective medium theory. Our results are different from previous studies. The reason may be that the differences in previous studies were caused by fractal characteristics but not models. Our findings indicate that how the individual primary particles are coated has little effect on the single scattering properties of soot particles with acentric core-shell monomers. This work provides a suggestion for scattering model simplification and model selection.

  13. Pseudomonas syringae evades host Immunity by degrading flagellin monomers with alkaline protease AprA

    OpenAIRE

    Pel, M.J.C.; Van Dijken, A.J.H.; Bardoel, B.W.; Seidl, M.F; Van der Ent, S.; Van Strijp, J.A.G.

    2014-01-01

    Bacterial flagellin molecules are strong inducers of innate immune responses in both mammals and plants. The opportunistic pathogen Pseudomonas aeruginosa secretes an alkaline protease called AprA that degrades flagellin monomers. Here, we show that AprA is widespread among a wide variety of bacterial species. In addition, we investigated the role of AprA in virulence of the bacterial plant athogen P. syringae pv. tomato DC3000. The AprA-deficient DC3000 ΔaprA knockout mutant was significantl...

  14. Inverse problem for the mean-field monomer-dimer model with attractive interaction

    International Nuclear Information System (INIS)

    Contucci, Pierluigi; Luzi, Rachele; Vernia, Cecilia

    2017-01-01

    The inverse problem method is tested for a class of monomer-dimer statistical mechanics models that contain also an attractive potential and display a mean-field critical point at a boundary of a coexistence line. The inversion is obtained by analytically identifying the parameters in terms of the correlation functions and via the maximum-likelihood method. The precision is tested in the whole phase space and, when close to the coexistence line, the algorithm is used together with a clustering method to take care of the underlying possible ambiguity of the inversion. (paper)

  15. Migration of formaldehyde and melamine monomers from kitchen- and tableware made of melamine plastic

    DEFF Research Database (Denmark)

    Lund, K.H.; Petersen, J.H.

    2006-01-01

    Migration of one or both formaldehyde and/or melamine monomers was found in seven of ten tested melamine samples bought on the Danish market. The samples were a bowl, a jug, a mug, a ladle, and different cups and plates. No violation of the European Union-specific migration limits for melamine (30...... mg kg(-1)) and formaldehyde (15 mg kg(-1)) was found after three successive exposures to the food stimulant 3% acetic acid after 2 h at 70 degrees C. To investigate the effects of long-term use, migration tests were performed with two types of cups from a day nursery. Furthermore, medium-term use...

  16. Radiation induced grafting of monomers onto natural rubber : processes and applications

    International Nuclear Information System (INIS)

    Sunny Sebastian, M.

    2001-01-01

    Full text: Certain inherent mechanical properties of natural rubber (NR) can be modified by grafting vinyl monomers onto the polymer backbone. This paper described the gamma radiation induced graft copolymerization of methyl methacrylate (MMA), styrene and acrylonitrile (AN) onto NR. The graft copolymers can be crosslinked by sulphur and organic accelerators. The crosslinked graft copolymers show improved modulus and hardness in their films compared to NR. However the tensile strength of the films is reduced by grafting. The methods for preparing the graft copolymers, their properties and applications are briefly described

  17. Radiation grafting from binary monomer mixtures. II. Vinyl ether of monoethanolamine and N-vinylpyrrolidone

    International Nuclear Information System (INIS)

    Nurkeeva, Zauresh S.; Abdel Aal, A.-S.; Kupchishin, Anatoliy I.; Khutoryanskiy, Vitaliy V.; Mun, Grigoriy A.; Beksyrgaeva, Aida G.

    2003-01-01

    Radiation grafting from binary monomer mixtures of vinyl ether of monoethanolamine and N-vinylpyrrolidone onto polyethylene films has been studied. The structure of the grafted films was characterized by FTIR spectroscopy. Water uptake and contact angle measurements confirmed that the grafting leads to a considerable hydrophilization of the films surface. The presence of the more active N-vinylpyrrolidone enhances the grafting of the less active vinyl ether of monoethanolamine. Sorption properties of grafted films with respect to copper (II) ions have been studied

  18. INS as a probe of inter-monomer angles in polymers

    CERN Document Server

    Eijck, L V; Grozema, F C; Schepper, I M D; Kearley, G J

    2002-01-01

    The angle between monomers in conjugated polymers plays an important role in their conductivity. The vibrational spectrum is sensitive to this angle and can be used to probe the distribution of angles in poorly crystalline systems. We show that the INS spectrum is correctly calculated for bithiophene and shows the molecule to be planar in the solid - in agreement with crystallographic measurements. Poor agreement between observed and calculated spectra in the 700-cm sup - sup 1 region may be due to dynamic coupling, but this does not detract from the angle-sensitivity of the spectra. (orig.)

  19. Effect of Rhizopus oryzae Fermentation on Kenaf-Based Polylactic Acid’s Monomer

    OpenAIRE

    Nur Aimi Mohd Nasir; Mohd Adlan Mustafa Kamalbahrin; Nurhafizah Mohamad; Hazleen Anuar; Maizirwan Mel; and Rashidi Othman

    2011-01-01

    Kenaf biomass is the potential as raw materials used to produce polylactic acid's monomer which is lactic acid via fermentation by Rhizopus oryzae. Kenaf biomass' structure is complex due to its lignin and cellulose content. This matter had encouraged it to undergo pre- treatment process as the initial step before fermentation process can be done. In this paper, kenaf biomass was treated with dilute sulphuric acid (H2SO4) to hydrolyze the cellulose content in it as well as to convert the cell...

  20. Communication: Remarkable electrophilicity of the oxalic acid monomer: An anion photoelectron spectroscopy and theoretical study

    International Nuclear Information System (INIS)

    Buonaugurio, Angela; Graham, Jacob; Buytendyk, Allyson; Bowen, Kit H.; Ryder, Matthew R.; Gutowski, Maciej; Keolopile, Zibo G.; Haranczyk, Maciej

    2014-01-01

    Our experimental and computational results demonstrate an unusual electrophilicity of oxalic acid, the simplest dicarboxylic acid. The monomer is characterized by an adiabatic electron affinity and electron vertical detachment energy of 0.72 and 1.08 eV (±0.05 eV), respectively. The electrophilicity results primarily from the bonding carbon-carbon interaction in the singly occupied molecular orbital of the anion, but it is further enhanced by intramolecular hydrogen bonds. The well-resolved structure in the photoelectron spectrum is reproduced theoretically, based on Franck-Condon factors for the vibronic anion → neutral transitions

  1. Effect of the fluorinated groups on nematic liquid crystal alignment on monomer crosslinked film

    International Nuclear Information System (INIS)

    Yu Tao; Peng Zenghui; Ruan Shengping; Xuan Li

    2004-01-01

    It was found in this work that photosensitive monomers, bisphenol A dicinnamate ester and hexafluorobiphenol a dicinnamate ester were crosslinked under irradiation of linearly polarized ultraviolet light. The exposed films induced homogeneous and homeotropic alignment of liquid crystals (LC), respectively. We verified through experiments that it was fluorinated groups that caused the generation of LC homeotropic alignment on the crosslinked film. Photoreaction process was revealed by Fourier transform infrared spectra. There was no clear morphological anisotropy on these aligned films observed through atomic force microscope analysis. The surface energies were measured and homeotropic alignment reason was discussed in this work

  2. Synthesis and properties of 1,3-dioxo-1H-inden-2(3H)-ylidene fragment and (3-(dicyanomethylene)-5,5-dimethylcyclohex-1-enyl)vinyl fragment containing derivatives of azobenzene for holographic recording materials

    Science.gov (United States)

    Zarins, Elmars; Kokars, Valdis; Ozols, Andris; Augustovs, Peteris

    2011-06-01

    New glassy 1,3-dioxo-1H-inden-2(3H)-ylidene fragment und (3-(dicyanomethylene)-5,5-dimethylcyclohex-1-enyl)vinyl fragment containing push-pull type derivatives of azobenzene able to create thin layers have been synthesized. Thin films of synthesized glasses for holographic recording were prepared using spin coating technique from saturated chloroform solution. Holographic grating recording in films of 6a-b, 7 and 12 has been experimentally studied at 633 and 532 nm in both transmission and reflection modes with p-p recording beam polarizations. The film 12 was found to be the most efficient at both wavelengths in transmission mode exhibiting the maximum self-diffraction efficiency of 9.9% at 633 nm, and 15.3% at 532 nm. The film of 6a was the most efficient in reflection mode with the maximum selfdiffraction efficiency of about 3%.

  3. Initial Reactivity of Linkages and Monomer Rings in Lignin Pyrolysis Revealed by ReaxFF Molecular Dynamics.

    Science.gov (United States)

    Zhang, Tingting; Li, Xiaoxia; Guo, Li

    2017-10-24

    The initial conversion pathways of linkages and their linked monomer units in lignin pyrolysis were investigated comprehensively by ReaxFF MD simulations facilitated by the unique VARxMD for reaction analysis. The simulated molecular model contains 15 920 atoms and was constructed on the basis of Adler's softwood lignin model. The simulations uncover the initial conversion ratio of various linkages and their linked aryl monomers. For linkages and their linked monomer aryl rings of α-O-4, β-O-4 and α-O-4 & β-5, the C α /C β ether bond cracking dominates the initial pathway accounting for at least up to 80% of their consumption. For the linkage of β-β & γ-O-α, both the C α -O ether bond cracking and its linked monomer aryl ring opening are equally important. Ring-opening reactions dominate the initial consumption of other 4-O-5, 5-5, β-1, β-2, and β-5 linkages and their linked monomers. The ether bond cracking of C α -O and C β -O occurs at low temperature, and the aryl ring-opening reactions take place at relatively high temperature. The important intermediates leading to the stable aryl ring opening are the phenoxy radicals, the bridged five-membered and three-membered rings and the bridged six-membered and three-membered rings. In addition, the reactivity of a linkage and its monomer aryl ring may be affected by other linkages. The ether bond cracking of α-O-4 and β-O-4 linkages can activate its neighboring linkage or monomer ring through the formed phenoxy radicals as intermediates. The important intermediates revealed in this article should be of help in deepening the understanding of the controlling mechanism for producing aromatic chemicals from lignin pyrolysis.

  4. Effects of (monomer - crosslinker – initiator) composition during non imprinted polymers synthesis for catechin retention

    Science.gov (United States)

    Triadhi, U.; Zulfikar, M. A.; Setiyanto, H.; Amran, M. B.

    2018-05-01

    MISPE (molecularly imprinted Solid Phase Extraction) is a separation technique using a solid adsorbent as a principle of MI (molecularly imprinted). Methacrylic acid (MAA) was used as a monomer, ethylene glycol dimethacrylate (EGDMA) as a crosslinker, benzoyl peroxide (BPO) as an initiator and acetonitrile (ACN) as a porogen. Catechin will be used as the template. Thermal and microwave methods were employed in the synthesis method. When analyzed using FTIR spectra, it was found that there were no significant differences between NIP (non-imprinted polymer) resulting from thermal method and that resulting from microwave method. Preparation of polymers by microwave method required 4 mins at 60-65 °C, significantly less than thermal method, that took 60 minutes at the same temperature. The variations of mole ratios of the monomer, the crosslinker, and the initiator were also performed. Based on the FTIR spectra, intensity of some peaks were changed due to the decreases of concentration. The optimum composition for NIP synthesis was MAA: EGDMA: BPO ratio of 5:30:0.5 (in mmole). The TGA curve showed that the NIP sythesized using microwave method experienced mass loss of around 98.50% at 604.8 °C.

  5. Influence of monomer on structure, processing and application characteristics of UV curable urethane acrylate composite coatings

    International Nuclear Information System (INIS)

    Grigale-Sorocina, Z; Kalnins, M; Gross, K A

    2016-01-01

    Increased interest in the esthetical natural nail coatings have encouraged more in-depth studies particularly of UV curable coatings: their formation, processing, structure, characteristics and removing. Typical requirement for nail coatings is good adhesion, but preferably for the short time of functioning (usual 2-4 weeks). This study investigated the impact of four different monomers (tertiobutyl cyclohexyl acrylate (TBCHA), ethylene glycol dimethacrylate (EGDMA), tetrahydrofurfuryl acrylate (THFA), hydroxypropyl methacrylate (HPMA)) to viscosity of uncured mixture and degree of conversion, mechanical properties, surface gloss, micro hardness and adhesion loss for cured films. Specific coating application requires comparatively high coating flexibility and stability of deformation characteristics. This can be achieved with composition containing 30% of monomer TBCHA, what shows ultimate elongation ε B = 0,23 - 0,24, modulus of elasticity E = 670-710 MPa and comparatively constant properties in 72 hours (ΔE = 1.3%, Δε B =6.0%). A composition with 40% of TBCHA shows the fastest coating destruction achieving adhesion loss within 3 min. (paper)

  6. Electron beam initiated modification of acrylic elastomer in presence of polyfunctional monomers

    International Nuclear Information System (INIS)

    Vijayabaskar, V.; Bhattacharya, S.; Tikku, V.K.; Bhowmick, A.K.

    2004-01-01

    The structural changes of an acrylic rubber (ACM) in presence and absence of polyfunctional monomers like trimethylolpropane triacrylate, tripropyleneglycol diacrylate, trimethylolmethane tetraacrylate and trimethylolpropane trimethacrylate at different doses of electron beam (EB) irradiations were investigated with the help of FTIR spectroscopy (in the attenuated total reflectance mode) and sol-gel analysis. As the radiation dose increases, the concentration of carbonyl group increases in the ACM rubber due to aerial oxidation. This is corroborated from the increase in the absorbance values at 1734 and 1160 cm -1 , which are due to carbonyl and C-O-C stretching frequencies, respectively. The increase in crosslinking is revealed by the increase in percentage gel content with radiation dose. The lifetime of spurs formed and the critical dose, an important criterion for overlapping of spurs have been determined for both grafted and ungrafted ACM rubber using a mathematical model. The predominance of crosslinking by electronic stopping with energetic EB projectile and the increase in effective radius of crosslinking have also been verified by this model. The doses at which the synergistic occurrence of both dislinking and endlinking steps originate have been calculated using linear energy transfer of EB. The ratio of scissioning to crosslinking for ACM rubber has been determined by using Charlesby-Pinner equation. The mechanical properties have been studied for different modified and unmodified systems and the tensile strength is found to increase with grafting of polyfunctional monomers

  7. Assembly of one-dimensional supramolecular objects: From monomers to networks

    Science.gov (United States)

    Sayar, Mehmet; Stupp, Samuel I.

    2005-07-01

    One-dimensional supramolecular aggregates can form networks at exceedingly low concentrations. Recent experiments in several laboratories, including our own, have demonstrated the formation of gels by these systems at concentrations well under 1% by weight. The systems of interest in our laboratory form either cylindrical nanofibers or ribbons as a result of strong noncovalent interactions among monomers. The stiffness and interaction energies among these thread-like objects can vary significantly depending on the chemical structure of the monomers used. We have used Monte Carlo simulations to study the structure of the threads and their ability to form networks through bundle formation. The persistence length of the threads was found to be strongly affected not only by stiffness, but also by the strength of attractive two-body interactions among thread segments. The relative values of stiffness and attractive two-body interaction strength determine if threads collapse or create bundles. Only in the presence of sufficiently long threads and bundle formation can these systems assemble into networks of high connectivity.

  8. Inhibition of Protein Tyrosine Phosphatase 1B by Aurintricarboxylic Acid and Methylenedisalicylic Acid: Polymer versus Monomer

    International Nuclear Information System (INIS)

    Shrestha, Suja; Lee, Keun Hyeung; Cho, Hyeong Jin

    2004-01-01

    In this study, we examined whether the in vitro inhibitory activity of ATA against PTPases resides in the monomer or high molecular weight components. Not to mention commercial ATA, the ATA sample synthesized according to the method previously reported to produce monomer was also found to contain polymeric materials as described below. Therefore, monomeric component of ATA was prepared absolutely free of polymer. Also synthesized in a pure form was methylenedisalicylic acid (MDSA), one of the low molecular weight components formed in the conventional preparation of ATA. Commercial MDSA was also proved to contain polymeric substances. The inhibitory potency of ATA and MDSA synthesized in a polymer-free form was evaluated against human protein tyrosine phosphatase 1B (PTP1B). Commercial ATA, however, contains significant amounts of polymeric materials schematically represented as. In general, ATA is prepared by condensation of salicylic acid with formaldehyde and the branching reaction results in the formation of polymers of molecular weights up to several thousands Dalton

  9. Roasting conditions for preserving cocoa flavan-3-ol monomers and oligomers: interesting behaviour of Criollo clones.

    Science.gov (United States)

    De Taeye, Cédric; Bodart, Marie; Caullet, Gilles; Collin, Sonia

    2017-09-01

    Cocoa bean roasting is important for creating the typical chocolate aroma through Maillard reactions, but it is also a key step deleterious to the polyphenol content and profile. Compared with usual roasting at 150 °C, keeping the beans for 30 min at 120 °C or for 1 h at 90 °C proved much better for preventing strong degradation of native P1, P2 and P3 flavan-3-ols in cocoa (shown for Forastero, Trinitatio and Criollo cultivars). Surprisingly, Cuban, Mexican and Malagasy white-seeded beans behaved atypically when roasted for 30 min at 150 °C, releasing a pool of catechin. Enantiomeric chromatographic separation proved that this pool contained mainly (-)-catechin issued from (-)-epicatechin by epimerisation. As the (-)-epicatechin content remained relatively constant through Criollo bean roasting, flavan-3-ol monomers must have been regenerated from oligomers. This emergence of (-)-catechin in Criollo beans only, reported here for the first time, could be due to increased flavan-3-ol monomer stability in the absence of anthocyanidin-derived products. The degradation rate of flavan-3-ols through roasting is higher in cocoa beans containing anthocyani(di)ns. The liberation of a pool of (-)-catechin when submitted to roasting at 150 °C allows to distinguish white-seeded cultivars. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  10. Redesign of the monomer–monomer interface of Cre recombinase yields an obligate heterotetrameric complex

    Science.gov (United States)

    Zhang, Chi; Myers, Connie A.; Qi, Zongtai; Mitra, Robi D.; Corbo, Joseph C.; Havranek, James J.

    2015-01-01

    Cre recombinase catalyzes the cleavage and religation of DNA at loxP sites. The enzyme is a homotetramer in its functional state, and the symmetry of the protein complex enforces a pseudo-palindromic symmetry upon the loxP sequence. The Cre-lox system is a powerful tool for many researchers. However, broader application of the system is limited by the fixed sequence preferences of Cre, which are determined by both the direct DNA contacts and the homotetrameric arrangement of the Cre monomers. As a first step toward achieving recombination at arbitrary asymmetric target sites, we have broken the symmetry of the Cre tetramer assembly. Using a combination of computational and rational protein design, we have engineered an alternative interface between Cre monomers that is functional yet incompatible with the wild-type interface. Wild-type and engineered interface halves can be mixed to create two distinct Cre mutants, neither of which are functional in isolation, but which can form an active heterotetramer when combined. When these distinct mutants possess different DNA specificities, control over complex assembly directly discourages recombination at unwanted half-site combinations, enhancing the specificity of asymmetric site recombination. The engineered Cre mutants exhibit this assembly pattern in a variety of contexts, including mammalian cells. PMID:26365240

  11. Radiation-induced crosslinking of polyethylene in the presence of bifunctional vinyl monomers

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, M.S.

    1976-10-06

    The apparent crosslinking produced by the radiation grafting of two monomers to polyethylene, acrylic acid and acrylonitrile, was investigated. Evidence is presented to show that covalent crosslinks are not produced during the radiation grafting step; covalent crosslinks are produced by the post-irradiation heat treatment associated with measurements of gel; the enhancement in gel fraction and physical properties arises from true crosslinks rather than chain entanglements; and there may be practical value associated with the sensitization of crosslinking produced by the methods employed in this work. The effect of monomer-solvent composition on the graft and gel yield was studied. Viscoelastic properties of grafted films were determined above the melting point of pure polyethylene. The kinetic data, infrared spectra, and viscoelastic properties are the bases for the following mechanism: (1) Acrylic acid-g-PE: Acrylic acid enters the film in the form of a hydrogen bonded dimer and undergoes a grafting reaction that produces hydrogen-bond crosslinks. The heat treatment during the conventional methods for determining of crosslinks convert them into intermolecular anhydride bonds. (2) Acrylonitrile-g-PE: In this, the post-grafting crosslinking is the result of a thermally induced chain reaction leading to an uninterrupted conjugated sequence. The length of the ring structure increases with time and temperature, and the intensity of color increases with the length of the ring structure.

  12. Radiation-induced crosslinking of polyethylene in the presence of bifunctional vinyl monomers

    International Nuclear Information System (INIS)

    Joshi, M.S.

    1976-01-01

    The apparent crosslinking produced by the radiation grafting of two monomers to polyethylene, acrylic acid and acrylonitrile, was investigated. Evidence is presented to show that covalent crosslinks are not produced during the radiation grafting step; covalent crosslinks are produced by the post-irradiation heat treatment associated with measurements of gel; the enhancement in gel fraction and physical properties arises from true crosslinks rather than chain entanglements; and there may be practical value associated with the sensitization of crosslinking produced by the methods employed in this work. The effect of monomer-solvent composition on the graft and gel yield was studied. Viscoelastic properties of grafted films were determined above the melting point of pure polyethylene. The kinetic data, infrared spectra, and viscoelastic properties are the bases for the following mechanism: (1) Acrylic acid-g-PE: Acrylic acid enters the film in the form of a hydrogen bonded dimer and undergoes a grafting reaction that produces hydrogen-bond crosslinks. The heat treatment during the conventional methods for determining of crosslinks convert them into intermolecular anhydride bonds. (2) Acrylonitrile-g-PE: In this, the post-grafting crosslinking is the result of a thermally induced chain reaction leading to an uninterrupted conjugated sequence. The length of the ring structure increases with time and temperature, and the intensity of color increases with the length of the ring structure

  13. Multiple routes and milestones in the folding of HIV-1 protease monomer.

    Directory of Open Access Journals (Sweden)

    Massimiliano Bonomi

    Full Text Available Proteins fold on a time scale incompatible with a mechanism of random search in conformational space thus indicating that somehow they are guided to the native state through a funneled energetic landscape. At the same time the heterogeneous kinetics suggests the existence of several different folding routes. Here we propose a scenario for the folding mechanism of the monomer of HIV-1 protease in which multiple pathways and milestone events coexist. A variety of computational approaches supports this picture. These include very long all-atom molecular dynamics simulations in explicit solvent, an analysis of the network of clusters found in multiple high-temperature unfolding simulations and a complete characterization of free-energy surfaces carried out using a structure-based potential at atomistic resolution and a combination of metadynamics and parallel tempering. Our results confirm that the monomer in solution is stable toward unfolding and show that at least two unfolding pathways exist. In our scenario, the formation of a hydrophobic core is a milestone in the folding process which must occur along all the routes that lead this protein towards its native state. Furthermore, the ensemble of folding pathways proposed here substantiates a rational drug design strategy based on inhibiting the folding of HIV-1 protease.

  14. Preliminary study of acrylamide monomer decomposition during methane fermentation of dairy waste sludge.

    Science.gov (United States)

    Mroczek, Ewelina; Konieczny, Piotr; Lewicki, Andrzej; Waśkiewicz, Agnieszka; Dach, Jacek

    2016-07-01

    Polyacrylamide (PAM) used in sludge dewatering exists widely in high-solid anaerobic digestion. Acrylamide is registered in the list of chemicals demonstrating toxic, carcinogenic and mutagenic properties. Therefore, it is reasonable to ask about the mobility of such residual substances in the environment. The study was carried out to assess the impact of the mesophilic (39±1°C) and thermophilic (54±1°C) fermentation process on the level of acrylamide monomer (AMD) content in the dairy sludge. The material was analysed using high-performance liquid chromatography (HPLC) for quantification of AMD. The results indicate that the process of methane fermentation continues regardless of the temperature effects on the degradation of AMD in dairy sludge. The degree of reduction of acrylamide monomer for thermophilic fermentation is 100%, while for mesophilic fermentation it is 91%. In practice, this means that biogas technology eliminates the risk of AMD migration to plant tissue. Moreover, it should be stressed that 90% of cumulative biogas and methane production was reached one week earlier under thermophilic conditions - the dynamics of the methanisation process were over 20% faster. Copyright © 2016. Published by Elsevier B.V.

  15. [Preparation of clear thermosetting resin for veneered crown from several bisMEPP monomers (author's transl)].

    Science.gov (United States)

    Tanaka, T; Nakabayashi, N; Masuhara, E

    1978-07-01

    The whitish translucent shade of a thermosetting resin cured from a mixture of a 2,2-Bis (p-methacryloxy (ethoxy)1-2 phenyl)-propane monomer and PMMA pearls makes it difficult to reconstruct a shade of the natural tooth. The attempt to improve the transparency of the mixed polymer was made in this study. Varying the molecular weight of BisMEPP monomer, PMMA polymer and curing temperature, cured specimens were prepared and their transparency was measured with a spectrophotometer. The results obtained are as follows. 1) In any molecular weight of PMMA, BisMEPP with 2.3 to 3.3 average number of ethylene oxide linkage showed the highest transpalency on the specimen. 2) With increasing the curing temperature, transpalency of the specimens made from BisME4.0 PP increased. With another molecular of BisMEPP, transpalency of the cured specimens showed the highest transpalency at the curing temperature of 120 degrees C. 3) With increasing the molecular weight of PMMA, the transpalency increased.

  16. 13C Kinetic isotopic effect of polymerization on monomers with multiple bond

    International Nuclear Information System (INIS)

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

    1988-01-01

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

  17. Silver Nanocube and Nanobar Growth via Anisotropic Monomer Addition and Particle Attachment Processes.

    Science.gov (United States)

    Xiao, Dongdong; Wu, Zhigang; Song, Miao; Chun, Jaehun; Schenter, Gregory K; Li, Dongsheng

    2018-01-30

    Understanding the growth mechanism of noble metal nanocrystals during solution synthesis is of significant importance for shape and property control. However, much remains unknown about the growth pathways of metal nanoparticles due to the lack of direct observation. Using an in situ transmission electron microscopy technique, we directly observed Ag nanocube and nanobar growth in an aqueous solution through both classical monomer-by-monomer addition and nonclassical particle attachment processes. During the particle attachment process, Ag nanocubes and nanobars were formed via both oriented and nonoriented attachment. Our calculations, along with the dynamics of the observed attachment, showed that the van der Waals force overcomes hydrodynamic and friction forces and drives the particles toward each other at separations of 10-100 nm in our experiments. During classical growth, anisotropic growth was also revealed, and the resulting unsymmetrical shape constituted an intermediate state for Ag nanocube growth. We hypothesized that the temporary symmetry breaking resulted from different growth rates on (001) surfaces due to a local surface concentration variation caused by the imbalance between the consumption of Ag + near the surface and the diffusion of Ag + from the bulk to the surface.

  18. Synthesis and characterisation of new Schiff base monomers containing N-(alkyl and phenyl) pyrrole moieties

    Science.gov (United States)

    Amer, Ahcene Ait; Ilikti, Hocine; Maschke, Ulrich

    2017-11-01

    This article deals with the synthesis and characterisation of seven new functional Schiff base monomers, such as: M1: 1-(3-Pyrrole-1-yl-propylimino-methyl)-naphtalen-2-ol; M2: 2-(3-Pyrrole-1-yl-phenylimino-methyl)-phenol; M3: 1-(3-Pyrrole-1-yl-phenylimino-methyl)-naphtalen-2-ol; M4: N-(pyridin-2-yl-methylene)-2-(pyrrol-1-yl)-benzenamine; M5: N-(pyridin-2-yl-methylene)-3-(pyrrol-1-yl)-propan-1-amine; M6: 2-(3-pyrrol-1-yl-propylimino-methyl)-quinolin-8-ol; M7: 2-(3-pyrrol-1-yl-phenylimino-methyl)-quinolin-8-ol. Two series of compounds emerged from this study, N-propyl pyrrole derivatives (M1, M5, M6) and N-phenyl pyrrole compounds (M2, M3, M4, M7). All monomers were elaborated by condensation reactions between appropriate amines and aldehydes, and their molecular structures were confirmed by spectroscopic analysis methods like FT-IR, 1H NMR, 13C NMR, and GC-MS.

  19. Direct nanoimprint lithography of Al2O3 using a chelated monomer-based precursor

    International Nuclear Information System (INIS)

    Ganesan, Ramakrishnan; Dinachali, Saman Safari; Lim, Su Hui; Saifullah, M S M; He, Chaobin; Low, Hong Yee; Chong, Wee Tit; Lim, Andrew H H; Yong, Jin Jie; Thian, Eng San

    2012-01-01

    Nanostructuring of Al 2 O 3 is predominantly achieved by the anodization of aluminum film and is limited to obtaining porous anodized aluminum oxide (AAO). One of the main restrictions in developing approaches for direct fabrication of various types of Al 2 O 3 patterns, such as lines, pillars, holes, etc, is the lack of a processable aluminum-containing resist. In this paper, we demonstrate a stable precursor prepared by reacting aluminum tri-sec-butoxide with 2-(methacryloyloxy)ethyl acetoacetate, a chelating monomer, which can be used for large area direct nanoimprint lithography of Al 2 O 3 . Chelation in the precursor makes it stable against hydrolysis whilst the presence of a reactive methacrylate group renders it polymerizable. The precursor was mixed with a cross-linker and their in situ thermal free-radical co-polymerization during nanoimprinting rigidly shaped the patterns, trapped the metal atoms, reduced the surface energy and strengthened the structures, thereby giving a ∼100% yield after demolding. The imprinted structures were heat-treated, leading to the loss of organics and their subsequent shrinkage. Amorphous Al 2 O 3 patterns with line-widths as small as 17 nm were obtained. Our process utilizes the advantages of sol–gel and methacrylate routes for imprinting and at the same time alleviates the disadvantages associated with both these methods. With these benefits, the chelating monomer route may be the harbinger of the universal scheme for direct nanoimprinting of metal oxides. (paper)

  20. Copolymerization of 4-Acetylphenyl Methacrylate with Ethyl Methacrylate: Synthesis, Characterization, Monomer Reactivity Ratios, and Thermal Properties

    Directory of Open Access Journals (Sweden)

    Gamze Barim

    2014-01-01

    Full Text Available Methacrylates have high glass transition temperature (Tg values and high thermal stability. A new methacrylate copolymer, poly(4-acetylphenyl methacrylate-co-ethyl methacrylate (APMA-co-EMA, was synthesized. The thermal behaviors of copolymers were investigated by differential scanning calorimetry and thermogravimetric analysis. They behaved as new single polymers with single Tg’s and the thermal stability of the copolymers increased with increasing 4-acetylphenyl methacrylate (APMA fraction, leading to the manufacture of copolymers with desired Tg values. Structure and composition of copolymers for a wide range of monomer feed ratios were determined by Fourier transform infrared (FT-IR and 1H-nuclear magnetic resonance (1H-NMR spectroscopic techniques. Copolymerization reactions were continued up to 40% conversions. The monomer reactivity ratios for copolymer system were determined by the Kelen-Tüdös (ra(APMA=0.81; rb(EMA=0.61 and extended Kelen-Tüdös (ra=0.77; rb=0.54 methods and a nonlinear least squares (ra=0.74; rb=0.49 method.

  1. An investigation of the chemical stability of a monomer/polymer gel dosimeter

    International Nuclear Information System (INIS)

    De Deene, Y.; De Wagter, C.; De Neve, W.; Achten, E.

    2000-01-01

    The aim of this work is to investigate the temporal stability of a polyacrylamide gelatin hydrogel used for 3D monomer/polymer gel dosimetry techniques involving different methods of analysis. Long-term instabilities for a similar gel have recently been reported, but differ markedly from those described in this work. Two kinds of long-term instabilities are described. One affects the slope of the dose-R 2 plot and is related to post-irradiation polymerization of the comonomer/polymer aggregates. It is observed that post-irradiation polymerization only lasts 12 hours after irradiation. The other instability affects the intercept of the dose-R 2 plot, lasts for up to 30 days and is related to the gelation process of gelatin. Further studies were performed on gelatin gels of varying compositions to obtain a better understanding of the molecular mechanism that causes the instability due to gelation. The studies included observations of the spin-spin and spin-lattice relaxation rates in combination with diffusion measurements and optical measurements. It is shown that the heating history during the manufacture of the gel affects the absolute R 2 value of the gel but not its variation. The findings presented in this study may help in producing more stable and reproducible monomer/polymer gel dosimeters. (author)

  2. Monomer-dimer control of the ColE1 P(cer) promoter.

    Science.gov (United States)

    Chatwin, H M; Summers, D K

    2001-11-01

    XerCD-mediated recombination at cer converts multimers of plasmid ColE1 to monomers, maximizing the number of independently segregating molecules and minimizing the frequency of plasmid loss. In addition to XerCD, recombination requires the accessory factors ArgR and PepA. The promoter P(cer), located centrally within cer, is also required for stable plasmid maintenance. P(cer) is active in plasmid multimers and directs transcription of a short RNA, Rcd, which appears to inhibit cell division. It has been proposed that Rcd is part of a checkpoint which ensures that multimer resolution is complete before the cell divides. This study has shown that ArgR does not act as a transcriptional repressor of P(cer) in plasmid monomers. P(cer) is unusual in that the -35 and -10 hexamers are separated by only 15 bp and this study has demonstrated that increasing this to a more conventional spacing results in elevated activity. An increase to 17 bp resulted in a 10- to 20-fold increase in activity, while smaller effects were seen when the spacer was increased to 16 bp or 18 bp. These observations are consistent with the hypothesis that P(cer) activation involves realignment of the -35 and -10 sequences within a recombinational synaptic complex. This predicts that a 17 bp spacer promoter derivative should be down-regulated by plasmid multimerization, and this is confirmed experimentally.

  3. Radical Copolymerization Kinetics of Bio-Renewable Butyrolactone Monomer in Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Sharmaine B. Luk

    2017-10-01

    Full Text Available The radical copolymerization kinetics of acrylamide (AM and the water-soluble monomer sodium 4-hydroxy-4-methyl-2-methylene butanoate (SHMeMB, formed by saponification of the bio-sourced monomer γ-methyl-α-methylene-γ-butyrolactone (MeMBL, are investigated to explain the previously reported slow rates of reaction during synthesis of superabsorbent hydrogels. Limiting conversions were observed to decrease with increased temperature during SHMeMB homopolymerization, suggesting that polymerization rate is limited by depropagation. Comonomer composition drift also increased with temperature, with more AM incorporated into the copolymer due to SHMeMB depropagation. Using previous estimates for the SHMeMB propagation rate coefficient, the conversion profiles were used to estimate rate coefficients for depropagation and termination (kt. The estimate for kt,SHMeMB was found to be of the same order of magnitude as that recently reported for sodium methacrylate, with the averaged copolymerization termination rate coefficient dominated by the presence of SHMeMB in the system. In addition, it was found that depropagation still controlled the SHMeMB polymerization rate at elevated temperatures in the presence of added salt.

  4. Noise-and delay-induced phase transitions of the dimer–monomer surface reaction model

    International Nuclear Information System (INIS)

    Zeng Chunhua; Wang Hua

    2012-01-01

    Highlights: ► We study the dimer–monomer surface reaction model. ► We show that noise induces first-order irreversible phase transition (IPT). ► Combination of noise and time-delayed feedback induce first- and second-order IPT. ► First- and second-order IPT is viewed as noise-and delay-induced phase transitions. - Abstract: The effects of noise and time-delayed feedback in the dimer–monomer (DM) surface reaction model are investigated. Applying small delay approximation, we construct a stochastic delayed differential equation and its Fokker–Planck equation to describe the state evolution of the DM reaction model. We show that the noise can only induce first-order irreversible phase transition (IPT) characteristic of the DM model, however the combination of the noise and time-delayed feedback can simultaneously induce first- and second-order IPT characteristics of the DM model. Therefore, it is shown that the well-known first- and second-order IPT characteristics of the DM model may be viewed as noise-and delay-induced phase transitions.

  5. New Insights Toward Quantitative Relationships between Lignin Reactivity to Monomers and Their Structural Characteristics.

    Science.gov (United States)

    Ma, Ruoshui; Zhang, Xiumei; Wang, Yi; Zhang, Xiao

    2018-04-27

    The heterogeneous and complex structural characteristics of lignin present a significant challenge to predict its processability (e.g. depolymerization, modifications etc) to valuable products. This study provides a detailed characterization and comparison of structural properties of seven representative biorefinery lignin samples derived from forest and agricultural residues, which were subjected to representative pretreatment methods. A range of wet chemistry and spectroscopy methods were applied to determine specific lignin structural characteristics such as functional groups, inter-unit linkages and peak molecular weight. In parallel, oxidative depolymerization of these lignin samples to either monomeric phenolic compounds or dicarboxylic acids were conducted, and the product yields were quantified. Based on these results (lignin structural characteristics and monomer yields), we demonstrated for the first time to apply multiple-variable linear estimations (MVLE) approach using R statistics to gain insight toward a quantitative correlation between lignin structural properties and their conversion reactivity toward oxidative depolymerization to monomers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

    Directory of Open Access Journals (Sweden)

    Dagmar R. D'hooge

    2014-04-01

    Full Text Available Based on kinetic Monte Carlo simulations of the monomer sequences of a representative number of copolymer chains (≈ 150,000, optimal synthesis procedures for linear gradient copolymers are proposed, using bulk Initiators for Continuous Activator Regeneration Atom Transfer Radical Polymerization (ICAR ATRP. Methyl methacrylate and n-butyl acrylate are considered as comonomers with CuBr2/PMDETA (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine as deactivator at 80 °C. The linear gradient quality is determined in silico using the recently introduced gradient deviation ( polymer property. Careful selection or fed-batch addition of the conventional radical initiator I2 allows a reduction of the polymerization time with ca. a factor 2 compared to the corresponding batch case, while preserving control over polymer properties ( ≈ 0.30; dispersity ≈ 1.1. Fed-batch addition of not only I2, but also comonomer and deactivator (50 ppm under starved conditions yields a below 0.25 and, hence, an excellent linear gradient quality for the dormant polymer molecules, albeit at the expense of an increase of the overall polymerization time. The excellent control is confirmed by the visualization of the monomer sequences of ca. 1000 copolymer chains.

  7. Chemo-enzymatic Synthesis of Clickable Xylo-oligosaccharide Monomers from Hardwood 4-O-Methylglucuronoxylan.

    Science.gov (United States)

    MacCormick, Benjamin; Vuong, Thu V; Master, Emma R

    2018-02-12

    A chemo-enzymatic pathway was developed to transform 4-O-methylglucuronic acid (MeGlcpA) containing xylo-oligosaccharides from beechwood into clickable monomers capable of polymerizing at room temperature and in aqueous conditions to form unique polytriazoles. While the gluco-oligosaccharide oxidase (GOOX) from Sarocladium strictum was used to oxidize C6-propargylated oligosaccharides, the acid-amine coupling reagents 1-ethyl-3-(3-(dimethylamino)propyl) carbodiimide (EDAC) and 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM) were employed and compared for their ability to append click functionalities to carboxylic acid groups of enzyme-treated oligosaccharides. While DMT-MM was a superior coupling reagent for this application, a triazine side product was observed during C-1 amidation. Resulting bifunctional xylo-oligosaccharide monomers were polymerized using a Cu(I) catalyst, forming a soft gel which was characterized by 1 H NMR, confirming the triazole product.

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

    Science.gov (United States)

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

    2015-01-01

    Demineralized lesions in tooth enamel around orthodontic brackets are caused by acids from cariogenic biofilm. This study aimed to develop a novel antibacterial orthodontic cement by incorporating a quaternary ammonium monomer dimethylaminododecyl methacrylate (DMADDM) into a commercial orthodontic cement, and to investigate the effects on microcosm biofilm response and enamel bond strength. DMADDM, a recently-synthetized antibacterial monomer, was incorporated into orthodontic cement at 0%, 1.5%, 3% and 5% mass fractions. Bond strength of brackets to enamel was measured. A microcosm biofilm model was used to measure metabolic activity, lactic acid production, and colony-forming units (CFU) on orthodontic cements. Shear bond strength was not reduced at 3% DAMDDM (p > 0.1), but was slightly reduced at 5% DMADDM, compared to 0% DMADDM. Biofilm viability was substantially inhibited when in contact with orthodontic cement containing 3% DMADDM. Biofilm metabolic activity, lactic acid production, and CFU were much lower on orthodontic cement containing DMADDM than control cement (p orthodontic cement containing 3% DMADDM inhibited oral biofilms without compromising the enamel bond strength, and is promising to reduce or eliminate demineralization in enamel around orthodontic brackets. PMID:25035230

  9. Synthesis of Molecularly Imprinted Polymers for Amino Acid Derivates by Using Different Functional Monomers

    Directory of Open Access Journals (Sweden)

    Sonia Scorrano

    2011-03-01

    Full Text Available Fmoc-3-nitrotyrosine (Fmoc-3-NT molecularly imprinted polymers (MIPs were synthesized to understand the influence of several functional monomers on the efficiency of the molecular imprinting process. Acidic, neutral and basic functional monomers, such as acrylic acid (AA, methacrylic acid (MAA, methacrylamide (MAM, 2-vinylpyridine (2-VP, 4-vinylpyridine (4-VP, have been used to synthesize five different polymers. In this study, the MIPs were tested in batch experiments by UV-visible spectroscopy in order to evaluate their binding properties. The MIP prepared with 2-VP exhibited the highest binding affinity for Fmoc-3NT, for which Scatchard analysis the highest association constant (2.49 × 104 M−1 was obtained. Furthermore, titration experiments of Fmoc-3NT into acetonitrile solutions of 2-VP revealed a stronger bond to the template, such that a total interaction is observed. Non-imprinted polymers as control were prepared and showed no binding affinities for Fmoc-3NT. The results are indicative of the importance of ionic bonds formed between the –OH residues of the template molecule and the pyridinyl groups of the polymer matrix. In conclusion, 2-VP assists to create a cavity which allows better access to the analytes.

  10. Silver Nanocube and Nanobar Growth via Anisotropic Monomer Addition and Particle Attachment Processes

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Dongdong [Physical; Wu, Zhigang [School; Song, Miao [Physical; Chun, Jaehun [Physical; Schenter, Gregory K. [Physical; Li, Dongsheng [Physical

    2018-01-11

    Understanding the growth mechanism of noble metal nanocrystals during solution synthesis is of significant importance for shape and property control. However, much remains unknown about the growth pathways of metal nanoparticles due to lack of direct observation. Using an in-situ transmission electron microscopy technique, we directly observed Ag nanocube and nanobar growth in aqueous solution through both classical monomer-by-monomer addition and non-classical particle attachment processes. During the particle attachment process, Ag nanocubes and nanobars formed via both oriented and non-oriented attachment. Our calculations, along with dynamics of the observed attachment, showed that van der Waals force overcame hydrodynamic and friction forces and drove the particles toward each other. During classical growth, an anisotropic growth was also revealed, and the resulting unsymmetrical shape constituted an intermediate state for Ag nanocube growth. We hypothesized that the temporary symmetry breaking resulted from different growth rates on {001} surfaces due to a local surface concentration variation caused by the imbalance between the consumption of Ag+ near the surface and the diffusion of Ag+ from bulk to surface.

  11. Preparation of a Bis-GMA-Free Dental Resin System with Synthesized Fluorinated Dimethacrylate Monomers

    Directory of Open Access Journals (Sweden)

    Shuzhen Luo

    2016-12-01

    Full Text Available With the aim of reducing human exposure to Bisphenol A (BPA derivatives in dentistry, a fluorinated dimethacrylate monomer was synthesized to replace 2,2-bis[4-(2-hydroxy-3-methacryloy-loxypropyl-phenyl]propane (Bis-GMA as the base monomer of dental resin. After mixing with reactive diluent triethyleneglycol dimethacrylate (TEGDMA, fluorinated dimethacrylate (FDMA/TEGDMA was prepared and compared with Bis-GMA/TEGDMA in physicochemical properties, such as double bond conversion (DC, volumetric shrinkage (VS, water sorption (WS and solubility (WSL, flexural strength (FS and modulus (FM. The results showed that, when compared with Bis-GMA based resin, FDMA-based resin had several advantages, such as higher DC, lower VS, lower WS, and higher FS after water immersion. All of these revealed that FDMA had potential to be used as a substitute for Bis-GMA. Of course, many more studies, such as biocompatibility testing, should be undertaken to prove whether FDMA could be applied in clinic.

  12. Effects of molecular chirality on self-assembly and switching in liquid crystals at the cross-over between rod-like and bent shapes.

    Science.gov (United States)

    Ocak, Hale; Poppe, Marco; Bilgin-Eran, Belkız; Karanlık, Gürkan; Prehm, Marko; Tschierske, Carsten

    2016-09-21

    A bent-core compound derived from a 4-cyanoresorcinol core unit with two terephthalate based rod-like wings and carrying chiral 3,7-dimethyloctyloxy side chains has been synthesized in racemic and enantiomerically pure form and characterized by polarizing microscopy, differential scanning calorimetry, X-ray diffraction and electro-optical investigations to study the influence of molecular chirality on the superstructural chirality and polar order in lamellar liquid crystalline phases. Herein we demonstrate that the coupling of molecular chirality with superstructural layer chirality in SmCsPF domain phases (forming energetically distinct diastereomeric pairs) can fix the tilt direction and thus stabilize synpolar order, leading to bistable ferroelectric switching in the SmC* phases of the (S)-enantiomer, whereas tristable modes determine the switching of the racemate. Moreover, the mechanism of electric field induced molecular reorganization changes from a rotation around the molecular long axis in the racemate to a rotation on the tilt-cone for the (S)-enantiomer. At high temperature the enantiomer behaves like a rod-like molecule with a chirality induced ferroelectric SmC* phase and an electroclinic effect in the SmA'* phase. At reduced temperature sterically induced polarization, due to the bent molecular shape, becomes dominating, leading to much higher polarization values, thus providing access to high polarization ferroelectric materials with weakly bent compounds having only "weakly chiral" stereogenic units. Moreover, the field induced alignment of the SmCsPF(()*()) domains gives rise to a special kind of electroclinic effect appearing even in the absence of molecular chirality. Comparison with related compounds indicates that the strongest effects of chirality appear for weakly bent molecules with a relatively short coherence length of polar order, whereas for smectic phases with long range polar order the effects of the interlayer interfaces can override the chirality effects.

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

    Science.gov (United States)

    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

  14. pKa value and buffering capacity of acidic monomers commonly used in self-etching primers.

    Science.gov (United States)

    Salz, Ulrich; Mücke, Angela; Zimmermann, Jörg; Tay, Franklin R; Pashley, David H

    2006-06-01

    The aim of this investigation was to characterize acidic monomers used in self-etching primers/adhesives by determination of their pKa values and by calculation of their calcium dissolving capacity in comparison with phosphoric and hydrochloric acid. The following acidic monomers were included in this study: 4-methacryloyloxyethyl trimellitate anhydride (4-META), 10-methacryloyloxydecyl dihydrogen phosphate (MDP), dimethacryloyloxyethyl hydrogen phosphate (di-HEMA-phosphate), ethyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (EAEPA), 2-[4-(dihydroxyphosphoryl)-2-ox-abutyl]acrylic acid (HAEPA), and 2,4,6 trimethylphenyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (MAEPA). The pKa values were obtained by titration with 0.1 mol/l NaOH in aqueous solution. The inflection points of the resulting potentiometric titration curve were determined as pKa values. In the case of the sparingly water-soluble acidic monomers MAEPA and 4-META, the co-solvent method using different water/ethanol ratios for MAEPA or water/acetone ratios for 4-META was used. The dissolving capacity of each acidic monomer is defined as the amount of hydroxyapatite (HA) dissolved by 1 g of acid. For each monomer, the HA dissolving capacity was calculated bythe corresponding pKa value and the molecular weight. To confirm the calculated dissolving capacities, increasing amounts of HA powder (100 mg portions) were slowly added to 15 mmol/l aqueous solutions of the monomers to determine how much HA could be dissolved in the acidic solutions. For all the investigated acidic monomers, pKal values between 1.7 to 2.5 were observed. The pKa2 values for the phosphate/phosphonate derivatives are between 7.0 and 7.3, and are comparable to phosphoric acid. For dicarboxylic acid derivatives, the pKa2 values are in the range of 4.2 to 4.5. Due to their comparable molecular weights and pKal values, the three tested acids di-HEMA phosphate, MDP and 4-META all possess comparable dissolving capacities for HA (ie, 0

  15. Low-temperature radiation-induced polymerization of vinyl monomers in the crystal matrix of polydimethyl siloxane

    International Nuclear Information System (INIS)

    Mujdinov, M.R.; Kiryukhin, D.P.; Barkalov, I.M.; Gol'danskij, V.I.

    1979-01-01

    It is shown that in the process of the slow cooling of vinyl monomer solution in dimethyl siloxane rubber (SKT mark) crystallization of SKT takes place, at that, considerable part of vinyl monomers (up to 70 wt. % of rubber) is sorbed in the pores of crystal matrix and it does not form its proper crystal phase. Slight anomalies in heat capacity in the 120-140 K range, the melting of non-sorbed part of MA and the melting of SKT + MA ''complex'' have been observed on the calorimetric curve at the SKT - methylacrylate (MA) system heating. In the process of heating such samples, irradiated at 77 K by γ-rays of 60 Co, heat evolution connected with sorbed monomer polarization, has been observed starting from 125-130 K. In the 140-200 K range already before MA and SKT melting intense polymerization takes place, which results in practically full monomer consumption and formation of graft copolymer. Radiation-chemical yield of monomer reduction reaches G(-M) approximately equal to 2x10 5 molecules for 100 eV, radiation yield of postpolymerization of crystal MA does not exceed G(-M) approximately equal to 50 molecules for 100 eV

  16. Quantitative analysis of detailed lignin monomer composition by pyrolysis-gas chromatography combined with preliminary acetylation of the samples.

    Science.gov (United States)

    Sonoda, T; Ona, T; Yokoi, H; Ishida, Y; Ohtani, H; Tsuge, S

    2001-11-15

    Detailed quantitative analysis of lignin monomer composition comprising p-coumaryl, coniferyl, and sinapyl alcohol and p-coumaraldehyde, coniferaldehyde, and sinapaldehyde in plant has not been studied from every point mainly because of artifact formation during the lignin isolation procedure, partial loss of the lignin components inherent in the chemical degradative methods, and difficulty in the explanation of the complex spectra generally observed for the lignin components. Here we propose a new method to quantify lignin monomer composition in detail by pyrolysis-gas chromatography (Py-GC) using acetylated lignin samples. The lignin acetylation procedure would contribute to prevent secondary formation of cinnamaldehydes from the corresponding alcohol forms during pyrolysis, which are otherwise unavoidable in conventional Py-GC process to some extent. On the basis of the characteristic peaks on the pyrograms of the acetylated sample, lignin monomer compositions in various dehydrogenative polymers (DHP) as lignin model compounds were determined, taking even minor components such as cinnamaldehydes into consideration. The observed compositions by Py-GC were in good agreement with the supplied lignin monomer contents on DHP synthesis. The new Py-GC method combined with sample preacetylation allowed us an accurate quantitative analysis of detailed lignin monomer composition using a microgram order of extractive-free plant samples.

  17. Effect of pH and Monomer Dosing Rate in the Anionic Polymerization of Ethyl Cyanoacrylate in Semicontinuous Operation

    Directory of Open Access Journals (Sweden)

    Hened Saade

    2015-01-01

    Full Text Available Nanoparticles of poly(ethyl cyanoacrylate with more than 10% solids content were prepared by semicontinuous heterophase polymerization at monomer-starved conditions varying the initial pH in the interval of 1–1.75 and at two monomer dosing rates. Measurements by scanning-transmission electron microscopy allowed us to identify an inverse dependence of particle size on pH. Furthermore, all the polymerizations conducted at the slower monomer dosing rate rendered two particle populations, with the larger one formed from the aggregation of a fraction of the smaller particles. It was believed that the so slow addition of the monomer caused the formation of very small but instable particles, thereby a fraction of which aggregated to reduce the total interface particles-aqueous phase, increasing the latex stability. An increase in the monomer dosing rate led to larger and more stable particles in such way that only one population of nanoparticles with around 40 nm in average diameter was obtained.

  18. Thermal and Optical Properties of CdS Nanoparticles in Thermotropic Liquid Crystal Monomers

    Directory of Open Access Journals (Sweden)

    Marc Alnot

    2010-03-01

    Full Text Available Two new mesogenic monomers, namely 3,3’-dimethoxy-4,4’-di(hydroxyhexoxy-N-benzylidene-o-Tolidine (Ia and 4,4’-di(6-hydroxyhexoxy-N-benzylidene-o-Tolidine (IIa, were reacted with cadmium sulfide (CdS via an in situ chemical precipitation method in ethanol to produce CdS nanocomposites. A series of different mass compositions of CdS with Ia and IIa ranging from 0.1:1.0 to 1.0:1.0 (w/w were prepared and characterized using X-ray Diffraction (XRD, Raman spectroscopy, Fourier Transform Infrared Spectroscopy (FT-IR, Transmission Electron Microscopy (TEM, Polarizing Optical Microscopy (POM and Differential Scanning Calorimetry (DSC, X-ray Photoelectron Spectroscopy (XPS and Photoluminescence Spectroscopy (PL. XRD showed that the broad peaks are ascribed to the formation of cubic CdS nanoparticles in both Ia and IIa. The average particle size for both nanocomposites was less than 5 nm with a narrower size distribution when compared with pure CdS nanoparticles. The analyses from POM and DSC demonstrated that mass composition from 0.1:1.0 up to 0.5:1.0 of CdS:Ia nanocomposites showed their enantiotropic nematic phase. On the other hand, polarizing optical microscopy (POM for IIa nanocomposites showed that the liquid crystal property vanished completely when the mass composition was at 0.2:1.0. PL emissions for CdS: Ia or IIa nanocomposites indicated deep trap defects occurred in these both samples. The PL results revealed that addition of CdS to Ia monomers suppressed the photoluminescence intensity of Ia. However, the introduction of CdS to IIa monomers increased the photoluminescence and was at a maximum when the mass composition was 0.3:1.0, then decreased in intensity as more CdS was added. The XPS results also showed that the stoichiometric ratios of S/Cd were close to 1.0:1.0 for both types of nanocomposites for a mass composition of 1.0:1.0 (CdS:matrix.

  19. Cycling performance of lithium polymer cells assembled by in situ polymerization of a non-flammable ionic liquid monomer

    International Nuclear Information System (INIS)

    Lee, Yoon-Sung; Kim, Dong-Won

    2013-01-01

    Highlights: • Gel polymer electrolytes were synthesized by in situ polymerization of ionic liquid in the lithium polymer cells. • Flammability of the electrolyte was significantly reduced by polymerizing electrolyte containing a non-flammable ionic liquid monomer. • The cells assembled with polymeric ionic liquid-based electrolytes exhibited reversible cycling behavior with good capacity retention. -- Abstract: Lithium polymer cells composed of a lithium negative electrode and a LiCoO 2 positive electrode were assembled with a gel polymer electrolyte obtained by in situ polymerization of an electrolyte solution containing an ionic liquid monomer with vinyl groups. The polymerization of the electrolyte solution containing the non-flammable ionic liquid monomer resulted in a significant reduction of the flammability of the gel polymer electrolytes. The lithium polymer cell assembled with the stable gel polymer electrolyte delivered a discharge capacity of 134.3 mAh g −1 at ambient temperature and exhibited good capacity retention

  20. Pulse radiolysis study of monomer and dimer cations of styrene, 1-methylstyrene and 1,1'-diphenylethylene

    International Nuclear Information System (INIS)

    Mehnert, R.; Helmstreit, W.; Boes, J.; Brede, O.

    1977-01-01

    In pulse-irradiated solutions of styrene, 1-methylstyrene and 1,1'-diphenylethylene, the decay kinetics of the olefin monomer cations and the formation kinetics of the corresponding dimer cations have been studied at room temperature. The solutions were irradiated with 15-nsec 15-ampere pulses of 1-MeV electrons from an Elit-type accelerator. The total dose per pulse was approximately 10 krad. The monomer cations were generated with rate constants of about 10 11 M -1 sec -1 . From the time decay of the monomer light absorption and the growth in time of the dimer absorption rate constants for the dimer formation between 0.8x10 10 and 1.2x10 10 M -1 sec -1 have been determined. (T.I.)

  1. The role of monomer fraction data in association theories—Can we improve the performance for phase equilibrium calculations?

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Bøgh, David; Karakatsani, Eirini

    2014-01-01

    with different ethanol content as inhibitor. There are some differences in the performance of CPA with the two sets but on average the results are similar. This may indicate that monomer fraction data are not very useful in this case or that ethanol monomer fraction data are not accurate and both possibilities...... accurate and how useful are such data today and how successful is their use in the context of association models? In this work we attempt to answer these questions in the case of the CPA model and for ethanol. CPA has been already successfully used to describe thermodynamic properties of many ethanol...... containing mixtures, using an ethanol parameter set that was adjusted to experimental vapor pressure and liquid density data. We present in this work a new parameter set for ethanol which is estimated using experimental vapor pressure, liquid density data as well as the experimental monomer fractions...

  2. Microwave plasma initiated graft copolymerization modification of monomers onto PTFE surface

    International Nuclear Information System (INIS)

    Guan Weishu; Wen Yunjian; Fang Yan; Yin Yongxiang

    1996-02-01

    A graft copolymerization modification technique of monomers onto polytetrafluoroethylene (PTFE) surface initiated by a 2.45 GHz non-equilibrium microwave plasma has been investigated. Standard X-Ray Photoelectron Spectroscopy (XPS), Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), Scanning Electron Microscopy (sEM) and wetting techniques were used for examination and analysis of samples. Considerable changes in chemical structure, composition and in morphology of grafted surface of PTFE were found. Results showed the occurrence of noticeable defluorination and cross-linked structure on grafted surface, and indicated that different kinds and contents of oxygen-containing functional groups were introduced into the surface of PTFE. Wetting and adhesion experiment of the sample proved that significant improvements in hydrophilicity and adhesion of surface were exhibited. These results confirmed the success of grafting. (8 refs., 7 figs., 1 tab.)

  3. Lurgi MegaMethanol technology. Delivering the building blocks for the future fuel and monomer demand

    Energy Technology Data Exchange (ETDEWEB)

    Wurzel, T. [Lurgi AG, Frankfurt/Main (Germany)

    2006-07-01

    The paper describes the central role of methanol within a changing environment with respect to feedstock availability as well as steadily growing demand in fuel and monomer demand. The current large-scale production facilities are described with respect to the technological challenges in order to ensure the availability of sufficient methanol for down-stream applications. Different down-stream applications are described which clearly confirm that methanol is the dominant C1-building block due to its chemical flexibility. It is concluded that by means of the implementation of two MTP (Methanol to Propylene) projects in China initiated the era of ''down-stream methanol'' has begun in the industry. (orig.)

  4. Monte Carlo simulation of star/linear and star/star blends with chemically identical monomers

    Energy Technology Data Exchange (ETDEWEB)

    Theodorakis, P E [Department of Materials Science and Engineering, University of Ioannina, 45110 Ioannina (Greece); Avgeropoulos, A [Department of Materials Science and Engineering, University of Ioannina, 45110 Ioannina (Greece); Freire, J J [Departamento de Ciencias y Tecnicas FisicoquImicas, Universidad Nacional de Educacion a Distancia, Facultad de Ciencias, Senda del Rey 9, 28040 Madrid (Spain); Kosmas, M [Department of Chemistry, University of Ioannina, 45110 Ioannina (Greece); Vlahos, C [Department of Chemistry, University of Ioannina, 45110 Ioannina (Greece)

    2007-11-21

    The effects of chain size and architectural asymmetry on the miscibility of blends with chemically identical monomers, differing only in their molecular weight and architecture, are studied via Monte Carlo simulation by using the bond fluctuation model. Namely, we consider blends composed of linear/linear, star/linear and star/star chains. We found that linear/linear blends are more miscible than the corresponding star/star mixtures. In star/linear blends, the increase in the volume fraction of the star chains increases the miscibility. For both star/linear and star/star blends, the miscibility decreases with the increase in star functionality. When we increase the molecular weight of linear chains of star/linear mixtures the miscibility decreases. Our findings are compared with recent analytical and experimental results.

  5. Monte Carlo simulation of star/linear and star/star blends with chemically identical monomers

    Science.gov (United States)

    Theodorakis, P. E.; Avgeropoulos, A.; Freire, J. J.; Kosmas, M.; Vlahos, C.

    2007-11-01

    The effects of chain size and architectural asymmetry on the miscibility of blends with chemically identical monomers, differing only in their molecular weight and architecture, are studied via Monte Carlo simulation by using the bond fluctuation model. Namely, we consider blends composed of linear/linear, star/linear and star/star chains. We found that linear/linear blends are more miscible than the corresponding star/star mixtures. In star/linear blends, the increase in the volume fraction of the star chains increases the miscibility. For both star/linear and star/star blends, the miscibility decreases with the increase in star functionality. When we increase the molecular weight of linear chains of star/linear mixtures the miscibility decreases. Our findings are compared with recent analytical and experimental results.

  6. Monte Carlo simulation of star/linear and star/star blends with chemically identical monomers

    International Nuclear Information System (INIS)

    Theodorakis, P E; Avgeropoulos, A; Freire, J J; Kosmas, M; Vlahos, C

    2007-01-01

    The effects of chain size and architectural asymmetry on the miscibility of blends with chemically identical monomers, differing only in their molecular weight and architecture, are studied via Monte Carlo simulation by using the bond fluctuation model. Namely, we consider blends composed of linear/linear, star/linear and star/star chains. We found that linear/linear blends are more miscible than the corresponding star/star mixtures. In star/linear blends, the increase in the volume fraction of the star chains increases the miscibility. For both star/linear and star/star blends, the miscibility decreases with the increase in star functionality. When we increase the molecular weight of linear chains of star/linear mixtures the miscibility decreases. Our findings are compared with recent analytical and experimental results

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

    International Nuclear Information System (INIS)

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

    1996-01-01

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

  8. A method for polymerizing insaturated monomers through irradiation in the presence of a salt

    International Nuclear Information System (INIS)

    Phalangas, C.J.; Restaino, A.J.; Yun, Hanbo.

    1975-01-01

    The method consists in irradiating an aqueous solution with a pH between about 2 and 12, comprising from 10 to 40% about an ethylene-insaturated monomer or of mixtures thereof with vinyl-sulfonic acid, an alkaline metal salt of said acid or acrylamide diacetone and at least 3% of a potassium, sodium, lithium, ammonium or aluminium salt, by means of highly powerful radiations, e.g. gamma rays, the radiation intensity being between 1000 and 200000 rads per hour and the overall radiation dose being in the 1000-30000 rads. The obtained product is a polymer aqueous solution either in the liquid state or in the form of a gel [fr

  9. Progress of research in treatment of hyperlipidemia by monomer or compound recipe of Chinese herbal medicine.

    Science.gov (United States)

    Dou, Xiao-bing; Wo, Xing-de; Fan, Chun-lei

    2008-03-01

    Hyperlipidemia (HLP) is the No.1 risk factor for patients with atherosclerosis (AS) and is directly related to the occurrence of coronary artery disease (CAD) and cerebrovascular disease. Therefore, prevention and treatment of AS is of great importance and of practical significance in controlling the incidence and mortality of CAD. With its peculiar syndrome-dependent therapy, traditional Chinese medicine (TCM) has accumulated abundant practical experiences in this field and good clinical effects have been achieved. Chinese herbal medicine, with its particularly unique advantages and high potentials yet to be tapped, displays its huge strength in HLP prevention and treatment. The progress of studies concerning prevention and treatment of HLP by Chinese herbal medicines, in the form of monomers or compound recipes, is reviewed in this paper.

  10. Role of Monomer Sequence, Hydrogen Bonding and Mesoscale Architecture in Marine Antifouling Coatings

    Science.gov (United States)

    Segalman, Rachel

    Polypeptoids are non-natural, sequence specific polymers that offer the opportunity to probe the effect of monomer sequence, chirality, and chain shape on self-assembly and surface properties. Additionally, polypeptoid synthesis is more scaleable than traditional polypeptides suggesting their utility in large area applications. We have designed efficient marine anti-fouling coatings by using triblock copolymer scaffolds to which polypeptoids are tethered in order to tune both the modulus and surface energies with great precision. Surprisingly, when short sequences are tethered to a polymer backbone, polypeptoids consistently outperform analogous polypeptides in antifouling properties. We hypothesize that the hydrogen bonding inherent to the polypeptide backbone drives the observed differences in performance. We also find that the polymer scaffold housing the polypeptoids also plays a crucial role in directing surface presentation and therefore the overall coating properties.

  11. Vanadate monomers and dimers both inhibit the human prostatic acid phosphatase.

    Science.gov (United States)

    Crans, D C; Simone, C M; Saha, A K; Glew, R H

    1989-11-30

    A combination of enzyme kinetics and 51V NMR spectroscopy was used to identify the species of vanadate that inhibits acid phosphatases. Monomeric vanadate was shown to inhibit wheat germ and potato acid phosphatases. At pH 5.5, the vanadate dimer inhibits the human prostatic acid phosphatase whereas at pH 7.0 it is the vanadate monomer that inhibits this enzyme. The pH-dependent shift in the affinity of the prostatic phosphatase for vanadate is presumably due to deprotonation of an amino acid side chain in or near the binding site resulting in a conformational change in the protein. pH may be a subtle effector of the insulin-like vanadate activity in biological systems and may explain some of the differences in selectivity observed with the protein phosphatases.

  12. Solvent polarity scale on the fluorescence spectra of a dansyl monomer copolymerizable in aqueous media

    Science.gov (United States)

    Ren, Biye; Gao, Feng; Tong, Zhen; Yan, Yu

    1999-06-01

    A copolymerizable fluorescent monomer N-[2-[[[5-(N,N-dimethylamino)-1-naphthalenyl]sulfonyl]-amino]ethyl]-2-propenamide (DANSAEP) was synthesized, which exhibits dual fluorescence due to the twisted intramolecular charge transfer in the excited state. The emission maximum λem shifts from 463.3 nm in n-hexane to 530.0 nm in water, showing solvent polarity dependence. The relations between λem and the conventional solvent polarity parameters ET(30) or Z are linear, dividing solvents into protic and aprotic groups. Kamlet's linear solvation energy relationship gives a good description for λem as a solvent polarity scale. The increment of dipole moment Δ μ at the excited state was estimated as 5.09 D with the solvatochromic analysis.

  13. Radiation Induced Grafting of Acrylate onto Waste Rubber: The Effect of Monomer Type

    Directory of Open Access Journals (Sweden)

    Shirajuddin Siti Salwa M.

    2017-01-01

    Full Text Available The effect of three different acrylate group monomers, namely n-butyl acrylate, methacrylic acid and tripropylene glycol diacrylate of radiation induced grafting onto waste rubber was studied. The electron beam accelerator operated at voltage of 2MeV was used to irradiate the waste rubber at 10 kGy and 100 kGy absorbed radiation dose, respectively. The formation of grafting was observed from the increase in the grafting yield and confirmed by Transformed Infra-Red Spectroscopy results. According to the result obtained, only tripropylene glycol diacrylate was selected to graft onto waste rubber. The carbonyl bond from acrylate groups was seen at 1726 cm-1 band which confirmed the presence of TPGDA in the polymer matrix. This indicates the successful preparation of the TPGDA-grafted waste rubber via radiation induced grafting techniques.

  14. Radiation curing of mixture of diallylphthalate prepolymer and vinyl monomer, 11

    International Nuclear Information System (INIS)

    Gotoda, Masao; Yagi, Toshiaki; Yoshizawa, Iwao; Okugawa, Hideo.

    1975-01-01

    Preparation of Wood-Polymer Composite (WPC) piled plywood for flooring, was attempted by electron beam irradiation of American Hemlock veneer, impregnated with low molecular weight diallylphthalate prepolymer (DAPsub(p).L)/vinyl monomer mixtures, in comparison with that by thermal curing reported previously. For the improvement of the mechanical properties of WPC piled plywood, 5-15 parts of low molecular weight polyvinylacetate (PVAc) was added to DAPsub(p).L/methyl acrylate/hydroxyethyl acrylate/benzoyl peroxide (50/40/10/2) mixture. The addition of PVAc did not give much influence to the degree of impregnation in the veneer and to the curability by electron beam irradiation. As to the resistance to hot and cold cycle test, WPC piled plywood, prepared by the resin containing 5 parts of PVAc gave the best results. As a general conclusion, due to the superior mechanical properties, the WPC piled plywood processed by electron beam irradiation is suitable for flooring use. (author)

  15. HMI design of MIRROR PLANT for Safe Operation and Application to Vinyl Acetate Monomer Process

    International Nuclear Information System (INIS)

    Hatsugai, Emiko; Nakaya, Makoto

    2014-01-01

    Dynamic plant simulators have always been used off-line for operator training and control loop design prior to the plant construction phase. Here, we propose on-line use of a dynamic simulator for the development of new plant operation. The developed MIRROR PLANT is an on-line dynamic plant simulator that can perfectly simulate dynamic plant behavior, and can also be used to forecast future plant behavior by making the computer run the simulation faster than real-time. Using the estimated and forecast data, the plant operator can detect abnormal situations in the plant. Before activating an alarm from the conventional control system, the operator will be able to perform proactive operation to maintain safety. In this paper, we propose a new human-machine interface (HMI) design to realize proactive operation and discuss application of the HMI to the vinyl acetate monomer process as an example of MIRROR PLANT

  16. Effect of microwave postpolymerization treatment on residual monomer content and the flexural strength of autopolymerizing reline resin

    Directory of Open Access Journals (Sweden)

    Patil Padmakar

    2009-01-01

    Full Text Available Background : Microwave postpolymerization has been suggested as a method to improve the flexural strength of an autopolymerizing denture reline resin. However, the effect of microwave postpolymerization on the residual monomer content and its influence on flexural strength have not been investigated. Objectives : This study analyzed the effect of microwave postpolymerization on the residual monomer content and its influence on the flexural strength of an autopolymerizing reline resin (Denture Liner. Materials and Methods : A total of 70 specimens (64 Χ 10 Χ 3.3 mm were polymerized according to the manufacturer′s instructions and divided into 7 groups (n = 10. Control group specimens were not subjectedto any further processing. Before testing, the specimens were subjected to postpolymerization in a microwave oven using different power (550 and 650 W and time (3, 4, and 5 min settings. Two specimens of each group were then manually ground into fine powder and samples extracted from the specimens using reflux method. The samples were then subjected to gas chromatography for residual monomer determination in area%. Eight specimens were subjected to a three-point bending device with a span of 50 mm and crosshead speed of 5 mm/min, and the flexural strength was determined in MPa. Data analyses included Student′s t-test and one-way analysis of variance. Results : For the Denture Liner reline resin, the residual monomer content decreased and the flexural strength increased significantly with the application of microwave irradiation using different time/power combinations. The specimens with the lowest residual monomer content were the similar specimens which presented with the highest flexural strength. Conclusion : Microwave postpolymerization irradiation can be an effective method for increasing the flexural strength of denture liner (at 650 W for 5 min by reducing the residual monomer content by further polymerization at free radical sites.

  17. Computational studies at the density functional theory (DFT) level about the surface functionalization of hexagonal monolayers by chitosan monomer

    Science.gov (United States)

    Ebrahimi, Javad; Ahangari, Morteza Ghorbanzadeh; Jahanshahi, Mohsen

    2018-05-01

    Theoretical investigations based on density functional theory have been carried out to understand the underlying interactions between the chitosan monomer and several types of hexagonal monolayers consisting of pristine and defected graphene and boron-nitride nanosheets. Based on the obtained results, it was found that the type of the interaction for all the systems is of non-covalent nature and the chitosan monomer physically interacts with the surface of mentioned nanostructures. The interaction strength was evaluated by calculating the adsorption energies for the considered systems and it was found that the adsorption of chitosan monomer accompanies by the release of about -0.67 and -0.66 eV energy for pristine graphene and h-BN monolayer, respectively. The role of structural defect has also been considered by embedding a Stone-Wales defect within the structure of mentioned monolayers and it was found that the introduced defect enhances the interactions between the chitosan monomer and nanostructures. The role of dispersion interactions has also been taken into account and it was found that these long-range interactions play the dominating role in the attachment of chitosan monomer onto the graphene sheet, while having strong contribution together with the electrostatic interactions for the stabilization of chitosan onto the surface of h-BN monolayer. For all the cases, the adsorption of chitosan monomer did not change the inherent electronic properties of the nanostructures based on the results of charge transfer analysis and energy gap calculations. The findings of the present work would be very useful in future investigations to explore the potential applications of these hybrid materials in materials science and bio-related fields.

  18. Pseudomonas syringae evades host immunity by degrading flagellin monomers with alkaline protease AprA.

    Science.gov (United States)

    Pel, Michiel J C; van Dijken, Anja J H; Bardoel, Bart W; Seidl, Michael F; van der Ent, Sjoerd; van Strijp, Jos A G; Pieterse, Corné M J

    2014-07-01

    Bacterial flagellin molecules are strong inducers of innate immune responses in both mammals and plants. The opportunistic pathogen Pseudomonas aeruginosa secretes an alkaline protease called AprA that degrades flagellin monomers. Here, we show that AprA is widespread among a wide variety of bacterial species. In addition, we investigated the role of AprA in virulence of the bacterial plant pathogen P. syringae pv. tomato DC3000. The AprA-deficient DC3000 ΔaprA knockout mutant was significantly less virulent on both tomato and Arabidopsis thaliana. Moreover, infiltration of A. thaliana Col-0 leaves with DC3000 ΔaprA evoked a significantly higher level of expression of the defense-related genes FRK1 and PR-1 than did wild-type DC3000. In the flagellin receptor mutant fls2, pathogen virulence and defense-related gene activation did not differ between DC3000 and DC3000 ΔaprA. Together, these results suggest that AprA of DC3000 is important for evasion of recognition by the FLS2 receptor, allowing wild-type DC3000 to be more virulent on its host plant than AprA-deficient DC3000 ΔaprA. To provide further evidence for the role of DC3000 AprA in host immune evasion, we overexpressed the AprA inhibitory peptide AprI of DC3000 in A. thaliana to counteract the immune evasive capacity of DC3000 AprA. Ectopic expression of aprI in A. thaliana resulted in an enhanced level of resistance against wild-type DC3000, while the already elevated level of resistance against DC3000 ΔaprA remained unchanged. Together, these results indicate that evasion of host immunity by the alkaline protease AprA is important for full virulence of strain DC3000 and likely acts by preventing flagellin monomers from being recognized by its cognate immune receptor.

  19. Micrococcus radiodurans surface exonuclease. Dimer to monomer conversion by ionizing radiation-generated aqueous free radicals

    Energy Technology Data Exchange (ETDEWEB)

    Mitchel, R E.J.

    1980-01-01

    Micrococcus radiodurans possesses an exonuclease firmly bound to a middle cell wall membrane layer. Aqueous OH/sup -/ radicals generated chemically or by ionizing radiation cause the immediate release of this enzyme into the surrounding medium. The enzyme is located in a hydrophobic site and can also be released by aqueous n-butanol. When extracted by this solvent it is a non-covalently linked dimer and has a molecular weight of 260,000 as determined by gel filtration. When released by radiation generated OH/sup -/ radicals, the enzyme initially appears in solution as the dimer but is rapidly split by further aqueous radical attack into two 130,000 molecular weight subunits. Hydroxyl radicals are most effective but reducing radicals are also able to monomerize the enzyme. Only the released dimer enzyme is subject to free radical monomerization. Bound dimer enzyme is not split prior to release. No detectable loss of activity or change in catalytic properties accompanies the free radical cleavage of the enzyme. Both subunits of the dimer enzyme possess a tightly bound metal ion (probably Ca/sup 2 +/) required for activity. The monomer but not the dimer enzyme will bind to an anion exchanger. The monomer is susceptible to loss of its metal ion, and consequent inactivation, when exposed to the exchanger in the absence of Ca/sup 2 +/. Besides providing information on some of the immediate non-lethal effects of ionizing radiation, the behavior of this enzyme system demonstrates a potential cellular mechanism by which internally or externally generated free radicals could be utilized by the cell to control various enzymic reactions.

  20. [Chinese medicinal monomer and compound for 60Co-gamma-induced spermatogenic disturbance in mice].

    Science.gov (United States)

    Zhang, Wei-xing; Wang, Hua-li; Wang, Rui; Li, Rui; He, Wei; Zhang, Tian-biao

    2010-05-01

    To explore the effects of the monomer and compound of the Chinese herbal drugs resveratrol, lycium barbarum polysaccharide (LBP) and icariin on 60Co-gamma-induced spermatogenic disturbance in mice based on the theory of modern Chinese medicine. A total of 105 male Kunming mice were randomly divided into seven groups, with 15 in each. Group A were normally raised and Groups B, C, D, E, F and G irradiated by 60Co-gamma 6 Gy followed by 60Co-gamma 4 Gy at the interval of 7 days. A week later, Groups C, D, E, F and G received intragastrically the suspension of resveratrol, resveratrol + LBP, resveratrol + icariin, resveratrol + LBP + icariin and resveratrol + LBP + icariin + L-carnitine, respectively, at the dose of 80 mg/(kg x d) for 60 days. The general condition, physical signs and body weight changes of the mice were recorded, and 24 hours after the intragastric medication, their testes were harvested to obtain the testicular weight and indexes, the levels of FSH, LH, T and E2 determined by ELISA, the T/E2 ratio calculated, and the histology of the testis tissues observed under the microscope. The testicular indexes of the mice were decreased by radiation-induced damage, but restored to some extent after intragastric medication, especially in Groups E, F and G. The levels of FSH, LH and T were obviously improved by LBP. The T level and testis weight were increased by Icariin. The level of T/E2 was elevated in Groups E, F and G. The best results were achieved in Group F, which exhibited almost complete recovery from reproductive endocrine disorder and spermatogenic damage. The Chinese medicinal monomer is effective for 60Co-gamma-induced spermatogenic disturbance in mice, and the compound suspension of resveratrol + LBP + icariin produces the best result.

  1. Structural effect of monomer type on properties of copolyimides and copolyimide-silica hybrid materials

    Directory of Open Access Journals (Sweden)

    Kizilkaya Canan

    2015-01-01

    Full Text Available In this work, the effect of two different diamine monomers, containing phosphine oxide, on thermal, mechanical and morphological properties of copolyimides and their hybrid materials was investigated. Gas separation properties of the synthesized copolyimides were also analysed. Two different diamine monomers with phosphine oxide were bis(3-aminophenyl phenylphosphine oxide (BAPPO and bis(3-aminophenoxy-4-phenyl phenylphosphine oxide (m-BAPPO. In the synthesis of copolyimides 3,3’-diamino-diphenyl sulfone (DDS was also used as the diamine, as well as 2,2’-bis(3,4-dicarboxyphenylhexafluoropropane dianhydride (6FDA. Copolyimide films were prepared by thermal imidization. Hybrid materials containing 5 % SiO2 were synthesised further by sol-gel technique. The Fourier-transform infrared spectroscopy (FTIR, Nuclear magnetic resonance spectroscopy (NMR confirmed the expected structure. Dynamic mechanical analysis (DMA demonstrated that m-BAPPO based copolyimides had lower glass transition temperatures (Tg than BAPPO based copolyimides. m-BAPPO containing copolyimide without silica shifted the thermal decomposition temperature to a higher value. The moduli and strength values of BAPPO diamine containing copolyimide and its hybrid were higher than those of m-BAPPO containing materials. The contact angle measurements showed the hydrophobicity. Scanning electron microscope (SEM analysis exhibited the silica particles dispersion in the copolyimides. These copolyimides may be used in the coating industry. The CO2 permeability and the permselectivity were the highest among the other values in this study, when m-BAPPO containing copolyimide in the absence of silica was used. The gas permeabilities obtained from this work were in this decreasing order: PCO2 > PO2 > PN2.

  2. Prediction of monomer reactivity in radical copolymerizations from transition state quantum chemical descriptors

    Directory of Open Access Journals (Sweden)

    Zhengde Tan

    2013-01-01

    Full Text Available In comparison with the Q-e scheme, the Revised Patterns Scheme: the U, V Version (the U-V scheme has greatly improved both its accessibility and its accuracy in interpreting and predicting the reactivity of a monomer in free-radical copolymerizations. Quantitative structure-activity relationship (QSAR models were developed to predict the reactivity parameters u and v of the U-V scheme, by applying genetic algorithm (GA and support vector machine (SVM techniques. Quantum chemical descriptors used for QSAR models were calculated from transition state species with structures C¹H3 - C²HR³• or •C¹H2 - C²H2R³ (formed from vinyl monomers C¹H²=C²HR³ + H•, using density functional theory (DFT, at the UB3LYP level of theory with 6-31G(d basis set. The optimum support vector regression (SVR model of the reactivity parameter u based on Gaussian radial basis function (RBF kernel (C = 10, ε = 10- 5 and γ = 1.0 produced root-mean-square (rms errors for the training, validation and prediction sets being 0.220, 0.326 and 0.345, respectively. The optimal SVR model for v with the RBF kernel (C = 20, ε = 10- 4 and γ = 1.2 produced rms errors for the training set of 0.123, the validation set of 0.206 and the prediction set of 0.238. The feasibility of applying the transition state quantum chemical descriptors to develop SVM models for reactivity parameters u and v in the U-V scheme has been demonstrated.

  3. Lignin monomer composition affects Arabidopsis cell-wall degradability after liquid hot water pretreatment

    Directory of Open Access Journals (Sweden)

    Ladisch Michael

    2010-12-01

    Full Text Available Abstract Background Lignin is embedded in the plant cell wall matrix, and impedes the enzymatic saccharification of lignocellulosic feedstocks. To investigate whether enzymatic digestibility of cell wall materials can be improved by altering the relative abundance of the two major lignin monomers, guaiacyl (G and syringyl (S subunits, we compared the degradability of cell wall material from wild-type Arabidopsis thaliana with a mutant line and a genetically modified line, the lignins of which are enriched in G and S subunits, respectively. Results Arabidopsis tissue containing G- and S-rich lignins had the same saccharification performance as the wild type when subjected to enzyme hydrolysis without pretreatment. After a 24-hour incubation period, less than 30% of the total glucan was hydrolyzed. By contrast, when liquid hot water (LHW pretreatment was included before enzyme hydrolysis, the S-lignin-rich tissue gave a much higher glucose yield than either the wild-type or G-lignin-rich tissue. Applying a hot-water washing step after the pretreatment did not lead to a further increase in final glucose yield, but the initial hydrolytic rate was doubled. Conclusions Our analyses using the model plant A. thaliana revealed that lignin composition affects the enzymatic digestibility of LHW pretreated plant material. Pretreatment is more effective in enhancing the saccharification of A. thaliana cell walls that contain S-rich lignin. Increasing lignin S monomer content through genetic engineering may be a promising approach to increase the efficiency and reduce the cost of biomass to biofuel conversion.

  4. Improvement of antithrombogenicity of a fluoro polymer by radiation-induced grafting of hydrophilic monomer

    International Nuclear Information System (INIS)

    Otsuhata, Kazushige; Razzak, M.T.; Tabata, Yoneho; Ohashi, Fumito; Takeuchi, Atsushi.

    1985-01-01

    Fluoro polymers have been used as biomaterials in medical field since they have good compatibility with both tissue and blood, and their biomaterial application are of variety. Blood compatibility of fluoro polymers, however, are not always enough for every applications. Especially, there is a large difficulty in the application for artificial vessel with small radius below than 4 mm. In the present study, grafting of a hydrophilic monomer onto a fluoro polymer has been carried out to improve blood compatibility of the fluoro polymer. The technique of grafting employed here was simultaneous irradiation method of gamma rays from a 60 Co source. The fluoro polymer and the hydrophilic monomer used in the experiment were alternative copolymer of ethylene and tetrafluoethylene(AFLON) and N,N-dimethylacry lamide(DMAA), respectively. After grafting, it was found by in vitro tests that antithrombogenicity of AFLON was improved by grafting of DMAA. It was, however, also found that degree of the improvement is affected by grafting conditions. When ethyl acetate was used as a solvent for the graft copolymerization, the improvement was affected by dose rate. Blood compatibility of DMAA-g-AFLON obtained at a higher dose rate of 1 x 10 5 rad/h was not improved, while it was improved in the sample of DMAA-g-AFLON obtained at a lower dose rate of 1 x 10 4 rad/h. On the other hand, when acetone was used as a solvent for the grafting, the degree of grafting gave a significant effect on the improvement. Blood compatibility of all samples with grafting percent more than 20 % was improved by grafting of DMAA. (author)

  5. Vulcanization Kinetics and Mechanical Properties of Ethylene Propylene Diene Monomer Thermal Insulation

    Directory of Open Access Journals (Sweden)

    Mohamad Irfan Fathurrohman

    2015-07-01

    Full Text Available The vulcanization kinetics of Ethylene-propylene diene monomer (EPDM rubber thermal insulation was studied by using rheometer under isothermal condition at different temperatures. The rheometry analysis was used to determining the cure kinetic parameters and predicting the cure time of EPDM thermal insulation. The experimental results revealed that the curing curves of EPDM thermal insulation were marching and the optimum curing time decreased with increasing the temperature. The kinetic parameters were determined from the autocatalytic model showed close fitting with the experimental results, indicating suitability of autocatalytic model in characterizing the cure kinetics. The activation energy was determined from the autocatalytic model is 46.3661 kJ mol-1. The cure time were predicted from autocatalytic model and the obtained kinetic parameter by using the relationship among degree of conversion, cure temperature, and cure time. The predictions of cure time provide information for the actual curing characteristic of EPDM thermal insulation. The mechanical properties of EPDM thermal insulation with different vulcanization temperatures showed the same hardness, tensile strength and modulus at 300%, except at temperature 70 °C, while the elongation at breaking point decreased with increasing temperature of vulcanization. © 2015 BCREC UNDIP. All rights reservedReceived: 8th April 2014; Revised: 7th January 2015; Accepted: 16th January 2015How to Cite: Fathurrohman, M.I., Maspanger, D.R., Sutrisno, S. (2015. Vulcanization Kinetics and Mechanical Properties of Ethylene Propylene Diene Monomer Thermal Insulation. Bulletin of Chemi-cal Reaction Engineering & Catalysis, 10 (2, 104-110. (doi:10.9767/bcrec.10.2.6682.104-110Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.6682.104-110 

  6. Study on grafting of monomer onto natural rubber latex by radiation technique

    International Nuclear Information System (INIS)

    Nguyen Tan Man; Le Hai; Tran Thi Tam; Le Huu Tu, Pham Thi Sam; Dao Minh Phuong; Ha Thuc Huy

    2004-01-01

    Radiation vulcanization of natural rubber latex has been extensively developed through programmers assisted by the IAEA and UNDP under RCA in Asia and Pacific Region. R-D has been done in most of the Member States with technical assistance from Japan's Takasaki Radiation Chemistry Establishment. Radiation vulcanized natural rubber latex (RVNRL) has many advantages over the conventional sulfur vulcanized latex, such as absence of nitrosamine and low cytotoxicity. Radiation crosslinking is a room temperature process, itself an important cost advantage, it is easily controlled and desired extend of crosslinking is easily achieved by controlling the dose (irradiation time). Disadvantages of RVNRL to be improved are poor physical properties of film such as low tensile strength and tear strength. The research groups of Japan, Thailand and Indonesia concentrated on the improvement of physical properties of RVNRL using radiation grafted PMMA as additive [2]. F. Sundardi and W. Sofiarti have reported that tensile strength and hardness increased by radiation grafting of styrene onto NR [5]. Ono et al have reported the grafting of MMA onto NR by gamma irradiation at a dose of 5 kGy for producing thermoplastic elastomers [4]. The objective of this project is to report the results of studies of radiation graft-copolymerization of methyl methacrylate (MMA) or styrene (St) onto natural rubber latex in order to improve their physico-mechanical properties and evaluation of grafted material using Small-Angle Neutron Scattering through FNCA Project. The grafting degree of MMA and St onto NR increased with the increase of irradiation dose and monomer concentration. The alteration of grafted products structure was determined by IR method. Tensile strength, Shore A hardness, 100% modulus of grafted products increased with the increase of monomer concentration and irradiation dose while elongation at break decreased. The grafted products were characterized by Transmission Electron

  7. Evaluation of level of impregnation monomers in hydrotalcite; Avaliacao do grau de impregnacao de monomeros em hidrotalcita

    Energy Technology Data Exchange (ETDEWEB)

    Carmo, Danieli M. do, E-mail: danielimcarmo@hotmail.com [Instituto de Macromoleculas Professora Eloisa Mano - IMA, Universidade Federal do Rio de Janeiro - UFRJ, RJ (Brazil); Machado, Jacson S.C.; Oliveira, Marcelo F.L.; Oliveira, Marcia G. [Instituto Nacional de Tecnologia - INT, Rio de Janeiro, RJ (Brazil); Soares, Bluma G. [Instituto de Macromoleculas Professora Eloisa Mano - IMA, Universidade Federal do Rio de Janeiro - UFRJ, RJ (Brazil)

    2011-07-01

    To evaluate the impregnation degree of 1,6-hexamethylene diisocyanate and 1,4-butanediol monomers in hydrotalcite clays it was prepared dispersions with mixing ratio 1:100 (clay/monomer), using the Ultraturrax and Ultrasound. Subsequently the samples were characterized by Fourier Transform Infrared Spectroscopy and X-ray Diffraction. Swelling tests and Tyndall effect were used to illustrate the different dispersions. The results indicated a strong interaction between the hydrotalcite with 1,6-hexamethylene diisocyanate, favoring the formation of intercalated structures. (author)

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

    Directory of Open Access Journals (Sweden)

    Guzmán Pablo E.

    2016-03-01

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

  9. Reticuloendothelial hyperphagocytosis occurs in streptozotocin-diabetic rats. Studies with colloidal carbon, albumin microaggregates, and soluble fibrin monomers

    International Nuclear Information System (INIS)

    Cornell, R.P.

    1982-01-01

    In contrast to previous studies of diabetic humans and animals, which reported unchanged or depressed function, reticuloendothelial system (RES) hyperphagocytosis of colloidal carbon, 125 I-albumin microaggregates, and 125 I-fibrin monomers were observed in rats as early as 14 days after the induction of diabetes with streptozotocin (STZ). The fact that enhanced phagocytosis by RE macrophages was prevented by chronic insulin replacement therapy indicates that the diabetic internal environment of hyperglycemia and hypoinsulinemia was perhaps responsible for the observed changes. Experiments involving organ localization of intravenously administered particles, perfusion of isolated livers, and microscopic examination of the liver all suggested that increased Kupffer cell activity was the primary event in RES hyperphagocytosis by STZ-diabetic rats. Both hypertrophy and hyperplasia of Kupffer cells were apparent in livers of STZ-diabetic animals as evidenced by photomicrographs and hepatic cell quantification. Plasma fibronectin, which binds fibrin monomers to RE macrophages before phagocytosis, was significantly decreased in the circulation of STZ-diabetic rats, but the level of cell-associated fibronectin was not measured. Renal localization of urea-soluble 125 I-fibrin monomers exceeded splenic and pulmonary uptake in normal control rats and was enhanced in animals with STZ-diabetes. Changes in fibronectin levels, fibrin monomer localization, and Kupffer cell size and numbers in experimental diabetes in rats may have implications for the pathogenesis of vascular disease involving phagocytic mesangial and foam cells in diabetic humans

  10. Reticuloendothelial hyperphagocytosis occurs in streptozotocin-diabetic rats. Studies with colloidal carbon, albumin microaggregates, and soluble fibrin monomers.

    Science.gov (United States)

    Cornell, R P

    1982-02-01

    In contrast to previous studies of diabetic humans and animals, which reported unchanged or depressed function, reticuloendothelial system (RES) hyperphagocytosis of colloidal carbon, 125I-albumin microaggregates, and 125I-fibrin monomers were observed in rats as early as 14 days after the induction of diabetes with streptozotocin (STZ). The fact that enhanced phagocytosis by RE macrophages was prevented by chronic insulin replacement therapy indicates that the diabetic internal environment of hyperglycemia and hypoinsulinemia was perhaps responsible for the observed changes. Experiments involving organ localization of intravenously administered particles, perfusion of isolated livers, and microscopic examination of the liver all suggested that increased Kupffer cell activity was the primary event in RES hyperphagocytosis by STZ-diabetic rats. Both hypertrophy and hyperplasia of Kupffer cells were apparent in livers of STZ-diabetic animals as evidenced by photomicrographs and hepatic cell quantification. Plasma fibronectin, which binds fibrin monomers to RE macrophages before phagocytosis, was significantly decreased in the circulation of STZ-diabetic rats, but the level of cell-associated fibronectin was not measured. Renal localization of urea-soluble 125I-fibrin monomers exceeded splenic and pulmonary uptake in normal control rats and was enhanced in animals with STZ-diabetes. Changes in fibronectin levels, fibrin monomer localization, and Kupffer cell size and numbers in experimental diabetes in rats may have implications for the pathogenesis of vascular disease involving phagocytic mesangial and foam cells in diabetic humans.

  11. Effect of increased exposure times on amount of residual monomer released from single-step self-etch adhesives.

    Science.gov (United States)

    Altunsoy, Mustafa; Botsali, Murat Selim; Tosun, Gonca; Yasar, Ahmet

    2015-10-16

    The aim of this study was to evaluate the effect of increased exposure times on the amount of residual Bis-GMA, TEGDMA, HEMA and UDMA released from single-step self-etch adhesive systems. Two adhesive systems were used. The adhesives were applied to bovine dentin surface according to the manufacturer's instructions and were polymerized using an LED curing unit for 10, 20 and 40 seconds (n = 5). After polymerization, the specimens were stored in 75% ethanol-water solution (6 mL). Residual monomers (Bis-GMA, TEGDMA, UDMA and HEMA) that were eluted from the adhesives (after 10 minutes, 1 hour, 1 day, 7 days and 30 days) were analyzed by high-performance liquid chromatography (HPLC). The data were analyzed using 1-way analysis of variance and Tukey HSD tests. Among the time periods, the highest amount of released residual monomers from adhesives was observed in the 10th minute. There were statistically significant differences regarding released Bis-GMA, UDMA, HEMA and TEGDMA between the adhesive systems (p<0.05). There were no significant differences among the 10, 20 and 40 second polymerization times according to their effect on residual monomer release from adhesives (p>0.05). Increasing the polymerization time did not have an effect on residual monomer release from single-step self-etch adhesives.

  12. Biocatalytic synthesis and polymerization via ROMP of new biobased phenolic monomers: a greener process towards sustainable antioxidant polymers

    Science.gov (United States)

    Diot-Néant, Florian; Migeot, Loïs; Hollande, Louis; Reano, Felix A.; Domenek, Sandra; Allais, Florent

    2017-12-01

    Antioxidant norbornene-based monomers bearing biobased sterically hindered phenols (SHP) - NDF (norbornene dihydroferulate) and NDS (norbornene dihydrosinapate) - have been successfully prepared through biocatalysis from naturally occurring ferulic and sinapic acids, respectively, in presence of Candida antarctica Lipase B (Cal-B). The ring opening metathesis polymerization (ROMP) of these monomers was investigated according to ruthenium catalyst type (GI) vs. (HGII) and monomer to catalyst molar ratio ([M]/[C]). The co-polymerization of antioxidant functionalized monomer (NDF or NDS) and non-active norbornene (N) has also been performed in order to adjust the number of SHP groups present per weight unit and tune the antioxidant activity of the copolymers. The polydispersity of the resulting copolymers was readily improved by a simple acetone wash to provide antioxidant polymers with well-defined structures. After hydrogenation with p-toluenesulfonylhydrazine (p-TSH), the radical scavenging ability of the resulting saturated polymers was evaluated using α,α-diphenyl-β-picrylhydrazyl (DPPH) analysis. Results demonstrated that polymers bearing sinapic acid SHP exhibited higher antiradical activity than the polymer bearing ferulic acid SHP. In addition it was also shown that only a small SHP content was needed in the copolymers to exhibit a potent antioxidant activity.

  13. Monomers and polymers in a centrifugal field : a new method to produce refractive-index gradients in polymers

    NARCIS (Netherlands)

    Duijnhoven, van F.G.H.; Bastiaansen, C.W.M.

    1999-01-01

    A new method is presented to generate and to fixate compositional gradients in blends of two miscible and amorphous polymers. A compositional gradient is introduced into a solution of a polymer in a monomer by use of a centrifugal field, and this gradient is subsequently fixated by polymerization of

  14. Structural similarity between β(3)-peptides synthesized from β(3)-homo-amino acids and aspartic acid monomers.

    Science.gov (United States)

    Ahmed, Sahar; Sprules, Tara; Kaur, Kamaljit

    2014-07-01

    Formation of stable secondary structures by oligomers that mimic natural peptides is a key asset for enhanced biological response. Here we show that oligomeric β(3)-hexapeptides synthesized from L-aspartic acid monomers (β(3)-peptides 1, 5a, and 6) or homologated β(3)-amino acids (β(3)-peptide 2), fold into similar stable 14-helical secondary structures in solution, except that the former form right-handed 14-helix and the later form left-handed 14-helix. β(3)-Peptides from L-Asp monomers contain an additional amide bond in the side chains that provides opportunities for more hydrogen bonding. However, based on the NMR solution structures, we found that β(3)-peptide from L-Asp monomers (1) and from homologated amino acids (2) form similar structures with no additional side-chain interactions. These results suggest that the β(3)-peptides derived from L-Asp are promising peptide-mimetics that can be readily synthesized using L-Asp monomers as well as the right-handed 14-helical conformation of these β(3)-peptides (such as 1 and 6) may prove beneficial in the design of mimics for right-handed α-helix of α-peptides. © 2014 Wiley Periodicals, Inc.

  15. Preparation of polyurethane foams using liquefied oil palm mesocarp fibre (OPMF) and renewable monomer from waste cooking oil

    Science.gov (United States)

    Kormin, Shaharuddin; Rus, Anika Zafiah M.; Azahari, M. Shafiq M.

    2017-09-01

    The aim of this research is the production of polyurethane (PU) foams with biopolyols from liquefied oil palm mesocarp fibre (OPMF) and renewable monomer. Liquefaction of OPMF was studied using polyhydric alcohol (PA) which is PEG-400 as liquefaction solvents in conventional glass flask. In the second part of this paper was obtained the PU foams which presented good results when compared with commercial foams and include polyols from of fossil fuels. PU foams were prepared by mixing liquefied OPMF biopolyol, renewable monomer from waste cooking, additives and methylene diphenyl diisocyanate (MDI). Water was used as an environmental friendly blowing agent. The factors that influence the cell structure of foams (i.e., catalyst, surfactant, dosage of blowing agent, and mass ratio of biopolyol to renewable monomer were studied. The synthesized PU foams were characterized by FTIR and SEM. The formulation of the PU foams should be improved, but the results show that is possible the use biopolyols and renewable monomer to produce industrial foams with lower cost.

  16. Dimer monomer transition and dimer re-formation play important role for ATM cellular function during DNA repair

    International Nuclear Information System (INIS)

    Du, Fengxia; Zhang, Minjie; Li, Xiaohua; Yang, Caiyun; Meng, Hao; Wang, Dong; Chang, Shuang; Xu, Ye; Price, Brendan; Sun, Yingli

    2014-01-01

    Highlights: • ATM phosphorylates the opposite strand of the dimer in response to DNA damage. • The PETPVFRLT box of ATM plays a key role in its dimer dissociation in DNA repair. • The dephosphorylation of ATM is critical for dimer re-formation after DNA repair. - Abstract: The ATM protein kinase, is a serine/threonine protein kinase that is recruited and activated by DNA double-strand breaks, mediates responses to ionizing radiation in mammalian cells. Here we show that ATM is held inactive in unirradiated cells as a dimer and phosphorylates the opposite strand of the dimer in response to DNA damage. Cellular irradiation induces rapid intermolecular autophosphorylation of serine 1981 that causes dimer dissociation and initiates cellular ATM kinase activity. ATM cannot phosphorylate the substrates when it could not undergo dimer monomer transition. After DNA repair, the active monomer will undergo dephosphorylation to form dimer again and dephosphorylation is critical for dimer re-formation. Our work reveals novel function of ATM dimer monomer transition and explains why ATM dimer monomer transition plays such important role for ATM cellular activity during DNA repair

  17. Folding Landscape of Mutant Huntingtin Exon1: Diffusible Multimers, Oligomers and Fibrils, and No Detectable Monomer.

    Directory of Open Access Journals (Sweden)

    Bankanidhi Sahoo

    Full Text Available Expansion of the polyglutamine (polyQ track of the Huntingtin (HTT protein above 36 is associated with a sharply enhanced risk of Huntington's disease (HD. Although there is general agreement that HTT toxicity resides primarily in N-terminal fragments such as the HTT exon1 protein, there is no consensus on the nature of the physical states of HTT exon1 that are induced by polyQ expansion, nor on which of these states might be responsible for toxicity. One hypothesis is that polyQ expansion induces an alternative, toxic conformation in the HTT exon1 monomer. Alternative hypotheses posit that the toxic species is one of several possible aggregated states. Defining the nature of the toxic species is particularly challenging because of facile interconversion between physical states as well as challenges to identifying these states, especially in vivo. Here we describe the use of fluorescence correlation spectroscopy (FCS to characterize the detailed time and repeat length dependent self-association of HTT exon1-like fragments both with chemically synthesized peptides in vitro and with cell-produced proteins in extracts and in living cells. We find that, in vitro, mutant HTT exon1 peptides engage in polyQ repeat length dependent dimer and tetramer formation, followed by time dependent formation of diffusible spherical and fibrillar oligomers and finally by larger, sedimentable amyloid fibrils. For expanded polyQ HTT exon1 expressed in PC12 cells, monomers are absent, with tetramers being the smallest molecular form detected, followed in the incubation time course by small, diffusible aggregates at 6-9 hours and larger, sedimentable aggregates that begin to build up at 12 hrs. In these cell cultures, significant nuclear DNA damage appears by 6 hours, followed at later times by caspase 3 induction, mitochondrial dysfunction, and cell death. Our data thus defines limits on the sizes and concentrations of different physical states of HTT exon1 along the

  18. Investigation of the Hydantoin Monomer and its Interaction with Water Molecules

    Science.gov (United States)

    Gruet, Sébastien; Perez, Cristobal; Schnell, Melanie

    2017-06-01

    Hydantoin (Imidazolidine-2,4-dione, C_3H_4N_2O_2) is a five-membered heterocyclic compound of astrobiological interest. This molecule has been detected in carbonaceous chondrites [1], and its formation can rise from the presence of glycolic acid and urea, two prebiotic molecules [2]. The hydrolysis of hydantoin under acidic conditions can also produce glycine [3], an amino acid actively searched for in the interstellar medium. Spectroscopic data of hydantoin is very limited and mostly dedicated to the solid phase. The high resolution study in gas phase is restricted to the work recently published by Ozeki et al. reporting the pure rotational spectra of the ground state and two vibrational states of the molecule in the millimeter-wave region (90-370 GHz)[4]. Using chirped-pulse Fourier-transform microwave (CP-FTMW) spectroscopy, we recorded the jet-cooled rotational spectra of hydantoin with water between 2 to 8 GHz. We observed the ground state of hydantoin monomer and several water complexes with one or two water molecules. All the observed species exhibit a hyperfine structure due to the two nitrogen atoms present in the molecule, which were fully resolved and analyzed. Additional experiments with a ^{18}O enriched water sample were realized to determine the oxygen-atom positions of the water monomers. These experiments yielded accurate structural information on the preferred water binding sites. The observed complexes and the interactions that hold them together, mainly strong directional hydrogen bonds, will be presented and discussed. [1] Shimoyama, A. and Ogasawara, R., Orig. Life Evol. Biosph., 32, 165-179, 2002. DOI:10.1023/A:1016015319112. [2] Menor-Salván, C. and Marín-Yaseli, M.R., Chem. Soc. Rev., 41(16), 5404-5415, 2012. DOI:10.1039/c2cs35060b. [3] De Marcellus P., Bertrand M., Nuevo M., Westall F. and Le Sergeant d'Hendecourt L., Astrobiology. 11(9), 847-854, 2011. DOI:10.1089/ast.2011.0677. [4] Ozeki, H., Miyahara R., Ihara H., Todaka S., Kobayashi

  19. Effect of Rhizopus oryzae Fermentation on Kenaf-Based Polylactic Acid’s Monomer

    Directory of Open Access Journals (Sweden)

    Nur Aimi Mohd Nasir

    2011-12-01

    Full Text Available Kenaf biomass is the potential as raw materials used to produce polylactic acid's monomer which is lactic acid via fermentation by Rhizopus oryzae. Kenaf biomass' structure is complex due to its lignin and cellulose content. This matter had encouraged it to undergo pre- treatment process as the initial step before fermentation process can be done. In this paper, kenaf biomass was treated with dilute sulphuric acid (H2SO4 to hydrolyze the cellulose content in it as well as to convert the cellulose into glucose- a carbon source for Rhizopus to grow. Then, the fermentation process was carried out in shake flask for 3 days at pH 6. Several conditions for fermentation process had been chosen which were 25oC at 150 rpm, 25 oC at 200 rpm, 37 oC at 150 rpm and 37oC at 200 rpm. In this fermentation process, 0.471 g/L, 0.428 g/L, 0.444 g/L and 0.38 g/L of lactic acid was produced respectively. Sample at 25oC at 200 rpm produced maximum amount of lactic acid compared to others.ABSTRAK: Biojisim kenaf berpotensi sebagai bahan mentah dalam penghasilan monomer asid polylactic (poliester alifatik termoplastik diterbitkan daripada sumber boleh diperbaharu seperti kanji jagung yang merupakan asid laktik menerusi penapaian oleh Rhizopus oryzae (sejenis fungus yang hidup dalam jirim organik yang telah mati. Struktur biojisim kenaf adalah kompleks disebabkan kandungan lignin dan selulosanya. Hal ini menyebabkan ia perlu melalui proses pra-rawatan sebagai langkah awal sebelum proses penapaian dijalankan. Dalam kertas ini, biojirim kenaf dirawat dengan asid sulfurik (H2SO4 yang dicairkan untuk menghidrolisis kandungan selulosa di dalamnya di samping menukar selulosa menjadi glukosa - sumber karbon bagi tumbesaran Rhizopus. Kemudian, proses penapaian dijalankan di dalam kelalang goncang selama 3 hari pada pH 6. Beberapa ciri proses penapaian telah dipilih iaitu 25 oC pada 150 rpm, 25 oC pada 200 rpm, 37 oC pada 150 rpm dan 37 oC pada 200 rpm. Dalam proses penapaian

  20. Design, synthesis and characterization of a highly luminescent Eu-complex monomer featuring thenoyltrifluoroacetone and 5-acryloxyethoxymethyl-8-hydroxyquinoline

    Energy Technology Data Exchange (ETDEWEB)

    Xu Cunjin [State Key Laboratory of Chemical Engineering, Department of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027 (China); College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 310036 (China); Li Bogeng, E-mail: bgli@zju.edu.cn [State Key Laboratory of Chemical Engineering, Department of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027 (China); Wan Jintao; Bu Zhiyang [State Key Laboratory of Chemical Engineering, Department of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027 (China)

    2011-08-15

    A multi-functional ligand, 5-acryloxyethoxymethyl-8-hydroxyquinoline (Hamq), was synthesized, which contained a polymerizable C=C double bond for the copolymerization with other vinyl monomers and acted as photon antenna able to transfer energy to Eu{sup 3+} ions effectively. The triplet state energy of Hamq was determined to be 22,370 cm{sup -1} via the phosphorescence spectra of Hamq and its gadolinium complex. The title complex monomer Eu(tta){sub 2}(amq) was prepared by coordination reaction of Hamq with europium isopropoxide and 2-thenoyltrifluoroacetone (Htta) in dry organic solvents under argon atmosphere and characterized by elemental analysis and IR spectrum. The photophysical properties of the complex were studied in detail with UV-vis, luminescence spectra, luminescence lifetime and quantum yield. The complex exhibited nearly monochromatic red emission at 612 nm, a remarkable luminescence quantum yield at room temperature (30.6%) upon ligand excitation and a long {sup 5}D{sub 0} lifetime (389 {mu}s), which indicated that the ligand Hamq could sensitize the luminescence of Eu(III) ion efficiently in Eu(tta){sub 2}(amq), resulting in a strong luminescence of its copolymer poly[MMA-co-Eu(TTA){sub 2}(amq)] under UV excitation. The excellent luminescence properties of the complex made it not only a promising light-conversion molecular device but also an excellent luminescent monomer. - Highlights: >iWe designed and synthesized a highly luminescent Eu-complex monomer. > Quantum yield and lifetime of the complex are 30.6% and 389 {mu}s, respectively. > Excellent luminescence of the complex made it an excellent luminescent monomer.

  1. The effect of the polymerization initiator and light source on the elution of residual Bis-GMA and TEGDMA monomers: A study using liquid chromatography with UV detection.

    Science.gov (United States)

    Denis, Aline B; Diagone, Cristina A; Plepis, Ana M G; Viana, Rommel B

    2015-12-05

    A method for the extraction and quantification of two residual monomers, bisphenol glycidyl dimethacrylate (Bis-GMA) and triethylene glycol dimethacrylate (TEGDMA), that were evaluated using high efficiency liquid chromatography with UV detection was developed and validated in this study. Three types of solvents were applied in the extraction of the monomers (methanol, ethanol and acetonitrile), where the highest extraction efficiency was obtained using acetonitrile. The different resins were prepared by photoactivation of Bis-GMA and TEGDMA monomers. Additionally, the effects of the addition of two photoinitiators (camphorquinone (CQ) and phenyl propanodione (PPD) and that of a co-initiator (N,N-dimethyl-p-toluidine) were also analyzed. When only the CQ photoinitiator was used, a smaller amount of residual monomers was obtained, whereas a larger amount was obtained with PPD. When the two photoinitiators were used in the same matrix, however, no significant changes were observed in relation to the amount of residual TEGDMA monomers. For the addition of the co-initiator, there were no large changes in the extraction of residual monomers. The effect of the two photoactivation sources (halogen lamp and LED) led to small differences in the elution of the two monomers, although all of the resins differed significantly when photoactivated with a LED. Quantum chemical calculations using Density Functional Theory were carried out to characterize several molecular properties of each monomer. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Synthesis and spectroscopy of clay intercalated Cu(II) bio-monomer complexes: coordination of Cu(II) with purines and nucleotides

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Leeman, H.; Schoonheydt, R.A.

    1999-01-01

    The spectroscopic properties of Cu(bio-monomer)nm+ complexes [BM=bio-monomer (purine, adenine, guanine, hypoxanthine, 5-ADP and 5-GMP)] in saponite clays have been investigated by diffuse reflectance spectroscopy (DRS) in the UV-Vis-NIR region and electron paramagnetic resonance (EPR) at X-band.

  3. N-Acetyl Cysteine Depletes Reactive Oxygen Species and Prevents Dental Monomer-Induced Intrinsic Mitochondrial Apoptosis In Vitro in Human Dental Pulp Cells.

    Directory of Open Access Journals (Sweden)

    Yang Jiao

    Full Text Available To investigate the involvement of intrinsic mitochondrial apoptosis in dental monomer-induced cytotoxicity and the influences of N-acetyl cysteine (NAC on this process.Human dental pulp cells (hDPCs were exposed to several dental monomers in the absence or presence of NAC, and cell viability, intracellular redox balance, morphology and function of mitochondria and key indicators of intrinsic mitochondrial apoptosis were evaluated using various commercial kits.Dental monomers exerted dose-dependent cytotoxic effects on hDPCs. Concomitant to the over-production of reactive oxygen species (ROS and depletion of glutathione (GSH, differential changes in activities of superoxide dismutase, glutathione peroxidase, and catalase were detected. Apoptosis, as indicated by positive Annexin V/propidium iodide (PI staining and activation of caspase-3, was observed after dental monomer treatment. Dental monomers impaired the morphology and function of mitochondria, and induced intrinsic mitochondrial apoptosis in hDPCs via up-regulation of p53, Bax and cleaved caspase-3, and down-regulation of Bcl-2. NAC restored cell viability, relieved oxidative stress and blocked the apoptotic effects of dental monomers.Dental monomers induced oxidative stress and mitochondrial intrinsic apoptosis in hDPCs. NAC could reduce the oxidative stress and thus protect hDPCs against dental monomer-induced apoptosis.

  4. Recognition of double-stranded DNA using energetically activated duplexes with interstrand zippers of 1-, 2-or 4-pyrenyl-functionalized O2 '-alkylated RNA monomers

    DEFF Research Database (Denmark)

    Karmakar, Saswata; Madsen, Andreas Stahl; Guenther, Dale C.

    2014-01-01

    '-alkylated uridine monomers X-Z by means of thermal denaturation experiments, optical spectroscopy, force-field simulations and recognition experiments using DNA hairpins as model targets. We demonstrate that Invaders with +1 interstrand zippers of X or Y monomers efficiently recognize mixed-sequence DNA...

  5. Production of bone cement composites: effect of fillers, co-monomer and particles properties

    Energy Technology Data Exchange (ETDEWEB)

    Santos Junior, J.G.F.; Melo, P.A.; Pinto, J.C., E-mail: jjunior@peq.coppe.ufrj.b, E-mail: melo@peq.coppe.ufrj.b, E-mail: pinto@peq.coppe.ufrj.b [Coordenacao dos Programas de Pos-Graduacao de Engenharia. (PEQ/COPPE/UFRJ), RJ (Brazil). Programa de Engenharia Quimica; Pita, V.J.R.R., E-mail: vjpita@ima.ufrj.b [Universidade Federal do Rio de Janeiro (IMA/UFRJ), RJ (Brazil). Inst. de Macromoleculas Eloisa Mano; Nele, M. [Universidade Federal do Rio de Janeiro (EQ/UFRJ), RJ (Brazil). Escola de Quimica

    2011-04-15

    Artificial bone cements (BCs) based on poly(methyl methacrylate) (PMMA) powders and methyl methacrylate (MMA) liquid monomer also present in their formulation small amounts of other substances, including a chemical initiator compound and radiopaque agents. Because inadequate mixing of the recipe components during the manufacture of the bone cement may compromise the mechanical properties of the final pieces, new techniques to incorporate the fillers into the BC and their effect upon the mechanical properties of BC pieces were investigated in the present study. PMMA powder composites were produced in situ in the reaction vessel by addition of X-ray contrasts to the reacting MMA mixture. It is shown that this can lead to much better mechanical properties of test pieces, when compared to standard bone cement formulations, because enhanced dispersion of the radiopaque agents can be achieved. Moreover, it is shown that the addition of hydroxyapatite (HA) and acrylic acid (AA) to the bone cement recipe can be beneficial for the mechanical performance of the final material. It is also shown that particle morphology can exert a tremendous effect upon the performance of test pieces, indicating that the suspension polymerization step should be carefully controlled when optimization of the bone cement formulation is desired. (author)

  6. Production of bone cement composites: effect of fillers, co-monomer and particles properties

    Directory of Open Access Journals (Sweden)

    J. G. F. Santos Jr.

    2011-06-01

    Full Text Available Artificial bone cements (BCs based on poly(methyl methacrylate (PMMA powders and methyl methacrylate (MMA liquid monomer also present in their formulation small amounts of other substances, including a chemical initiator compound and radiopaque agents. Because inadequate mixing of the recipe components during the manufacture of the bone cement may compromise the mechanical properties of the final pieces, new techniques to incorporate the fillers into the BC and their effect upon the mechanical properties of BC pieces were investigated in the present study. PMMA powder composites were produced in-situ in the reaction vessel by addition of X-ray contrasts to the reacting MMA mixture. It is shown that this can lead to much better mechanical properties of test pieces, when compared to standard bone cement formulations, because enhanced dispersion of the radiopaque agents can be achieved. Moreover, it is shown that the addition of hydroxyapatite (HA and acrylic acid (AA to the bone cement recipe can be beneficial for the mechanical performance of the final material. It is also shown that particle morphology can exert a tremendous effect upon the performance of test pieces, indicating that the suspension polymerization step should be carefully controlled when optimization of the bone cement formulation is desired.

  7. Determination of Residual Monomers Released from Soft Lining Materials with the use of HPLC

    Directory of Open Access Journals (Sweden)

    Afrodite Sofou

    2007-12-01

    Full Text Available A study was carried out to examine the post polymerized leachability of three non phthalic and four phthalic residual monomers, from twelve commercially available soft lining materials, using HPLC. Specimens of equal dimensions were constructed from each brand of material following a standardized procedure and were stored in three different conditions of storage i.e. distilled water, artificial saliva and a binary mixture of ethanol-water, with the resulting liquids providing samples for analysis in the HPLC apparatus. Three different experiments were performed for each brand of material and each condition of storage, in order to examine the parameters time and temperature. The results obtained from this study suggest that a wide spectrum of residues is diffusing out of the twelve examined soft lining materials. The non phthalic compounds were leaching at high concentrations while all the phthalates examined exhibited different degrees of elusion commensurate with the storage condition, brand of material and type of experiment. The main non phthalic component extracted from all the materials was methyl methacrylate, while the mainly extracted phthalic compound was different from each material. The level of elusion seems to be increasing dependent on time, medium of storage, and temperature as well.

  8. Electrostatic Interactions between Elongated Monomers Drive Filamentation of Drosophila Shrub, a Metazoan ESCRT-III Protein

    Directory of Open Access Journals (Sweden)

    Brian J. McMillan

    2016-08-01

    Full Text Available The endosomal sorting complex required for transport (ESCRT is a conserved protein complex that facilitates budding and fission of membranes. It executes a key step in many cellular events, including cytokinesis and multi-vesicular body formation. The ESCRT-III protein Shrub in flies, or its homologs in yeast (Snf7 or humans (CHMP4B, is a critical polymerizing component of ESCRT-III needed to effect membrane fission. We report the structural basis for polymerization of Shrub and define a minimal region required for filament formation. The X-ray structure of the Shrub core shows that individual monomers in the lattice interact in a staggered arrangement using complementary electrostatic surfaces. Mutations that disrupt interface salt bridges interfere with Shrub polymerization and function. Despite substantial sequence divergence and differences in packing interactions, the arrangement of Shrub subunits in the polymer resembles that of Snf7 and other family homologs, suggesting that this intermolecular packing mechanism is shared among ESCRT-III proteins.

  9. A spin labelling study of immunomodulating peptidoglycan monomer and adamantyltripeptides entrapped into liposomes.

    Science.gov (United States)

    Frkanec, Ruza; Noethig-Laslo, Vesna; Vranesić, Branka; Mirosavljević, Krunoslav; Tomasić, Jelka

    2003-04-01

    The interaction of immunostimulating compounds, the peptidoglycan monomer (PGM) and structurally related adamantyltripeptides (AdTP1 and AdTP2), respectively, with phospholipids in liposomal bilayers were investigated by electron paramagnetic resonance spectroscopy. (1). The fatty acids bearing the nitroxide spin label at different positions along the acyl chain were used to investigate the interaction of tested compounds with negatively charged multilamellar liposomes. Electron spin resonance (ESR) spectra were studied at 290 and 310 K. The entrapment of the adamantyltripeptides affected the motional properties of all spin labelled lipids, while the entrapment of PGM had no effect. (2). Spin labelled PGM was prepared and the novel compound bearing the spin label attached via the amino group of diaminopimelic acid was chromatographically purified and chemically characterized. The rotational correlation time of the spin labelled molecule dissolved in buffer at pH 7.4 was studied as a function of temperature. The conformational change was observed above 300 K. The same effect was observed with the spin labelled PGM incorporated into liposomes. Such effect was not observed when the spin labelled PGM was studied at alkaline pH, probably due to the hydrolysis of PGM molecule. The study of possible interaction with liposomal membrane is relevant to the use of tested compounds incorporated into liposomes, as adjuvants in vivo.

  10. TUNG OIL BASED MONOMER FOR THERMOSETTING POLYMERS: SYNTHESIS, CHARACTERIZATION AND COPOLYMERIZATION WITH STYRENE

    Directory of Open Access Journals (Sweden)

    Chengguo Liu,

    2011-11-01

    Full Text Available A tung oil (TO based monomer for rigid thermosetting polymer was synthesized, characterized, and copolymerized with styrene in this study. Tung oil was alcoholyzed with pentaerythritol (PER to get tung oil pentaerythritol alcoholysis products (TOPER, and the optimized conditions were explored according to the yields of TOPER analyzed by gas chromatography-mass spectrometry (GC-MS. The resulting alcoholysis products were maleinated to form tung oil maleate half ester (TOPERMA, and the reaction conditions were determined by monitoring the reaction extents of TOPER and maleic anhydride (MA with 1HNMR spectroscopy. The TO alcoholysis and maleinization reaction products were characterized by IR, 1HNMR, and electrospray ionization-mass spectrometry (ESI-MS techniques. At last, the TOPERMA mixture was cured with styrene (St, and the initiator tert-butyl peroxy benzoate (TPB. Differential scanning calorimetry (DSC was employed to characterize the curing process. Mechanical properties of the cured TOPERMA/St resin further confirmed the best procedure for the maleinization reaction. The loading of TO reached about 30% weight of the resulting thermosetting polymer. This promising material from renewable resources can be a potential substitution for petroleum products when used as sheet molding compounds.

  11. Vegetable oil-derived epoxy monomers and polymer blends: A comparative study with review

    Directory of Open Access Journals (Sweden)

    T. P. Schuman

    2013-03-01

    Full Text Available Glycidyl esters of epoxidized fatty acids derived from soybean oil (EGS and linseed oil (EGL have been synthesized to have higher oxirane content, more reactivity and lower viscosity than epoxidized soybean oil (ESO or epoxidized linseed oil (ELO. The EGS and ESO, for comparison, were used neat and in blends with diglycidyl ether of bisphenol A (DGEBA. Thermosetting resins were fabricated with the epoxy monomers and either BF3 catalyst or anhydride. The curing behaviors, glass transition temperatures, crosslink densities and mechanical properties were tested. The results indicated that polymer glass transition temperatures were mostly a function of oxirane content with additional influence of glycidyl versus internal oxirane reactivity, pendant chain content, and chemical structure and presence of saturated components. EGS provided better compatibility with DGEBA, improved intermolecular crosslinking and glass transition temperature, and yielded mechanically stronger polymerized materials than materials obtained using ESO. Other benefits of the EGS resin blend systems were significantly reduced viscosities compared to either DGEBA or ESO-blended DGEBA counterparts. Therefore, EGS that is derived from renewable sources has improved potential for fabrication of structural and structurally complex epoxy composites, e.g., by vacuum-assisted resin transfer molding.

  12. Water-resistive humidity sensor prepared by printing process using polyelectrolyte ink derived from new monomer.

    Science.gov (United States)

    Kim, Min-Ji; Gong, Myoung-Seon

    2012-03-21

    A simple strategy was developed based on a new monomer containing both photocurable function and ammonium salt, N-(2-cinnamoyloxy)ethyl-N-(2-(methacryloyloxy)ethyl)-N,N-dimethyl ammonium bromide (CMDAB) to obtain photocurable polyelectrolyte ink and stable humidity-sensitive membranes by printing process. Humidity-sensitive membranes are photocrosslinked polyelectrolytes obtained from copolymers of [2-(methacryloyloxy)ethyl] dimethyl propyl ammonium bromide (MEPAB), CMDAB and MMA. A flexible gold electrode/polyimide was pretreated with 2-(mercaptoethyl) cinnamamide (MEC) containing a thiol-coupling agent for the purpose of anchoring the humidity-sensitive polyelectrolyte to the gold electrode. The sensors using screen printing methods reduced the deflection of sensor characteristics showing humidity precision ±1%RH. The photocured copolymer MEPAB/CMDAB/MMA = 63/7/30 show good sensitivity (0.0586 logΩ/%RH) changing resistance approximately four orders of magnitude with relative humidity varying from 20% to 95% and fast response and recovery time. The resultant sensors showed acceptable linearity (Y = -0.04X + 7.0, R(2) = -0.9900) and small hysteresis. The reliability including water resistance and a long-term stability were estimated for the application of the flexible humidity sensor prepared by screen printing process.

  13. Effect of residual monomer from polyacrylamide on head lettuce grown in peat substrate.

    Science.gov (United States)

    Mroczek, Ewelina; Kleiber, Tomasz; Konieczny, Piotr; Waśkiewicz, Agnieszka

    2015-01-01

    The paper investigates the migration of the acrylamide monomer (AMD) to lettuce chosen as a test plant growing in an organic medium (peat substrate). Polyacrylamide (PAM)-based flocculant added to the growing medium contained no more than 1000 mg kg(-1) of AMD. Plants were grown with varied doses of PAM preparation (0.5-3.0 mg dm(-3) of peat substrate) to compare the results with the control sample. The determination of AMD content, chlorophyll content, weight of the lettuce head, and also analysis of macro- and micro-elements in lyophilised test material was made under the same analytical conditions. The results showed that lettuce plants absorb AMD to the leaves from the peat substrate. The AMD uptake has a negative impact on the growth of lettuce. It reduces the average fresh weight of heads and destabilises the mineral composition of the plant. Therefore, concern related to the transfer risk of the residual AMD from sludge used for organic fertilisation of edible plants still remains a crucial question from a food and consumer safety point of view. To ensure consumer safety, the fate of the AMD following the application of PAM to cropland should be carefully monitored in the whole food chain.

  14. Determination of residual monomers released from soft lining materials with the use of HPLC

    International Nuclear Information System (INIS)

    Sofou, A.; Tsoupi, I.; Karayannia, M.

    2007-01-01

    A study was carried out to examine the post polymerized leachability of three non phthalic and four phthalic residual monomers, from twelve commercially available soft lining materials, using HPLC. Specimens of equal: dimensions were constructed from each brand of material following a standardized procedure and were stored in three different conditions of storage i.e. distilled water, artificial saliva and a binary mixture of ethanol-water with the resulting liquids providing samples for analysis in the HPLC apparatus. Three different experiments were performed for each brand of material and each condition of storage, in order to examine the parameters time and temperature. The results obtained from this study suggest that a wide spectrum of residues is diffusing out of the twelve examined soft lining materials. The non phthalic compounds were leaching at high concentrations while all the phthalates examined exhibited different degrees of elusion commensurate with the storage condition, brand of material and type of experiment. The main non phthalic component extracted from all the materials was methyl methacrylate, while the mainly extracted phthalic compound was different from each material. The level of elusion seems to be increasing dependent on time, medium of storage and temperature as well. (author)

  15. Polymerization kinetics of monomers of importance in biomedicine investigated by γirradiation

    International Nuclear Information System (INIS)

    Bebe, S.; Monteiro, M.J.; Ganachaud, F.; Napper, D.H.; Gilbert, R.G.

    1998-01-01

    Gamma irradiation was used to initiate the polymerization of NIPAM in water below the LCST. Conversion as a function of time was followed with automated tracking dilatometry. The data were used to show that classical kinetics were obeyed. Relaxation experiments (i.e. where the dilatometer is removed from the γ source) then provide reliable values for the reactivity ratio, k i /k p , the ratio of the termination to propagation rate coefficients. It was found at a monomer concentration of 0.442 M, k i k p had a value of 8.1 at 27 deg C . This suggested that either k t was very low, perhaps because the radicals are constrained to some complexation or aggregation mechanism, or k p is extraordinarily high. Pulsed laser polymerizations (in conjunction with size exclusion chromatography, SEC) were performed to obtain accurate k p values for NIPAM in water over a temperature range below the LCST (2 - 27 deg C ). The main difficulty with most functional polymers is obtaining quantitative data from SEC. PNIPAM is no exception to the rule, and meticulous care in molecular weight analysis was necessary. Special insights were developed into sample preparation to obtain accurate molecular weight distributions (MWD). The value k p was found to be high, but not extraordinarily so, and hence the high value of k t must be due to a constrained polymer radical

  16. Alternate fuels and chemicals from synthesis gas: Vinyl acetate monomer. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Richard D. Colberg; Nick A. Collins; Edwin F. Holcombe; Gerald C. Tustin; Joseph R. Zoeller

    1999-01-01

    There has been a long-standing desire on the part of industry and the U.S. Department of Energy to replace the existing ethylene-based vinyl acetate monomer (VAM) process with an entirely synthesis gas-based process. Although there are a large number of process options for the conversion of synthesis gas to VAM, Eastman Chemical Company undertook an analytical approach, based on known chemical and economic principles, to reduce the potential candidate processes to a select group of eight processes. The critical technologies that would be required for these routes were: (1) the esterification of acetaldehyde (AcH) with ketene to generate VAM, (2) the hydrogenation of ketene to acetaldehyde, (3) the hydrogenation of acetic acid to acetaldehyde, and (4) the reductive carbonylation of methanol to acetaldehyde. This report describes the selection process for the candidate processes, the successful development of the key technologies, and the economic assessments for the preferred routes. In addition, improvements in the conversion of acetic anhydride and acetaldehyde to VAM are discussed. The conclusion from this study is that, with the technology developed in this study, VAM may be produced from synthesis gas, but the cost of production is about 15% higher than the conventional oxidative acetoxylation of ethylene, primarily due to higher capital associated with the synthesis gas-based processes.

  17. Development of a New Monomer for the Synthesis of Intrinsic Antimicrobial Polymers with Enhanced Material Properties.

    Science.gov (United States)

    Brodkorb, Florian; Fischer, Björn; Kalbfleisch, Katrin; Robers, Oliver; Braun, Carina; Dohlen, Sophia; Kreyenschmidt, Judith; Lorenz, Reinhard; Kreyenschmidt, Martin

    2015-08-24

    The use of biocidal compounds in polymers is steadily increasing because it is one solution to the need for safety and hygiene. It is possible to incorporate an antimicrobial moiety to a polymer. These polymers are referred to as intrinsic antimicrobial. The biocidal action results from contact of the polymer to the microorganisms, with no release of active molecules. This is particularly important in critical fields like food technology, medicine and ventilation technology, where migration or leaching is crucial and undesirable. The isomers N-(1,1-dimethylethyl)-4-ethenyl-benzenamine and N-(1,1-dimethyl-ethyl)-3-ethenyl-benzenamine (TBAMS) are novel (Co-)Monomers for intrinsic anti-microbial polymers. The secondary amines were prepared and polymerized to the corresponding water insoluble polymer. The antimicrobial activity was analyzed by the test method JIS Z 2801:2000. Investigations revealed a high antimicrobial activity against Staphylococcus aureus and Escherichia coli with a reduction level of >4.5 log10 units. Furthermore, scanning electron microscopy (SEM) of E. coli. in contact with the polymer indicates a bactericidal action which is caused by disruption of the bacteria cell membranes, leading to lysis of the cells.

  18. Copolymers of Vinyl-Containing Benzoxazine with Vinyl Monomers as Precursors for High Performance Thermosets

    Directory of Open Access Journals (Sweden)

    Tsutomu Takeichi

    2015-04-01

    Full Text Available A benzoxazine containing a vinyl group (P-4va was prepared by the reaction of phenol, 4-vinylaniline, and paraformaldehyde. A differential scanning calorimetry (DSC study revealed that ring-opening polymerization of the benzoxazine and chain polymerization of the vinyl group occurred in the same temperature range. When 2,2'-azobisisobutyronitrile was added as a radical initiator to P-4va, however, only the vinyl groups were polymerized at lower temperature, giving oligo(P-4va that contains pendent benzoxazine units. Radical copolymerization of P-4va with various vinyl monomers such as styrene, methyl methacrylate (MMA, and n-butyl acrylate (BuA was examined. The chemical structure of the copolymers was confirmed by FT-IR and 1H-NMR to be one of polyolefins bearing benzoxazine units as the pendant groups. The weight-average molecular weights of the copolymers determined by size exclusion chromatography were to be in the range of 1900–51,500 depending on the comonomers. DSC of the copolymers showed that the maxima of the exothermic peaks corresponding to the ring-opening polymerization of the pendent benzoxazine units were observed in the temperature range of 229–250 °C. Thermal cure up to 240 °C of the copolymer films afforded homogenous transparent films with improved thermal properties. Tough cured film was obtained by the copolymerization with MMA, while a tough and flexible film was obtained by the copolymerization with BuA.

  19. Radiation grafting of hydrophilic monomers on to plasticized poly(vinyl chloride) sheets: Pt. 1

    International Nuclear Information System (INIS)

    Kalliyana Krishnan, V.; Jayakrishnan, A.; Francis, J.D.

    1990-01-01

    Medical-grade plasticized polyvinyl chloride (PVC) sheets were surface modified using gamma-radiation grafting of a combination of hydrophilic monomers based on 2-hydroxyethyl methacrylate (HEMA) and N-vinyl pyrrolidone (NVP). The properties of the modified surfaces were evaluated using contact angle measurements, phase-contrast photomicroscopy and scanning electron microscopy. Surface energy calculations indicated that the surfaces became highly hydrophilic when grafted with even a 1% (v/v) solution of HEMA-NVP combination in the presence of 0.005 M CuSO 4 . Migration of the plasticizer di(2-ethylhexyl phthalate) from the grafted sheets was examined in hydrocarbon solvents such as n-hexane, n-heptane and n-octane and in extractant media such as cotton seed oil and polyethylene glycol-400 (PEG-400). The migration was found to be 0 C over a period of 5 h. Accelerated leaching studies in cotton seed oil and PEG-400 demonstrated that virtually no plasticizer migrated out in the former over a period of 96 h whereas the rate of migration in the latter medium showed only a mild reduction. The migration behaviour was Fickian in nature for grafted sheets. The method described may be useful as a simple, versatile technique for preventing plasticizer migration from plasticized PVC for medical applications. (author)

  20. Properties of PHA bi-, ter-, and quarter-polymers containing 4-hydroxybutyrate monomer units.

    Science.gov (United States)

    Zhila, Natalia; Shishatskaya, Ekaterina

    2018-05-01

    The present study investigates physicochemical, mechanical, and biological properties of polyhydroxyalkanoate (PHA) copolymers containing 4-hydroxybutyrate (4HB) synthesized in Cupriavidus eutrophus B10646 culture. In poly(3-hydroxybutyrate/4-hydroxybutyrate) [P(3HB/4HB)] bipolymers, 4HB varied between 10.4 and 75.0 mol%; in poly(3-hydroxybutyrate/3-hydroxyvalerate/4-hydroxybutyrate) terpolymers, 4HB constituted 28.7-55.6 mol%; and in poly(3-hydroxybutyrate/3-hydroxyvalerate/4-hydroxybutyrate/3-hydroxyhexanoate) quaterpolymers, 4HB varied between 9.3 and 13.3 mol%. The degree of crystallinity of P(3HB/4HB) copolymers decreased consistently with an increase in 4HB content, reaching 38%. The incorporation of 3-hydroxyvalerate and 3-hydroxyhexanoate into copolymers enhanced that effect. The effect of 4HB monomer units on temperature properties of copolymers was exhibited as lowering of the melting temperature and crystallization temperature, which improved the processing-related properties of the copolymers. All copolymers containing 4HB showed enhanced elongation at break compared to poly(3-hydroxybutyrate). Polymer films prepared from PHAs with different chemical composition had similar microstructure and porosity and had no toxic effect on mouse fibroblast NIH 3 T3 cells, proving their high biocompatibility. Copyright © 2018 Elsevier B.V. All rights reserved.

  1. Genetic loci simultaneously controlling lignin monomers and biomass digestibility of rice straw.

    Science.gov (United States)

    Hu, Zhen; Zhang, Guifen; Muhammad, Ali; Samad, Rana Abdul; Wang, Youmei; Walton, Jonathan D; He, Yuqing; Peng, Liangcai; Wang, Lingqiang

    2018-02-26

    Lignin content and composition are crucial factors affecting biomass digestibility. Exploring the genetic loci simultaneously affecting lignin-relevant traits and biomass digestibility is a precondition for lignin genetic manipulation towards energy crop breeding. In this study, a high-throughput platform was employed to assay the lignin content, lignin composition and biomass enzymatic digestibility of a rice recombinant inbred line population. Correlation analysis indicated that the absolute content of lignin monomers rather than lignin content had negative effects on biomass saccharification, whereas the relative content of p-hydroxyphenyl unit and the molar ratio of p-hydroxyphenyl unit to guaiacyl unit exhibited positive roles. Eight QTL clusters were identified and four of them affecting both lignin composition and biomass digestibility. The additive effects of clustered QTL revealed consistent relationships between lignin-relevant traits and biomass digestibility. Pyramiding rice lines containing the above four positive alleles for increasing biomass digestibility were selected and showed comparable lignin content, decreased syringyl or guaiacyl unit and increased molar percentage of p-hydroxyphenyl unit, the molar ratio of p-hydroxyphenyl unit to guaiacyl unit and sugar releases. More importantly, the lodging resistance and eating/cooking quality of pyramiding lines were not sacrificed, indicating the QTL information could be applied to select desirable energy rice lines.

  2. Thermometric sensing of nitrofurantoin by noncovalently imprinted polymers containing two complementary functional monomers.

    Science.gov (United States)

    Athikomrattanakul, Umporn; Gajovic-Eichelmann, Nenad; Scheller, Frieder W

    2011-10-15

    Molecularly imprinted polymers (MIPs) for nitrofurantoin (NFT) recognition addressing in parallel of two complementary functional groups were created using a noncovalent imprinting approach. Specific tailor-made functional monomers were synthesized: a diaminopyridine derivative as the receptor for the imide residue and three (thio)urea derivatives for the interaction with the nitro group of NFT. A significantly improved binding of NFT to the new MIPs was revealed from the imprinting factor, efficiency of binding, affinity constants and maximum binding number as compared to previously reported MIPs, which addressed either the imide or the nitro residue. Substances possessing only one functionality (either the imide group or nitro group) showed significantly weaker binding to the new imprinted polymers than NFT. However, the compounds lacking both functionalities binds extremely weak to all imprinted polymers. The new imprinted polymers were applied in a flow-through thermistor in organic solvent for the first time. The MIP-thermistor allows the detection of NFT down to a concentration of 5 μM in acetonitrile + 0.2% dimethyl sulfoxide (DMSO). The imprinting factor of 3.91 at 0.1 mM of NFT as obtained by thermistor measurements is well comparable to the value obtained by batch binding experiments. © 2011 American Chemical Society

  3. Response of ethylene propylene diene monomer rubber (EPDM) to simulant Hanford tank waste

    Energy Technology Data Exchange (ETDEWEB)

    NIGREY,PAUL J.

    2000-02-01

    This report presents the findings of the Chemical Compatibility Program developed to evaluate plastic packaging components that may be incorporated in packaging mixed-waste forms for transportation. Consistent with the methodology outlined in this report, the author performed the second phase of this experimental program to determine the effects of simulant Hanford tank mixed wastes on packaging seal materials. That effort involved the comprehensive testing of five plastic liner materials in an aqueous mixed-waste simulant. The testing protocol involved exposing the materials to {approximately}143, 286, 571, and 3,670 krad of gamma radiation and was followed by 7-, 14-, 28-, 180-day exposures to the waste simulant at 18, 50, and 60 C. Ethylene propylene diene monomer (EPDM) rubber samples subjected to the same protocol were then evaluated by measuring seven material properties: specific gravity, dimensional changes, mass changes, hardness, compression set, vapor transport rates, and tensile properties. The author has determined that EPDM rubber has excellent resistance to radiation, this simulant, and a combination of these factors. These results suggest that EPDM is an excellent seal material to withstand aqueous mixed wastes having similar composition to the one used in this study.

  4. Monitoring Conformational Landscape of Ovine Prion Protein Monomer Using Ion Mobility Coupled to Mass Spectrometry

    Science.gov (United States)

    Van der Rest, Guillaume; Rezaei, Human; Halgand, Frédéric

    2017-02-01

    Prion protein is involved in deadly neurodegenerative diseases. Its pathogenicity is linked to its structural conversion (α-helix to β-strand transition). However, recent studies suggest that prion protein can follow a plurality of conversion pathways, which hints towards different conformers that might coexist in solution. To gain insights on the plasticity of the ovine prion protein (PrP) monomer, wild type (A136, R154, Q171), mutants and deletions of ARQ were studied by traveling wave ion mobility experiments coupled to mass spectrometry. In order to perform the analysis of a large body of data sets, we designed and evaluated the performance of a processing pipeline based on Driftscope peak detection and a homemade script for automated peak assignment, annotation, and quantification on specific multiply charged protein data. Using this approach, we showed that in the gas phase, PrPs are represented by at least three conformer families differing in both charge state distribution and collisional cross-section, in agreement with the work of Hilton et al. (2010). We also showed that this plasticity is borne both by the N- and C-terminal domains. Effect of protein concentration, pH and temperature were also assessed, showing that (1) pH does not affect conformer distributions, (2) protein concentration modifies the conformational landscape of one mutant (I208M) only, and (3) heating leads to other unfolded species and to a modification of the conformer intensity ratios.

  5. 1-O-vinyl glycosides via Tebbe olefination, their use as chiral auxiliaries and monomers.

    Science.gov (United States)

    Yuan, Jialong; Lindner, Kristof; Frauenrath, Holger

    2006-07-21

    A series of anomerically pure 1-O-formyl glycosides 1 was prepared and converted into the corresponding 1-O-vinyl glycosides 2 by Tebbe olefination. The unsubstituted vinyl glycosides were obtained as anomerically pure compounds in good yields, and the method of preparation was compatible with the presence of a variety of functional groups. Remarkably, the anomeric formate group was regioselectively converted into the corresponding olefin in the presence of acetate and benzoate protecting groups. With the perspective to use the 1-O-vinyl glycosides as monomers for the preparation of glycosylated poly(vinyl alcohol) derivatives with controlled tacticity, their scope as chiral auxiliaries for a stereodifferentiation in addition reactions to the olefin function was investigated by using the [2+2] cycloaddition to dichloroketene as a model reaction. In particular, vinyl 2,3,4,6-tetra-O-benzoyl-alpha-d-mannopyranoside (2i) exhibited excellent diastereoselectivity. Finally, the 1-O-vinyl glycosides were successfully subjected to radical homopolymerization in bulk or used as electron-rich comonomers in radical copolymerizations with maleic anhydride, yielding alternating, glycosylated poly(vinyl alcohol-alt-maleic anhydride).

  6. The Continuation Study of the Measurement of Residual Monomer from theDenture Base After Three Month Worn by Gas Chromatography on the Radiationand Non Radiation Worker

    International Nuclear Information System (INIS)

    Isyuniarto; Winoto

    2000-01-01

    Residual monomer measurement on the radiation and non radiation workerafter three month worn the denture has been done. The aim of the research isto investigated residual monomer concentration on after three month worn. Thedenture base material, made of resin acrylic, sometimes is cause mucosairritation in the mouth, and dental irritation or allergic reaction, becauseof residual monomer that left on the mouth cavity. In this research two groupwere needed there are the radiation and non radiation worker, the level ofthe residual monomer count by gas chromatography analysis. The result of thisresearch showed that the level of residual monomer of two group are same orthere have same level of the limit value. The measurement result is in therange of 0.1783 ± 0.011 mg/l to 0.1790 ± 0.004 mg/l. (author)

  7. Conformational alteration in alpha-toxin from Staphylococcus aureus concomitant with the transformation of the water-soluble monomer to the membrane oligomer.

    Science.gov (United States)

    Ikigai, H; Nakae, T

    1985-07-16

    The membrane-damaging alpha-toxin aggregate of Staphylococcus aureus was characterized physicochemically. The aggregate weight of the toxin formed by various methods appeared to be 6 times higher than the molecular weight of the monomer as determined by the laser light scattering technique, suggesting the presence of a hexamer in the membrane. The aggregates fluoresced 20 to 50% more than the monomer at 336 nm. Circular dichroism measurements revealed that both the monomer and the oligomer showed essentially beta-sheet structure with the maximum ellipticity about -8,400 deg.cm2.dmol-1 at 215 nm. Circular dichroism spectrum of the oligomers showed ellipticity difference of -6,600, -44 and +84 deg.cm2.dmol-1, at 200, 250 and 280 nm, respectively, compared with the monomer. All these results suggest that the conformational change in the toxin molecule occurs concomitant with the transformation of the water-soluble monomer to the membrane-embedded hexamer.

  8. Cyclic fatty acid monomers from dietary heated fats affect rat liver enzyme activity.

    Science.gov (United States)

    Lamboni, C; Sébédio, J L; Perkins, E G

    1998-07-01

    This study was conducted to investigate the effects of dietary cyclic fatty acid monomers (CFAM), contained in heated fat from a commercial deep-fat frying operation, on rat liver enzyme activity. A partially hydrogenated soybean oil (PHSBO) used 7 d (7-DH) for frying foodstuffs, or 0.15% methylated CFAM diets was fed to male weanling rats in comparison to a control group fed a nonheated PHSBO (NH) diet in a 10-wk experiment. All diets were isocaloric with 15% fat. Animals fed either CFAM or 7-DH diets showed increased hepatic content of cytochrome (cyt.) b5 and P450 and increased activity of (E.C. 1.6.2.4) NADPH-cyt. P450 reductase in comparison to the control rats. In addition, the activities of (E.C. 2.3.1.21) carnitine palmitoyltransferase-I and (E.C. 1.1.1.42) isocitrate dehydrogenase were significantly decreased when compared to that of rats fed the NH diet. A significantly depressed activity of (E.C. 1.1.1.49) glucose 6-phosphate dehydrogenase was also observed for these animals compared to the control rats fed NH diet. Moreover, liver and microsomal proteins were significantly increased when CFAM or 7-DH diets were fed to animals in comparison to controls while liver glycogen was decreased significantly in experimental groups of rats. The results obtained in this study indicate that the CFAM in the diet from either synthetic sources or used fats increase the activity of liver enzyme systems that detoxify them.

  9. Green proteorhodopsin reconstituted into nanoscale phospholipid bilayers (nanodiscs) as photoactive monomers.

    Science.gov (United States)

    Ranaghan, Matthew J; Schwall, Christine T; Alder, Nathan N; Birge, Robert R

    2011-11-16

    Over 4000 putative proteorhodopsins (PRs) have been identified throughout the oceans and seas of the Earth. The first of these eubacterial rhodopsins was discovered in 2000 and has expanded the family of microbial proton pumps to all three domains of life. With photophysical properties similar to those of bacteriorhodopsin, an archaeal proton pump, PRs are also generating interest for their potential use in various photonic applications. We perform here the first reconstitution of the minimal photoactive PR structure into nanoscale phospholipid bilayers (nanodiscs) to better understand how protein-protein and protein-lipid interactions influence the photophysical properties of PR. Spectral (steady-state and time-resolved UV-visible spectroscopy) and physical (size-exclusion chromatography and electron microscopy) characterization of these complexes confirms the preparation of a photoactive PR monomer within nanodiscs. Specifically, when embedded within a nanodisc, monomeric PR exhibits a titratable pK(a) (6.5-7.1) and photocycle lifetime (∼100-200 ms) that are comparable to the detergent-solubilized protein. These ndPRs also produce a photoactive blue-shifted absorbance, centered at 377 or 416 nm, that indicates that protein-protein interactions from a PR oligomer are required for a fast photocycle. Moreover, we demonstrate how these model membrane systems allow modulation of the PR photocycle by variation of the discoidal diameter (i.e., 10 or 12 nm), bilayer thickness (i.e., 23 or 26.5 Å), and degree of saturation of the lipid acyl chain. Nanodiscs also offer a highly stable environment of relevance to potential device applications.

  10. Characterization of γ-radiation induced polymerization in ethyl methacrylate and methyl acrylate monomers solutions

    Science.gov (United States)

    Baccaro, Stefania; Casieri, Cinzia; Cemmi, Alessia; Chiarini, Marco; D'Aiuto, Virginia; Tortora, Mariagrazia

    2017-12-01

    The present work is focused on the γ-radiation induced polymerization of ethyl methacrylate (EMA) and methyl acrylate (MA) monomers mixture to obtain a co-polymer with specific features. The effect of the irradiation parameters (radiation absorbed dose, dose rate) and of the environmental atmosphere on the features of the final products was investigated. Attenuated Total Reflectance - Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Nuclear Magnetic Resonance high-resolution analyses of hydrogen and carbon nuclei (1H and 13C NMR) were applied to follow the γ-induced modifications by monitoring the co-polymerization process and allowed the irradiation parameters optimization. Diffusion-Ordered NMR (DOSY-NMR) data were used to evaluate the co-polymers polydispersity and polymerization degree. Since the last parameter is strongly influenced by the γ radiation and environmental conditions, a comparison among samples prepared and irradiated in air and under nitrogen atmosphere was carried out. In presence of oxygen, higher radiation was required to obtain a full solid co-polymer since a partial amount of energy released to the samples was involved in competitive processes, i.e. oxygen-containing free radicals formation and primary radicals recombination. Irrespectively to the environmental atmosphere, more homogeneous samples in term of polymerization degree dispersion was achieved at lower dose rates. At radiation absorbed doses higher than those needed for the formation of the co-polymer, while in case of samples irradiated in air heavy depolymerization was verified, a sensible increase of the samples stability was attained if the irradiation was performed under nitrogen atmosphere.

  11. Vibrational spectroscopy and molecular dynamics of water monomers and dimers adsorbed on polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Simon, Aude; Rapacioli, Mathias; Mascetti, Joëlle; Spiegelman, Fernand

    2012-05-21

    This paper reports structures, energetics, dynamics and spectroscopy of H2O and (H2O)2 systems adsorbed on coronene (C24H12), a compact polycyclic aromatic hydrocarbon (PAH). On-the-fly Born-Oppenheimer molecular dynamics simulations are performed for temperatures T varying from 10 to 300 K, on a potential energy surface obtained within the self-consistent-charge density-functional based tight-binding (SCC-DFTB) approach. Anharmonic infrared (IR) spectra are extracted from these simulations. We first benchmark the SCC-DFTB semi-empirical hamiltonian vs. DFT (Density Functional Theory) calculations that include dispersion, on (C6H6)(H2O)1,2 small complexes. We find that charge corrections and inclusion of dispersion contributions in DFTB are necessary to obtain consistent structures, energetics and IR spectra. Using this Hamiltonian, the structures, energetics and IR features of the low-energy isomers of (C24H12)(H2O)1,2 are found to be similar to the DFT ones, with evidence for a stabilizing edge-coordination. The temperature dependence of the motions of H2O and (H2O)2 on the surface of C24H12 is analysed, revealing ultra-fast periodic motion. The water dimer starts diffusing at a higher temperature than the water monomer (150 K vs. 10 K respectively), which appears to be consistent with the binding energies. Qualitative and quantitative analyses of the effects of T on the IR spectra are performed. Anharmonic factors in particular are derived and it is shown that they can be used as signatures for the presence of PAH-water complexes. Finally, this paper lays the foundations for the studies of larger (PAH)m(H2O)n clusters, that can be treated with the efficient computational approach benchmarked in this paper.

  12. Folding and unfolding pathway of chaperonin GroEL monomer and elucidation of thermodynamic parameters.

    Science.gov (United States)

    Puri, Sarita; Chaudhuri, Tapan K

    2017-03-01

    The conformation and thermodynamic stability of monomeric GroEL were studied by CD and fluorescence spectroscopy. GroEL denaturation with urea and dilution in buffer leads to formation of a folded GroEL monomer. The monomeric nature of this protein was verified by size-exclusion chromatography and native PAGE. It has a well-defined secondary and tertiary structure, folding activity (prevention of aggregation) for substrate protein and is resistant to proteolysis. Being a properly folded and reversibly refoldable, monomeric GroEL is amenable for the study of thermodynamic stability by unfolding transition methods. We present the equilibrium unfolding of monomeric GroEL as studied by urea and heat mediated unfolding processes. The urea mediated unfolding shows two transitions and a single transition in the heat mediated unfolding process. In the case of thermal unfolding, some residual structure unfolds at a higher temperature (70-75°C). The process of folding/unfolding is reversible in both cases. Analysis of folding/unfolding data provides a measure of ΔG NU H 2 O , T m , ΔH van and ΔS van of monomeric GroEL. The thermodynamic stability parameter ΔG NU H 2 O is similar with both CD and intrinsic fluorescence i.e. 7.10±1.0kcal/mol. The calculated T m , ΔH van and ΔS van from the thermal unfolding transition is 46±0.5°C, 43.3±0.1kcal/mol and 143.9±0.1cal/mol/k respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Coxibs interfere with the action of aspirin by binding tightly to one monomer of cyclooxygenase-1

    Energy Technology Data Exchange (ETDEWEB)

    Rimon, Gilad; Sidhu, Ranjinder S.; Lauver, D. Adam; Lee, Jullia Y.; Sharma, Narayan P.; Yuan, Chong; Frieler, Ryan A.; Trievel, Raymond C.; Lucchesi, Benedict R.; Smith, William L. (Michigan)

    2010-02-11

    Pain associated with inflammation involves prostaglandins synthesized from arachidonic acid (AA) through cyclooxygenase-2 (COX-2) pathways while thromboxane A{sub 2} formed by platelets from AA via cyclooxygenase-1 (COX-1) mediates thrombosis. COX-1 and COX-2 are both targets of nonselective nonsteroidal antiinflammatory drugs (nsNSAIDs) including aspirin whereas COX-2 activity is preferentially blocked by COX-2 inhibitors called coxibs. COXs are homodimers composed of identical subunits, but we have shown that only one subunit is active at a time during catalysis; moreover, many nsNSAIDS bind to a single subunit of a COX dimer to inhibit the COX activity of the entire dimer. Here, we report the surprising observation that celecoxib and other coxibs bind tightly to a subunit of COX-1. Although celecoxib binding to one monomer of COX-1 does not affect the normal catalytic processing of AA by the second, partner subunit, celecoxib does interfere with the inhibition of COX-1 by aspirin in vitro. X-ray crystallographic results obtained with a celecoxib/COX-1 complex show how celecoxib can bind to one of the two available COX sites of the COX-1 dimer. Finally, we find that administration of celecoxib to dogs interferes with the ability of a low dose of aspirin to inhibit AA-induced ex vivo platelet aggregation. COX-2 inhibitors such as celecoxib are widely used for pain relief. Because coxibs exhibit cardiovascular side effects, they are often prescribed in combination with low-dose aspirin to prevent thrombosis. Our studies predict that the cardioprotective effect of low-dose aspirin on COX-1 may be blunted when taken with coxibs.

  14. Monomer functionalized silica coated with Ag nanoparticles for enhanced SERS hotspots

    Science.gov (United States)

    Newmai, M. Boazbou; Verma, Manoj; Kumar, P. Senthil

    2018-05-01

    Mesoporous silica (SiO2) spheres are well-known for their excellent chromatographic properties such as the relatively high specific surface, large pore volume, uniform particle size, narrow pore size distribution with favorable pore connectivity; whereas the noble metal Ag nanoparticles have unique size/shape dependant surface plasmon resonance with wide ranging applications. Thus, the desire to synchronize both their properties for specific applications has naturally prompted research in the design and synthesis of core-shell type novel nanoAg@mesoSiO2 nanocomposites, which display potential utility in applications such as photothermal therapy, photocatalysis, molecular sensing, and photovoltaics. In the present work, SiO2 spheres were carefully functionalized with the monomer, N-vinyl pyrrolidone (NVP), which cohesively controls the uniform mass transfer of Ag+ metal ions, thereby enabling its sequential reduction to zerovalent Ag (in the presence of slightly excess NaOH) by electron transfer from nucleophilic attack of the NVP vinyl group by the water molecules even under ambient conditions. Complete metal nanoshell coverage of the silica surface was obtained after multiple Ag deposition cycles, as systematically confirmed from the BET, TEM, optical and FTIR characterization. Our present Ag-coated silica spheres were directly utilized as viable SERS substrates with high sensitivity in contrast with other long chain polymer/surfactant coated silica spheres, owing to the presence of significant number of nanogaps enhanced SERS 'hotspots', which were methodically analyzed utilizing two example analytes, such as crystal violet (CV) and calendula officinalis (CaF).

  15. Effect of temperature on the breakthrough of a charcoal tube during vinyl chloride monomer sampling.

    Science.gov (United States)

    Roh, J; Park, Y J; Kim, C N; Lim, N G; Lee, S H; Song, J S; Won, J U; Talaska, G

    2000-01-01

    This study evaluated the effects of temperature on breakthrough of two standard collection media at various concentrations during vinyl chloride monomer (VCM) sampling. The National Institute for Occupational Safety and Health (NIOSH) and Occupational Safety and Health Administration (OSHA) methods were evaluated. To determine whether breakthrough of VCM would occur at the extremes of exposure and temperature that might be encountered in some workplaces, air samples containing 4 ppm (10.24 mg/m3), 8 ppm (20.45 mg/m3), 16 ppm (40.98 mg/m3), and 32 ppm (81.80 mg/m3) of VCM were collected at temperatures of 4, 22, and 40 degrees C. Five liters of air was sampled at the rate of 0.05 L/min for 100 min using the activated charcoal tube recommended by NIOSH. A second tube was added to the sampling train to collect any VCM that might not have been absorbed in the first tube. To collect VCM air samples by the OSHA method, two carbon molecular sieve tubes were connected serially and 3 L of air was sampled at the rate of 0.05 L/min for 60 min. A gas chromatograph with a flame ionization detector and ultra 2 capillary column was used to analyze VCM. Significant breakthrough was found when sampling at higher temperatures with the NIOSH method. No breakthrough was found when samples were collected using the OSHA media at different temperatures and concentrations. Therefore, under hot ambient conditions (>22 degrees C), the possibility of breakthrough should be considered when sampling VCM by the NIOSH method.

  16. Generation and characterization of a transgenic pig carrying a DsRed-monomer reporter gene.

    Directory of Open Access Journals (Sweden)

    Chih-Jen Chou

    Full Text Available Pigs are an optimal animal for conducting biomedical research because of their anatomical and physiological resemblance to humans. In contrast to the abundant resources available in the study of mice, few fluorescent protein-harboring porcine models are available for preclinical studies. In this paper, we report the successful generation and characterization of a transgenic DsRed-Monomer porcine model.The transgene comprised a CMV enhancer/chicken-beta actin promoter and DsRed monomeric cDNA. Transgenic pigs were produced by using pronuclear microinjection. PCR and Southern blot analyses were applied for identification of the transgene. Histology, blood examinations and computed tomography were performed to study the health conditions. The pig amniotic fluid progenitor/stem cells were also isolated to examine the existence of red fluorescence and differentiation ability.Transgenic pigs were successfully generated and transmitted to offspring at a germ-line transmission rate of 43.59% (17/39. Ubiquitous expression of red fluorescence was detected in the brain, eye, tongue, heart, lung, liver, pancreas, spleen, stomach, small intestine, large intestine, kidney, testis, and muscle; this was confirmed by histology and western blot analyses. In addition, we confirmed the differentiation potential of amniotic fluid progenitor stem cells isolated from the transgenic pig.This red fluorescent pig can serve as a host for other fluorescent-labeled cells in order to study cell-microenvironment interactions, and can provide optimal red-fluorescent-labeled cells and tissues for research in developmental biology, regenerative medicine, and xenotransplantation.

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

    Science.gov (United States)

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

    2013-03-28

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

  18. Final Report: Investigation of Catalytic Pathways for Lignin Breakdown into Monomers and Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Gluckstein, Jeffrey A [ORNL; Hu, Michael Z. [ORNL; Kidder, Michelle [ORNL; McFarlane, Joanna [ORNL; Narula, Chaitanya Kumar [ORNL; Sturgeon, Matthew R [ORNL

    2010-12-01

    Lignin is a biopolymer that comprises up to 35% of woody biomass by dry weight. It is currently underutilized compared to cellulose and hemicellulose, the other two primary components of woody biomass. Lignin has an irregular structure of methoxylated aromatic groups linked by a suite of ether and alkyl bonds which makes it difficult to degrade selectively. However, the aromatic components of lignin also make it promising as a base material for the production of aromatic fuel additives and cyclic chemical feed stocks such as styrene, benzene, and cyclohexanol. Our laboratory research focused on three methods to selectively cleave and deoxygenate purified lignin under mild conditions: acidolysis, hydrogenation and electrocatalysis. (1) Acidolysis was undertaken in CH2Cl2 at room temperature. (2) Hydrogenation was carried out by dissolving lignin and a rhodium catalyst in 1:1 water:methoxyethanol under a 1 atm H2 environment. (3) Electrocatalysis of lignin involved reacting electrically generated hydrogen atoms at a catalytic palladium cathode with lignin dissolved in a solution of aqueous methanol. In all of the experiments, the lignin degradation products were identified and quantified by gas chromatography mass spectroscopy and flame ionization detection. Yields were low, but this may have reflected the difficulty in recovering the various fractions after conversion. The homogeneous hydrogenation of lignin showed fragmentation into monomers, while the electrocatalytic hydrogenation showed production of polyaromatic hydrocarbons and substituted benzenes. In addition to the experiments, promising pathways for the conversion of lignin were assessed. Three conversion methods were compared based on their material and energy inputs and proposed improvements using better catalyst and process technology. A variety of areas were noted as needing further experimental and theoretical effort to increase the feasibility of lignin conversion to fuels.

  19. Interaction of vinyl chloride monomer exposure and hepatitis B viral infection on liver cancer.

    Science.gov (United States)

    Wong, Ruey-Hong; Chen, Pau-Chung; Wang, Jung-Der; Du, Chung-Li; Cheng, Tsun-Jen

    2003-04-01

    Vinyl-chloride monomer (VCM), a human carcinogen, has caused angiosarcoma of the liver. Recent studies have shown that VCM exposure is associated with hepatocellular cancer. In Taiwanese studies, the majority of VCM-exposed workers with liver cancer had history of hepatitis B virus (HBV) infection. To determine the role of HBV on the development of liver cancer in the VCM-exposed workers, we conducted a case-control study from a previously established polyvinyl chloride (PVC) cohort consisting of 4096 male workers from six PVC polymerization plants. A total of 18 patients with liver cancer, and 68 control subjects matched for age and specific plant of employment were selected. Detailed history of the participants that included alcohol consumption status, cigarette use, occupation, and family history of chronic liver disease were obtained using an interviewer-administered questionnaire. When the HBV surface antigen (HBsAg)-negative subjects without history of tank-cleaning were used as the reference, the HBsAg-negative subjects with history of tank-cleaning demonstrated a 4.0-fold greater risk of liver cancer (95% confidence interval: 95% CI = 0.2-69.1). The HBsAg carriers without history of tank-cleaning revealed a 25.7-fold greater risk of liver cancer (95% CI = 2.9-229.4). Whereas the HBsAg carriers with history of tank-cleaning revealed the greatest risk (matched odds ratio (ORm) 396.0, 95% CI = 22.6 -infinity) of developing liver cancer among subjects with different VCM-exposure status and HBsAg status categories. Further analysis showed the interaction term was significant (P < .01). Therefore, our results suggest an interaction between occupational VCM exposure and HBV infection for the development of liver cancer.

  20. α-helix to β-hairpin transition of human amylin monomer

    Science.gov (United States)

    Singh, Sadanand; Chiu, Chi-cheng; Reddy, Allam S.; de Pablo, Juan J.

    2013-04-01

    The human islet amylin polypeptide is produced along with insulin by pancreatic islets. Under some circumstances, amylin can aggregate to form amyloid fibrils, whose presence in pancreatic cells is a common pathological feature of Type II diabetes. A growing body of evidence indicates that small, early stage aggregates of amylin are cytotoxic. A better understanding of the early stages of the amylin aggregation process and, in particular, of the nucleation events leading to fibril growth could help identify therapeutic strategies. Recent studies have shown that, in dilute solution, human amylin can adopt an α-helical conformation, a β-hairpin conformation, or an unstructured coil conformation. While such states have comparable free energies, the β-hairpin state exhibits a large propensity towards aggregation. In this work, we present a detailed computational analysis of the folding pathways that arise between the various conformational states of human amylin in water. A free energy surface for amylin in explicit water is first constructed by resorting to advanced sampling techniques. Extensive transition path sampling simulations are then employed to identify the preferred folding mechanisms between distinct minima on that surface. Our results reveal that the α-helical conformer of amylin undergoes a transformation into the β-hairpin monomer through one of two mechanisms. In the first, misfolding begins through formation of specific contacts near the turn region, and proceeds via a zipping mechanism. In the second, misfolding occurs through an unstructured coil intermediate. The transition states for these processes are identified. Taken together, the findings presented in this work suggest that the inter-conversion of amylin between an α-helix and a β-hairpin is an activated process and could constitute the nucleation event for fibril growth.