WorldWideScience

Sample records for azobenzene side groups

  1. Photoorientation of a liquid crystalline polyester with azobenzene side groups

    DEFF Research Database (Denmark)

    Zebger, I; Rutloh, M; Hoffmann, U

    2002-01-01

    The photoorientation process in a polyester with 4-cyano-4'-alkoxyazobenzene side group and long methylene spacers in the side and the main-chain was studied as a function of irradiation with linearly polarized light of 488 nm under systematic variation of the power density and temperature....... This model polymer is characterized by liquid crystallinity (g 24 S-X 26 S-A 34 n 47 i) and a strong aggregation tendency. The photoorientation is cooperative, i.e., the orientation of the photochromic side group induces the alignment of the ester unit (which is a part of the main-chain) and both methylene...... segments in the side- and main-chain. The very high values of the normalized linear dichroism up to 0.8 and the birefringence (above 0.3) are due to the interaction of photoorientation and thermotropic self-organization. The induction of anisotropy shows a pronounced dependence on the power density...

  2. Photoorientation in thin aligned layers of side-group liquid crystalline copolysiloxane doped with azobenzene and stilbene derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Wolarz, E.; Fischer, Th.; Stumpe, J

    2003-01-31

    Optically anisotropic films of side-group liquid crystalline copolysiloxane doped with photochromic azobenzene and stilbene derivatives were prepared by using standard liquid crystal cells of 4 {mu}m in thickness. The films were irradiated with high power density laser light with the electric field vector creating an angle equal to 45 deg. with the initial optical axis of the samples. As a result of irradiation, the photoorientation of the photochromic molecules, and the cooperative reorientation of the copolysiloxane side groups occurred. In the case of the copolymer layers containing azobenzene, the optical axis was turned by an angle of 45 deg. during sufficiently long irradiation. The angle of reorientation and the degree of anisotropy were determined for the irradiated areas of the samples.

  3. 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

  4. Photoorientation of azobenzene side groups in a liquid-crystalline polybutadiene-based polymer

    Czech Academy of Sciences Publication Activity Database

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

    2008-01-01

    Roč. 30, č. 8 (2008), s. 1335-1342 ISSN 0925-3467 R&D Projects: GA AV ČR IAA4112401; GA MŠk OC 138 Grant - others:German Bundesministerium für Bildung und Forschung(DE) CZE 03/016 Institutional research plan: CEZ:AV0Z40500505 Keywords : azobenzene * liquid crystalline polymer * polybutadiene Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.714, year: 2008

  5. Dynamic mechanical and thermal behavior of novel liquid-crystalline polybutadiene-diols with azobenzene groups in side chains

    Czech Academy of Sciences Publication Activity Database

    Poláková, Lenka; Sedláková, Zdeňka; Beneš, Hynek; Valentová, H.; Krakovský, I.; Rabie, F.

    2013-01-01

    Roč. 57, č. 5 (2013), s. 1297-1310 ISSN 0148-6055 Institutional support: RVO:61389013 Keywords : mesophase * azobenzene mesogens * thermal behavior Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.276, year: 2013

  6. Holographic Gratings in Azobenzene Side-Chain Polymethacrylates

    DEFF Research Database (Denmark)

    Andruzzi, Luisa; Altomare, Angelina; Ciardelli, Francesco

    1999-01-01

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

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

    DEFF Research Database (Denmark)

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

    2002-01-01

    Light scattering properties of liquid crystalline and amorphous azobenzene side-chain polyester layers used for optical data storage were examined by means of transmissive scatterometry. Comparative experiments show that the amorphous polyester has significantly lower light scattering characteris...... for the domain size in thin liquid crystalline polyester layers being responsible for the dominant light scattering. The characteristic domain Sizes obtained from the Fourier transformation of polarization microscopic Pictures confirm these values.......Light scattering properties of liquid crystalline and amorphous azobenzene side-chain polyester layers used for optical data storage were examined by means of transmissive scatterometry. Comparative experiments show that the amorphous polyester has significantly lower light scattering...... 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...

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

    DEFF Research Database (Denmark)

    Zebger, Ingo; Rutloh, Michael; Hoffmann, Uwe

    2003-01-01

    light. The polyester is characterized by smectic and nematic phases g24SX26SA34N46i and a strong tendency to form J-aggregates. The process requires a photochemical pretreatment by irradiation with UV light or an exposure to visible light of high power density to produce a certain concentration of the Z......In contrast to the conventional photoorientation process with blue light, an orientation of 4-cyano-4'-alkoxyazobenzene side groups parallel to the electric field vector of the incident light is generated upon irradiating films of a liquid-crystalline side-chain polymer with linearly polarized red......-isomer, which destroys any initial orientational order and J-aggregates. The orientation process is cooperative, whereas the light-induced orientation of the photochromic moiety causes an ordering of the alkylene spacers and even of the main-chain segments into the same direction. The most probable mechanism...

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

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Pedersen, M; Holme, NCR

    1998-01-01

    . Atomic force and scanning near-held optical microscopic investigations of gratings prepared with orthogonally polarized overlapping beams have demonstrated that the anisotropy is preserved in the film despite extensive mass transport and surface corrugation after the irradiation process. However......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...... on azobenzene, iii- the methylene main-chain segment length, and iv-the polyester molecular mass, all influence the optical storage properties. A general synthetic route to novel mesogenic azobenzene diols comprising parameters i and ii is outlined. Polyesters with molecular masses (parameter iv) up to 100...

  10. Multiresponsive self-assembled liquid crystals with azobenzene groups.

    Science.gov (United States)

    Xu, Miao; Chen, Liqin; Zhou, Yifeng; Yi, Tao; Li, Fuyou; Huang, Chunhui

    2008-10-15

    An optical and electric field-responsive self-assembled complex containing nitril azobenzene groups and 1,3,5-triazine-2,4-diamine was obtained and characterized. Both the azobenzene precursor and the complex form a liquid-crystalline phase in a certain temperature range. The transition temperature from crystalline phase to liquid-crystalline mesophase was obviously decreased in the complex by the self-assembling. The self-assembled liquid crystals revealed good response to both stimuli of light irradiation and electric field, and the induced molecular orientation could be held even after the removal of the stimuli. The structural and mechanical investigation proved that the formation of hydrogen bonds and assembly-induced molecular dipolar change contributed to the multiresponding action. This kind of self-assembled complex thus has potential applications in imaging and data storage.

  11. 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...... in the appearance of a surface relief with doubled frequency....

  12. Synthesis, characterization, and study of photoinduced optical anisotropy in polyimides containing side azobenzene units.

    Science.gov (United States)

    Schab-Balcerzak, Ewa; Siwy, Mariola; Kawalec, Michal; Sobolewska, Anna; Chamera, Agata; Miniewicz, Andrzej

    2009-07-30

    In this paper, novel processable aromatic polymers with imide rings and attached as side-chain azobenzene units are presented. Polymers differ in the chemical structures of chromophores and polymer backbones. Azopolymers were obtained by a two-step synthetic approach. This includes the preparation of a precursor poly(esterimide) and poly(etherimide) with pendant phenolic hydroxyl groups, followed by the covalent bonding of NLO chromophores onto the polyimide backbone by the Mitsunobu reaction. The degree of functionalization of polymers was estimated by UV-vis spectroscopy. Polymers were characterized and evaluated by FT-IR, (1)H NMR, X-ray, UV-vis, DSC, and TGA methods. The synthesized polymers exhibited glass transition temperatures in the range of 167-228 degrees C, thermal stability with decomposition temperatures in the range of 275-446 degrees C, and excellent solubilities in common organic solvents. The light-induced optical anisotropy was studied in obtained azopolymers with the help of a holographic grating recording technique. Two polarization geometries were applied for the grating inscription s-s and p-p. The influence of the polarization geometry on the diffraction efficiency dynamics and on the depth of the surface modulation was not observed, which is different from results reported in the literature. Surface relief gratings, which appeared after the light exposure, were observed by atomic force microscopy. Additionally, the optical anisotropy in poly(esterimide)s was investigated by photoinduced birefringence measurements. For the first time, in polyimide with covalently bonded azobenzene derivatives, the high photoinduced birefringence (Delta n = 0.01) was measured.

  13. Photo-induced deformations in azobenzene-containing side-chain polymers: molecular dynamics study

    Directory of Open Access Journals (Sweden)

    J.Ilnytskyi

    2006-01-01

    Full Text Available We perform molecular dynamics simulations of azobenzene containing side-chain liquid crystalline polymer subject to an external model field that mimicks the reorientations of the azobenzenes upon irradiation with polarized light. The smectic phase of the polymer is studied with the field applied parallel to the nematic director, forcing the trans isomers to reorient perpendicularly to the field (the direction of which can be assosiated with the light polarization. The coupling between the reorientation of azobenzenes and mechanical deformation of the sample is found to depend on the field strength. In a weak field the original smectic order is melted gradually with no apparent change in the simulation box shape, whereas in a strong field two regimes are observed. During the first one a rapid melting of the liquid crystalline order is accompanied by the contraction of the polymer along the field direction (the effect similar to the one observed experimentally in azobenzene containing elastomers. During the slower second regime, the smectic layers are rebuilt to accomodate the preferential direction of chromophores perperdicular to the field.

  14. Mechanism of Macroscopic Motion of Oleate Helical Assemblies : Cooperative Deprotonation of Carboxyl Groups Triggered by Photoisomerization of Azobenzene Derivatives

    OpenAIRE

    Kageyama, Yoshiyuki; Ikegami, Tomonori; Kurokome, Yuta; Takeda, Sadamu

    2016-01-01

    Macroscopic and spatially ordered motions of self-assemblies composed of oleic acid and a small amount of an azobenzene derivative, induced by azobenzene photoisomerization, was previously reported. However, the mechanism of the generation of submillimeter-scale motions by the nanosized structural transition of azobenzene was not clarified. Herein, an underlying mechanism of the motions is proposed in which deprotonation of carboxyl groups in co-operation with azobenzene photoisomerization ca...

  15. Azobenzene-functionalized cascade molecules

    DEFF Research Database (Denmark)

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

    1998-01-01

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

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

    DEFF Research Database (Denmark)

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

    2001-01-01

    We show that it is possible to fabricate topographic submicron features in a side-chain azobenzene polyester with a scanning near-field optical microscope, Through irradiation at a wavelength of 488 run at intensity levels of 12 W/cm(2), topographic features as narrow as 240 nm and as high as 6 nm...... in high-density optical storage and high-resolution lithography....

  17. Kinetics and thermodynamics of amine and diamine signaling by a trifluoroacetyl azobenzene reporter group.

    Science.gov (United States)

    Mertz, Eric; Beil, James B; Zimmerman, Steven C

    2003-08-21

    [reaction: see text] (Trifluoroacetyl)azobenzene dyes were previously employed as amine reporter groups (chemosensors) in a dendrimer-based monomolecular imprinting system. Kinetic and binding studies with a range of amines and diamines show that the highly selective signaling observed for alkane diamines by these imprinted dendrimers arises from a kinetic effect due to intramolecular general base-catalyzed carbinolamine formation with the dye itself. The relationship between diamine structure and carbinolamine stability and rate of formation is described.

  18. Mechanism of Macroscopic Motion of Oleate Helical Assemblies: Cooperative Deprotonation of Carboxyl Groups Triggered by Photoisomerization of Azobenzene Derivatives.

    Science.gov (United States)

    Kageyama, Yoshiyuki; Ikegami, Tomonori; Kurokome, Yuta; Takeda, Sadamu

    2016-06-13

    Macroscopic and spatially ordered motions of self-assemblies composed of oleic acid and a small amount of an azobenzene derivative, induced by azobenzene photoisomerization, was previously reported. However, the mechanism of the generation of submillimeter-scale motions by the nanosized structural transition of azobenzene was not clarified. Herein, an underlying mechanism of the motions is proposed in which deprotonation of carboxyl groups in cooperation with azobenzene photoisomerization causes a morphological transition of the self-assembly, which in turn results in macroscopic forceful dynamics. The photoinduced deprotonation was investigated by potentiometric pH titration and FTIR spectroscopy. The concept of hierarchical molecular interaction generating macroscale function is expected to promote the next stage of supramolecular chemistry. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. An Improved Method for Separating the Kinetics of the Induction of Anisotropic and Topographic Gratings in Side-Chain Azobenzene Polyesters

    DEFF Research Database (Denmark)

    Helgert, M.; Fleck, B.; Wenke, L.

    2000-01-01

    The induction of anisotropy gratings in side-chain azobenzene polyesters is accompanied by the formation of surface relief. We introduce an improved holographic method to separate the contributions of the anisotropic and the topographic part to the diffraction efficiency by analyzing the polariza......The induction of anisotropy gratings in side-chain azobenzene polyesters is accompanied by the formation of surface relief. We introduce an improved holographic method to separate the contributions of the anisotropic and the topographic part to the diffraction efficiency by analyzing...

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

    OpenAIRE

    Uichi Akiba; Daichi Minaki; Jun-ichi Anzai

    2017-01-01

    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, wh...

  1. Molecular structure and modeling studies of azobenzene derivatives containing maleimide groups.

    Science.gov (United States)

    Cojocaru, Corneliu; Airinei, Anton; Fifere, Nicusor

    2013-01-01

    The molecular orbital calculations have been carried out to investigate the structure and stability of (E) / (Z) isomers of some azobenzene derivatives containing maleimide groups. A special attention has been devoted to the compound (E)-1, (E)-1-(4-(phenyldiazenyl)phenyl)-1H-pyrrole-2,5-dione, for which the available crystallographic experimental data have been used to validate the modeling structures computed at the theoretical levels AM1, PM3, RHF/6-31+G(d,p) and B3LYP/6-31+G(d,p). To this end, the discrepancy between experimental and calculated structural parameters has been ascertained in terms of root-mean-square deviation (RMSD). The quantum calculations at the level RHF/6-31+G(d,p) yield the most accurate results on (E)-1 structure giving a deviation error from crystallographic data of about 5.00% for bond lengths and 0.97% for interatomic angles. The theoretical electronic absorption spectra of azobenzene derivatives of concern have been computed by means of configuration-interaction method (CI) at the level of semi-empirical Hamiltonians (AM1 and PM3). Likewise, the molecular energy spectra, electrostatic potential and some quantitative structure activity relationship (QSAR) properties of studied molecules have been computed and discussed in the paper.

  2. The azobenzene derivatives

    Science.gov (United States)

    Ionita, Ionica; Radulescu, Cristiana; Poinescu, Aurora Anca; Anghelina, Florina Violeta; Bunghez, Raluca; Ion, Rodica-Mariana

    2015-02-01

    Azobenzene derivatives constitute a group of dyes which have photochromic properties and have been investigated as promising systems for diverse applications in the unconventional optic area, their properties can be moulded with help of light.

  3. 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......-field optical microscopic scanning of the grating reveals, however, that the bulk of the film remains optically anisotropic. (C) 1996 American Institute of Physics....

  4. 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.

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

    Science.gov (United States)

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

    2013-04-01

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

  6. Chiro-and photooptical properties of a novel side-chain azobenzene-containing LC polymer

    Czech Academy of Sciences Publication Activity Database

    Bobrovsky, A.; Shibaev, V.; Hamplová, Věra; Kašpar, Miroslav; Glogarová, Milada

    2009-01-01

    Roč. 140, č. 7 (2009), s. 789-799 ISSN 0026-9247 R&D Projects: GA MŠk OC 175 Institutional research plan: CEZ:AV0Z10100520 Keywords : photooptical properties * side-chain polymer, * iquid crystalline * helical supermolecular structure Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.312, year: 2009

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

    Czech Academy of Sciences Publication Activity Database

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

    2005-01-01

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

  8. Mean-field theory of photoinduced molecular reorientation in azobenzene liquid crystalline side-chain polymers

    DEFF Research Database (Denmark)

    Pedersen, T.G.; Johansen, P.M.

    1997-01-01

    . The theory provides an explanation for the high long-term stability of the photoinduced anisotropy as well as a theoretical prediction of the temporal behavior of photoinduced birefringence. The theoretical results agree favorably with measurements in the entire range of writing intensities used......A novel mean-field theory of photoinduced reorientation and optical anisotropy in liquid crystalline side-chain polymers is presented and compared with experiments, The reorientation mechanism is based on photoinduced trans cis isomerization and a multidomain model of the material is introduced...

  9. 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 and ...

  10. Density functional theory calculations on azobenzene derivatives: a comparative study of functional group effect.

    Science.gov (United States)

    Piyanzina, Irina; Minisini, Benoit; Tayurskii, Dmitrii; Bardeau, Jean-François

    2015-02-01

    Density functional theory (DFT) calculations have been used to investigate the structural properties, dipole moments, polarizabilities, Gibbs energies, hardness, electronegativity, HOMO/LUMO energies, and chemical potentials of trans and cis configurations of eight para-substituted azobenzene derivatives. All properties have been obtained using the B3LYP functional and 6-31++G(d,p) basis set. The planar structures have been obtained for all optimized trans configurations. The energy difference between trans and cis configurations for considered derivatives was found to be between 64.2-73.1 kJ/mole. It has been obtained that the p-aminodiazo-benzene (ADAB) has the difference in the dipole moments between trans and cis forms higher than for trans and cis azobenzene.

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

    Science.gov (United States)

    Usami, Kiyoaki; Sakamoto, Kenji

    2011-08-01

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

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

    Science.gov (United States)

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

    2015-01-01

    Phase selective gelation (PSG) of organic phases from their non-miscible mixtures with water was achieved using tetrapeptides bearing a side-chain azobenzene moiety. The presence of the chromophore allowed PSG at the same concentration as the minimum gelation concentration (MGC) necessary to obtain the gels in pure organic phases. Remarkably, the presence of the water phase during PSG did not impact the thermal, mechanical, and morphological properties of the corresponding organogels. In the case of miscible oil/water mixtures, the entire mixture was gelled, resulting in the formation of quasi-hydrogels. Importantly, PSG could be triggered at room temperature by ultrasound treatment of the mixture or by adding ultrasound-aided concentrated solution of the peptide in an oil-phase to a mixture of the same oil and water. Moreover, the PSG was not affected by the presence of salts or impurities existing in water from natural sources. The process could be scaled-up, and the oil phases (e.g., aromatic solvents, gasoline, diesel fuel) recovered almost quantitatively after a simple distillation process, which also allowed the recovery and reuse of the gelator. Finally, these peptidic gelators could be used to quantitatively remove toxic dyes from aqueous solutions. PMID:26006247

  13. 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...... and erasing was tested. The ability of azobenzene polyester for rewriting was found satisfactory after many writing-erasing cycles....

  14. 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

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

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Ramanujam, P.S.

    2001-01-01

    The fundamental optical storage mechanism of the laser light addressable azobenzene moiety is briefly introduced. A modular and flexible synthesis design furnishes polyester matrices covalently integrating cyanoazobenzene in regularly spaced side chains. Thin films of these materials are particul...

  16. 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....

  17. Fluorescence Enhancement from Self-Assembled Aggregates II: Factors Influencing Florescence Color from Azobenzene Aggregates

    Science.gov (United States)

    Han, Mina

    2013-09-01

    We have chosen two types of azobenzene derivatives to elucidate the correlation between molecular structure and fluorescence color of light-driven azobenzene-based aggregates. The fluorescence color from azobenzene molecules (1 and 2), adopting a planar structure, was obviously red-shifted from that of the corresponding twisted ortho-alkylated azobenzene 3. The steric hindrance resulting from bulky alkyl groups at the ortho position of the azo linkage was considered to lessen the intermolecular π - π stacking between aromatic rings, leading to the relatively smaller spectral shift in fluorescence from the absorption band of the initial azobenzene solution. The substitution of electron-withdrawing groups into the azobenzene core gave rise to a blue-shift in fluorescence wavelength. That is, the extended π-conjugated system consisting of a planar azobenzene core as well as the electronic properties of the substituents are key factors influencing the fluorescence color from the light-driven azobenzene aggregates. Moreover, we could prepare fluorescent polymer films by mixing fluorescent azobenzene aggregates with polymers. The fluorescence colors from the polymer films were comparable to those from the azobenzene aggregates.

  18. Synthesis of Bifunctional Azobenzene Glycoconjugates for Cysteine-Based Photosensitive Cross-Linking with Bioactive Peptides.

    Science.gov (United States)

    Müller, Anne; Kobarg, Hauke; Chandrasekaran, Vijayanand; Gronow, Joana; Sönnichsen, Frank D; Lindhorst, Thisbe K

    2015-09-21

    Azobenzene linker molecules can be utilized to control peptide/protein function when they are ligated to appropriately spaced amino acid side chains of the peptide. This is because the photochemical E/Z isomerization of the azobenzene N=N double bond allows to switch peptide conformation between folded and unfolded. In this context, we have introduced carbohydrate-functionalized azobenzene derivatives in order to advance the biocompatible properties of azobenzene peptide linkers. Chloroacetamide-functionalized and O-allylated carbohydrate derivatives were synthesized and conjugated with azobenzene to achieve new bifunctional cross-linkers, in order to allow ligation to cysteine side chains by nucleophilic substitution or thiol-ene reaction, respectively. The photochromic properties of the new linker glycoconjugates were determined and first ligation reactions performed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Synthesis, phase behaviour and photooptical properties of bent-core methacrylate with azobenzene group and corresponding side-chain polymethacrylate

    Czech Academy of Sciences Publication Activity Database

    Novotná, Vladimíra; Bobrovsky, A.; Shibaev, V.; Pociecha, D.; Kašpar, Miroslav; Hamplová, Věra

    2016-01-01

    Roč. 6, č. 70 (2016), 65747-65755 ISSN 2046-2069 R&D Projects: GA ČR GA16-12150S; GA MŠk(CZ) LH15305 Institutional support: RVO:68378271 Keywords : liquid crystals * liquid crystalline polymers * photosensitivity Subject RIV: JJ - Other Materials Impact factor: 3.108, year: 2016

  20. 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...

  1. Toward efficient photomodulation of conjugated polymer emission: optimizing differential energy transfer in azobenzene-substituted PPV derivatives.

    Science.gov (United States)

    Grimes, Amy F; Call, Scott E; Vicente, Diego A; English, Douglas S; Harbron, Elizabeth J

    2006-10-05

    We present fluorescence studies of quenching behavior in photoaddressable azobenzene-substituted derivatives of the fluorescent conjugated polymer poly(p-phenylenevinylene) (PPV). The azobenzene side chains partially quench the PPV fluorescence, and we have shown previously that the quenching efficiency is greater when the azobenzene side chains are cis than when they are trans. This effect provides a photoaddressable means of modulating the fluorescence intensity of PPV derivatives. To optimize the efficiency of photoinduced intensity modulation, it is important to understand the molecular nature of quenching by both trans- and cis-azobenzene side chains. Here we investigate the photophysical origins of quenching by the two isomers using steady-state and time-resolved fluorescence spectroscopy. We present results from the azobenzene-modified PPV derivative poly(2-methoxy-5-((10-(4-(phenylazo)phenoxy)decyl)oxy)-1,4-phenylenevinylene) (MPA-10-PPV) and two new related polymers, a copolymer lacking half of the azobenzene side chains and an analogue of MPA-10-PPV with a tert-butyl-substituted azobenzene. These studies reveal that steric interactions influence the extent of PPV emission quenching by trans-azobenzene but do not affect the efficient quenching by cis-azobenzene. The difference in dynamic quenching efficiencies between trans- and cis-azobenzene isomers is consistent with fluorescence resonance energy transfer. These results show that it is possible to control the efficiency of photoswitchable fluorescence modulation through specific structural variations designed to encourage or block quenching by trans-azobenzene. This is a promising approach to providing useful general guidelines for designing photomodulated PPV derivatives.

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

    DEFF Research Database (Denmark)

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

    2004-01-01

    Birefringence induced in a series of liquid crystalline side-chain azobenzene polyesters with different substituent groups was investigated under irradiation with 488 and 633 nm linearly polarized lights. Two different initial conditions have been used: the effect of a previous irradiation with UV...... light irradiation creates a high concentration of cis isomers and breaks the aggregates, but they are formed again after a few days in dark at RT. Orientation of the chromophores perpendicular to the polarization of the 488 nm light and parallel to the polarization of the 633 nm light was confirmed...

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

    Directory of Open Access Journals (Sweden)

    2007-07-01

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

  4. Pretilt angle control of liquid crystal molecules by photoaligned films of azobenzene-containing polyimide with a different content of side-chain

    Science.gov (United States)

    Usami, Kiyoaki; Sakamoto, Kenji; Yokota, Junichiro; Uehara, Yoichi; Ushioda, Sukekatsu

    2008-12-01

    We have investigated the pretilt angle of liquid crystal (LC) molecules induced by photoaligned films of a series of polyimides. The polyimides were random copolymers synthesized from pyromellitic dianhydride and a mixture of 4,4'-diaminoazobenzene and 4-[4'-propylbi(cyclohexan)-4-yl]phenyl 3,5-diaminobenzoate (PBCP-DABA). PBCP-DABA is a diamine to introduce a side-chain structure into polyimide. We found that the pretilt angle of LC molecules can be controlled from 0° to 90° by varying the molar fraction (x) of PBCP-DABA from 0 to 0.5. Defect-free uniform LC alignment was observed for x ≤0.125 and x ≥0.3, but threadlike textures appeared for 0.15≤x≤0.25. Since the interaction between the polyimide backbone structure and the LC molecule may be blocked by relatively dense side-chains, the appearance of threadlike texture is tentatively attributed to weak azimuthal anchoring strength of the photoaligned polyimide films with x ≥0.15.

  5. Simulation of Photo-isomerization of Functionalized Azobenzene Derivatives

    Science.gov (United States)

    Tavazohi, Pedram; Herberger, Zachary; Lewis, James

    Photo-isomerization is the process of changing the isomer (cis , trans) of a molecule using light. In azobenzene this process can be utilized in a Metal Organic Framework (MOF) for adsorption of CO2. MOFs are created by two major components, metal ions, and organic molecules which are called linkers. The metal ions and linkers can be coordinated in a way that they form a porous material. In the cis isomer of azobenzene, the MOF's pore is available to be filled by CO2, but in the trans isomer the pore is filled with a benzene ring. The change from cis to trans will evacuate the pore if CO2 is present. The important considerations in using azobenzene photo-isomerization as a photo-switch in MOFs are, the quantum yield of the process, and the wavelength of the light which triggers photo-isomerization. By substitution of the functional groups of azobenzene and using the fewest switches surface-hopping algorithm in FIREBALL to simulate the photo-isomerization process we can tune the properties of the molecule as we desire and predict the best substitution sites for azobenzene functional groups. We studied the effects of functionalizing the molecule with OH, CH3, NH2, NO2 and COOH on isomerization quantum yield.

  6. Binary Supramolecular Gel of Achiral Azobenzene with a Chaperone Gelator: Chirality Transfer, Tuned Morphology, and Chiroptical Property.

    Science.gov (United States)

    Ji, Lukang; Ouyang, Guanghui; Liu, Minghua

    2017-10-31

    Binary supramolecular gels based on achiral azobenzene derivatives and a chiral chaperone gelator, long-alkyl-chain-substituted L-Histidine (abbreviated as LHC18) that could assist many nongelling acids in forming gels, were investigated in order to fabricate the chiroptical gel materials in a simple way. It was found that although the carboxylic acid-terminated achiral azobenzene derivatives could not form gels in any solvents, when mixed with LHC18 they formed the co-gels and self-assembled into various morphologies ranging from nanotubes and loose nanotubes to nanosheets, depending on the substituent groups on the azobenzene moiety. The ether linkage and the number of carboxylic acid groups attached to the azobenzene moiety played important roles. Upon gel formation, the localized molecular chirality in LHC18 could be transferred to the azobenzene moiety. Combined with the trans-cis isomerization of the azobenzene, optically and chiroptically reversible gels were generated. It was found that the gel based on azobenzene with two carboxylic acid groups and ether linkages showed clear optical reversibility but less chiroptical reversibility, whereas the gel based on azobenzene with one carboxylic acid and an ether linkage showed both optical and chiroptical reversibility. Thus, new insights into the relationship among the molecular structures of the azobenzene, self-assembled nanostructures in the gel and the optical and chiroptical reversibility were disclosed.

  7. Functionalization, self-assembly, and photoswitching quenching for azobenzene derivatives adsorbed on Au(111).

    Science.gov (United States)

    Cho, Jongweon; Berbil-Bautista, L; Levy, Niv; Poulsen, Daniel; Fréchet, Jean M J; Crommie, Michael F

    2010-12-21

    We have used scanning tunneling microscopy to investigate the structure and photoswitching behavior of azobenzene molecules functionalized with bulky spacer groups and adsorbed onto Au(111). We find that positioning tert-butyl "legs" in a canted arrangement on the azobenzene phenyl rings quenches photoisomerizability of the molecule on Au(111). Addition of cyano groups at the para positions changes the molecular self-assembly significantly, but does not alter the quenched photoisomerizability. This behavior likely arises from a combination of molecule-surface interactions, molecule-molecule interactions, and alteration of azobenzene electronic structure resulting from the position-specific addition of tert-butyl groups.

  8. 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.

  9. Synthesis and photoisomerization of fullerene- and oligo(phenylene ethynylene)-azobenzene derivatives.

    Science.gov (United States)

    Shirai, Yasuhiro; Sasaki, Takashi; Guerrero, Jason M; Yu, Byung-Chan; Hodge, Phillip; Tour, James M

    2008-01-01

    The presence of fullerenes and oligo(phenylene ethynylene)s (OPEs) in azobenzene derivatives have a large effect on the photoisomerization behavior of the molecules. Fullerenes reduce the photoisomerization yield for cis isomers, and the OPEs, when directly attached to the azobenzenes, have a similar yet smaller effect when compared with the fullerenes. While these effects have not been previously considered for fullerene--and OPE-azobenzene derivatives, they were clearly detected in our work using NMR and UV-vis spectroscopy methods. The intramolecular electronic energy transfer between the fullerene and azobenzene moiety was examined in two cases in which separation of the two functional groups was small, as in 1, or large, as in 2. Almost no photoisomerization was observed for 1, while significant photoisomerization was observed for 2, apparently due to the effective isolation and blocking of electronic communication between the two functional groups.

  10. Colorimetric Sugar Sensing Using Boronic Acid-Substituted Azobenzenes

    Directory of Open Access Journals (Sweden)

    Yuya Egawa

    2014-02-01

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

  11. Photoisomerization in different classes of azobenzene.

    Science.gov (United States)

    Bandara, H M Dhammika; Burdette, Shawn C

    2012-03-07

    Azobenzene undergoes trans→cis isomerization when irradiated with light tuned to an appropriate wavelength. The reverse cis→trans isomerization can be driven by light or occurs thermally in the dark. Azobenzene's photochromatic properties make it an ideal component of numerous molecular devices and functional materials. Despite the abundance of application-driven research, azobenzene photochemistry and the isomerization mechanism remain topics of investigation. Additional substituents on the azobenzene ring system change the spectroscopic properties and isomerization mechanism. This critical review details the studies completed to date on the 3 main classes of azobenzene derivatives. Understanding the differences in photochemistry, which originate from substitution, is imperative in exploiting azobenzene in the desired applications. This journal is © The Royal Society of Chemistry 2012

  12. 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

    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...

  13. Unusual photoanisotropic alignment in amorphous azobenzene polymers

    DEFF Research Database (Denmark)

    Ramanujam, P.S.

    2015-01-01

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

  14. Azobenzene photoisomerization quantum yields in methanol redetermined.

    Science.gov (United States)

    Ladányi, Vít; Dvořák, Pavel; Al Anshori, Jamaludin; Vetráková, Ľubica; Wirz, Jakob; Heger, Dominik

    2017-12-06

    The quantum yields of azobenzene photoisomerization in methanol solution were redetermined using newly obtained molar absorption coefficients of its cis- and trans-isomers. The results differ substantially from those published previously, especially in the range of the nπ* absorption band. Besides actinometry, these findings are relevant for applications of azobenzene derivatives in optical switching.

  15. Distinguishing the parallel and vertical orientations and optic axis characteristics determination of azobenzene mesogen by conoscopic polarized microscopy.

    Science.gov (United States)

    Liu, J; Wang, M; Dong, M; Gao, L; Tian, J

    2011-11-01

    Orientational behaviours under the action of linearly polarized light and circularly polarized light of a side-chain azobenzene containing polymer were studied by conoscopic polarized microscopy. The results suggest that the linearly polarized light (473 nm, 20 mW cm(-2)) results in an in-plane orientation of the azobenzene groups. The irradiation with circularly polarized light (473 nm, 20 mW cm(-2)) leads to a tilt orientation (out-of-plane) of the azobenzene groups with the long axis of mesogens aligned along the propagation direction of the actinic light. Characteristic features of the in-plane and out-of-plane orientated films were obtained from their interference figures. The in-plane orientated film shows an interference cross consisting of a broad fuzzy bar, and the cross-centre lies in the centre of view field. In-plane orientated film also yields a flash figure upon a less than 10° rotation of the sample under polarized microscopy. The interference figures yielded from the out-of-plane orientated films consist of narrow bar cross. The locations of those interference figures depend on the oblique angle of the irradiation light. A method for distinguishing the in-plane orientation of the mesogens from the vertically out-of-plane orientation is demonstrated, which is based on comparing the bar width of their interference figures, and by whether they can produce a flash figure upon a small angle rotation of the film. The liquid crystalline film is identified as positive and uniaxial anisotropy after annealing of the perpendicularly irradiated film. © 2011 The Authors Journal of Microscopy © 2011 Royal Microscopical Society.

  16. [New derivatives of azobenzene for the directed modification of proteins].

    Science.gov (United States)

    Khien, Le Tkhi; Shirling, B; Riazanova, A Iu; Zatsepin, T S; Volkov, E M; Kubareva, E A; Velichko, T I; Pingoud, A; Oretskaia, T S

    2009-01-01

    Derivatives of azobenzene which contained a maleimide group in one of the benzene rings (for binding to a protein cysteine residue) and maleimide, hydroxyl, or carboxyl substitutes in another benzene ring were synthesized. The reactivity of these compounds towards a cysteine residue of a protein and their optical properties in a free state and after their attachment to the mutant forms of the SsoII restriction endonuclease were studied.

  17. Photosensitive microgels containing azobenzene surfactants of different charges.

    Science.gov (United States)

    Schimka, Selina; Lomadze, Nino; Rabe, Maren; Kopyshev, Alexey; Lehmann, Maren; von Klitzing, Regine; Rumyantsev, Artem M; Kramarenko, Elena Yu; Santer, Svetlana

    2016-12-21

    We report on light sensitive microgel particles that can change their volume reversibly in response to illumination with light of different wavelengths. To make the anionic microgels photosensitive we add surfactants with a positively charged polyamine head group and an azobenzene containing tail. Upon illumination, azobenzene undergoes a reversible photo-isomerization reaction from a trans- to a cis-state accompanied by a change in the hydrophobicity of the surfactant. Depending on the isomerization state, the surfactant molecules are either accommodated within the microgel (trans-state) resulting in its shrinkage or desorbed back into water (cis-isomer) letting the microgel swell. We have studied three surfactants differing in the number of amino groups, so that the number of charges of the surfactant head varies between 1 and 3. We have found experimentally and theoretically that the surfactant concentration needed for microgel compaction increases with decreasing number of charges of the head group. Utilization of polyamine azobenzene containing surfactants for the light triggered remote control of the microgel size opens up a possibility for applications of light responsive microgels as drug carriers in biology and medicine.

  18. Surface-Relief Gratings in Halogen-Bonded Polymer–Azobenzene Complexes: A Concentration-Dependence Study

    Directory of Open Access Journals (Sweden)

    Jelle E. Stumpel

    2017-10-01

    Full Text Available In recent years, supramolecular complexes comprising a poly(4-vinylpyridine backbone and azobenzene-based halogen bond donors have emerged as a promising class of materials for the inscription of light-induced surface-relief gratings (SRGs. The studies up to date have focused on building supramolecular hierarchies, i.e., optimizing the polymer–azobenzene noncovalent interaction for efficient surface patterning. They have been conducted using systems with relatively low azobenzene content, and little is known about the concentration dependence of SRG formation in halogen-bonded polymer–azobenzene complexes. Herein, we bridge this gap, and study the concentration dependence of SRG formation using two halogen-bond-donating azobenzene derivatives, one functionalized with a tetrafluoroiodophenyl and the other with an iodoethynylphenyl group. Both have been previously identified as efficient molecules in driving the SRG formation. We cover a broad concentration range, starting from 10 mol % azobenzene content and going all the way up to equimolar degree of complexation. The complexes are studied as spin-coated thin films, and analyzed by optical microscopy, atomic force microscopy, and optical diffraction arising during the SRG formation. We obtained diffraction efficiencies as high as 35%, and modulation depths close to 400 nm, which are significantly higher than the values previously reported for halogen-bonded polymer–azobenzene complexes.

  19. Surface-Relief Gratings in Halogen-Bonded Polymer-Azobenzene Complexes: A Concentration-Dependence Study.

    Science.gov (United States)

    Stumpel, Jelle E; Saccone, Marco; Dichiarante, Valentina; Lehtonen, Ossi; Virkki, Matti; Metrangolo, Pierangelo; Priimagi, Arri

    2017-10-28

    In recent years, supramolecular complexes comprising a poly(4-vinylpyridine) backbone and azobenzene-based halogen bond donors have emerged as a promising class of materials for the inscription of light-induced surface-relief gratings (SRGs). The studies up to date have focused on building supramolecular hierarchies, i.e., optimizing the polymer-azobenzene noncovalent interaction for efficient surface patterning. They have been conducted using systems with relatively low azobenzene content, and little is known about the concentration dependence of SRG formation in halogen-bonded polymer-azobenzene complexes. Herein, we bridge this gap, and study the concentration dependence of SRG formation using two halogen-bond-donating azobenzene derivatives, one functionalized with a tetrafluoroiodophenyl and the other with an iodoethynylphenyl group. Both have been previously identified as efficient molecules in driving the SRG formation. We cover a broad concentration range, starting from 10 mol % azobenzene content and going all the way up to equimolar degree of complexation. The complexes are studied as spin-coated thin films, and analyzed by optical microscopy, atomic force microscopy, and optical diffraction arising during the SRG formation. We obtained diffraction efficiencies as high as 35%, and modulation depths close to 400 nm, which are significantly higher than the values previously reported for halogen-bonded polymer-azobenzene complexes.

  20. 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...

  1. Azobenzene-based inhibitors of human carbonic anhydrase II

    Directory of Open Access Journals (Sweden)

    Leander Simon Runtsch

    2015-07-01

    Full Text Available Aryl sulfonamides are a widely used drug class for the inhibition of carbonic anhydrases. In the context of our program of photochromic pharmacophores we were interested in the exploration of azobenzene-containing sulfonamides to block the catalytic activity of human carbonic anhydrase II (hCAII. Herein, we report the synthesis and in vitro evaluation of a small library of nine photochromic sulfonamides towards hCAII. All molecules are azobenzene-4-sulfonamides, which are substituted by different functional groups in the 4´-position and were characterized by X-ray crystallography. We aimed to investigate the influence of electron-donating or electron-withdrawing substituents on the inhibitory constant Ki. With the aid of an hCAII crystal structure bound to one of the synthesized azobenzenes, we found that the electronic structure does not strongly affect inhibition. Taken together, all compounds are strong blockers of hCAII with Ki = 25–65 nM that are potentially photochromic and thus combine studies from chemical synthesis, crystallography and enzyme kinetics.

  2. Isomerization and fluorescence characteristics of sterically hindered azobenzene derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Han, Mina, E-mail: mrhan@echem.titech.ac.j [Flucto-Order Functions Asian Collaboration Team, RIKEN Advanced Science Institute, RIKEN 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan)] [Department of Electronic Chemistry, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Ishikawa, Daisuke [Department of Electronic Chemistry, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Muto, Emi [Faculty of Education and Integrated Arts and Sciences, Waseda University, 1-6-1 Nishi-Waseda, Shinjuku, Tokyo 169-8050 (Japan); Hara, Masahiko [Flucto-Order Functions Asian Collaboration Team, RIKEN Advanced Science Institute, RIKEN 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan)] [Department of Electronic Chemistry, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)

    2009-10-15

    We report synthesis and isomerization behaviors of sterically hindered azobenzene derivatives (1 and 2) with decyloxy and hydroxy groups, respectively, and their fluorescence enhancement under UV light irradiation characterized by means of absorption and fluorescence spectroscopy measurements. Upon irradiation of as-prepared solution (1) with UV light (approx200 mJ/cm{sup 2}) a cis-rich photostationary state was reached. Obviously different from 2 showing very fast thermal cis-to-trans isomerization within 2 min, slow cis-to-trans thermal back isomerization of 1 with a long alkyl chain at ambient temperature was observed on the time scale of weeks. In contrast to no striking changes in absorption and fluorescence spectra of compound 2, the azobenzene 1 showed green fluorescence upon prolonged irradiation with UV light (about 3-8 J/cm{sup 2} exposure doses), although both the initial trans-rich and cis-rich states of azobenzene molecules were not fluorescent in solution. The stability of fluorescence efficiency caused by drying and redissolving processes was examined.

  3. The absorption spectrum of cis-azobenzene.

    Science.gov (United States)

    Vetráková, Ľubica; Ladányi, Vít; Al Anshori, Jamaludin; Dvořák, Pavel; Wirz, Jakob; Heger, Dominik

    2017-12-06

    Azobenzene is a prototypical photochromic molecule existing in two isomeric forms, which has numerous photochemical applications that rely on a precise knowledge of the molar absorption coefficients (ε). Careful analysis revealed that the previously reported absorption spectra of the "pure" isomers were in fact mutually contaminated by small amounts of the other isomer. Therefore, the absorption spectra of both trans- and cis-azobenzene in methanol were re-determined at temperatures of 5-45 °C. The thermodynamically more stable trans-azobenzene was prepared by warming the solution in the dark. To obtain the spectrum of cis-azobenzene three methods were used, which gave consistent results within the limits of error. The method based on the subtraction of derivative spectra coupled with a global analysis of the spectra recorded during thermal cis-trans isomerization is shown to give slightly more reliable results than the method using isomeric ratios determined by 1 H-NMR. The described methods are readily generalizable to other azobenzene derivatives and to other photochromic systems. The practical implication of the re-determined ε values is demonstrated by a very high precision of spectrophotometric species analysis in azobenzene isomeric mixtures. The new ε values imply that the previously reported quantum yields must be revised.

  4. Azobenzene-containing triazatriangulenium adlayers on Au(111): structural and spectroscopic characterization.

    Science.gov (United States)

    Jung, Ulrich; Kuhn, Sonja; Cornelissen, Ursula; Tuczek, Felix; Strunskus, Thomas; Zaporojtchenko, Vladimir; Kubitschke, Jens; Herges, Rainer; Magnussen, Olaf

    2011-05-17

    Adlayers of different azobenzene-functionalized derivatives of the triazatriangulenium (TATA) platform on Au(111) surfaces were studied by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), gap-mode surface-enhanced Raman spectroscopy (gap-mode SERS), and cyclic voltammetry (CV). The chemical composition of the adlayers is in good agreement with the molecular structure, i.e., different chemical groups attached to the azobenzene functionality were identified. Furthermore, the presence of the azobenzene moieties in the adlayers was verified by the vibration spectra and electrochemical data. These results indicate that the molecules remain intact upon adsorption with the freestanding functional groups oriented perpendicularly to the TATA platform and thus also to the substrate surface.

  5. Design of photocontrolled biomolecules based on azobenzene derivatives

    Science.gov (United States)

    Zatsepin, T. S.; Abrosimova, L. A.; Monakhova, M. V.; Thi Hien, Le; Pingoud, A.; Kubareva, E. A.; Oretskaya, T. S.

    2013-10-01

    This review focuses on methods of designing photocontrolled proteins and nucleic acids. Data on preparation and modification of proteins and nucleic acids with azobenzene derivatives are summarized. Examples of using photoswitchable proteins, their substrates, inhibitors and ligands containing azobenzene, as well as azobenzene derivatives of nucleic acids, for design of nanomachines are considered. The bibliography includes 122 references.

  6. Synthesis and Light Induced Characteristics of Siloxane Substituted Azobenzene: An Application for Optical Storage Device

    Directory of Open Access Journals (Sweden)

    A. R. Yuvaraj

    2016-01-01

    Full Text Available The light induced behaviour of siloxane substituted azobenzene compounds in the presence of alkylene spacers is reported for the first time. Firstly, these photosensitive compounds were synthesized and elucidated the molecular structure by spectral analysis such as NMR, FTIR, and UV/Vis. Photoisomerization effect was evaluated in solution and also in nematic phase. The photosaturation occurred exactly at 29 seconds, whereas thermal back relaxation was observed ranging from 19.8 to 23.8 hours. Long duration of the thermal back relaxation is due to the presence of sterically hindered siloxane group substituted to the azobenzene molecules. Decrease in the duration of cis-trans isomerization was found when the number of alkylene spacers was increased. These siloxane based azobenzene derivatives are useful for the fabrication of optical storage device and molecular switches.

  7. Polymers films with indandione derivatives as alternatives to azobenzene polymers for optical patterning

    Energy Technology Data Exchange (ETDEWEB)

    Stiller, B. [University of Potsdam, Institute of Physics, Am Neuen Palais 10, 14469 Potsdam (Germany)], E-mail: busti@rz.uni-potsdam.de; Saphiannikova, M. [Leibniz Institute of Polymer Research, Hohe Strasse 6, D-01069 Dresden (Germany); Morawetz, K. [University of Potsdam, Institute of Physics, Am Neuen Palais 10, 14469 Potsdam (Germany); Ilnytskyi, J. [Institute for Condensed Matter Physics, 1 Svientsitskii Str., 79011, Lviv (Ukraine); Neher, D. [University of Potsdam, Institute of Physics, Am Neuen Palais 10, 14469 Potsdam (Germany); Muzikante, I. [Institute of Solid State Physics, University of Latvia, Kengaraga Str. 8, Riga, LV 1063 (Latvia); Pastors, P.; Kampars, V. [Riga Technical University, Azenes Str. 14/24, Riga LV-1048 (Latvia)

    2008-10-31

    Surface relief gratings (SRGs) on organic thin films are studied extensively for both scientific interest and in relevance to the applications. Among the chromophores being used the azobenzenes showed the best performance, but the use of alternative photo-sensitive groups provides better general understanding of the phenomena. A thermodynamic theory and molecular dynamics simulations of photoinduced effects are discussed. In this study we use indandione derivatives, known as promising materials for photonics applications, as an alternative to the azobenzenes. We consider their photoreactions when incorporated into a polymer film. One of interesting features is the spectral dependence of the diffraction of indandione containing gratings, which is observed and discussed.

  8. 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.

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

    Science.gov (United States)

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

    2009-01-01

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

  10. Proof for the concerted inversion mechanism in the trans-->cis isomerization of azobenzene using hydrogen bonding to induce isomer locking.

    Science.gov (United States)

    Bandara, H M Dhammika; Friss, Tracey R; Enriquez, Miriam M; Isley, William; Incarvito, Christopher; Frank, Harry A; Gascon, Jose; Burdette, Shawn C

    2010-07-16

    Azobenzene undergoes reversible cistrans photoisomerization upon irradiation. Substituents often change the isomerization behavior of azobenzene, but not always in a predictive manner. The synthesis and properties of three azobenzene derivatives, AzoAMP-1, -2, and -3, are reported. AzoAMP-1 (2,2'-bis[N-(2-pyridyl)methyl]diaminoazobenzene), which possesses two aminomethylpyridine groups ortho to the azo group, exhibits minimal trans-->cis photoisomerization and extremely rapid cis-->trans thermal recovery. AzoAMP-1 adopts a planar conformation in the solid state and is much more emissive (Phi(fl) = 0.003) than azobenzene when frozen in a matrix of 1:1 diethylether/ethanol at 77 K. Two strong intramolecular hydrogen bonds between anilino protons and pyridyl and azo nitrogen atoms are responsible for these unusual properties. Computational data predict AzoAMP-1 should not isomerize following S(2)azobenzene. Confirmation that the AzoAMP-1 and -2 retain excited state photochemistry analogous to azobenzene was provided by ultrafast transient absorption spectroscopy of both compounds in the visible spectral region. The isomerization of azobenzene occurs via a concerted inversion mechanism where both aryl rings must adopt a collinear arrangement prior to inversion. The hydrogen bonding in AzoAMP-1 prevents both aryl rings from adopting this conformation. To further probe the mechanism of isomerization, AzoAMP-3, which has only one anilinomethylpyridine substituent for hydrogen bonding, was prepared and characterized. AzoAMP-3 does not isomerize and exhibits emission (Phi(fl) = 0.0008) at 77 K. The hydrogen bonding motif in AzoAMP-1 and AzoAMP-3 provides the first example where inhibiting the concerted inversion pathway in an azobenzene prevents isomerization. These molecules provide important supporting evidence for the spectroscopic and computational studies aimed at elucidating the isomerization mechanism in azobenzene.

  11. Photoinduced crystal-to-liquid phase transitions of azobenzene derivatives and their application in photolithography processes through a solid-liquid patterning.

    Science.gov (United States)

    Norikane, Yasuo; Uchida, Emi; Tanaka, Satoko; Fujiwara, Kyoko; Koyama, Emiko; Azumi, Reiko; Akiyama, Haruhisa; Kihara, Hideyuki; Yoshida, Masaru

    2014-10-03

    The direct and reversible transformation of matter between the solid and liquid phases by light at constant temperature is of great interest because of its potential applications in various manufacturing settings. We report a simple molecular design strategy for the phase transitions: azobenzenes having para-dialkoxy groups with a methyl group at the meta-position. The photolithography processes were demonstrated using the azobenzene as a photoresist in a single process combining development and etching of a copper substrate.

  12. 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

  13. Side-group size effects on interfaces and glass formation in supported polymer thin films

    Science.gov (United States)

    Xia, Wenjie; Song, Jake; Hsu, David D.; Keten, Sinan

    2017-05-01

    Recent studies on glass-forming polymers near interfaces have emphasized the importance of molecular features such as chain stiffness, side-groups, molecular packing, and associated changes in fragility as key factors that govern the magnitude of Tg changes with respect to the bulk in polymer thin films. However, how such molecular features are coupled with substrate and free surface effects on Tg in thin films remains to be fully understood. Here, we employ a chemically specific coarse-grained polymer model for methacrylates to investigate the role of side-group volume on glass formation in bulk polymers and supported thin films. Our results show that bulkier side-groups lead to higher bulk Tg and fragility and are associated with a pronounced free surface effect on overall Tg depression. By probing local Tg within the films, however, we find that the polymers with bulkier side-groups experience a reduced confinement-induced increase in local Tg near a strongly interacting substrate. Further analyses indicate that this is due to the packing frustration of chains near the substrate interface, which lowers the attractive interactions with the substrate and thus lessens the surface-induced reduction in segmental mobility. Our results reveal that the size of the polymer side-group may be a design element that controls the confinement effects induced by the free surface and substrates in supported polymer thin films. Our analyses provide new insights into the factors governing polymer dynamics in bulk and confined environments.

  14. Photoisomerization of azobenzene moiety in crosslinking polymer materials

    Science.gov (United States)

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

    2012-10-01

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

  15. Photoresponsive peptide azobenzene conjugates that specifically interact with platinum surfaces

    Science.gov (United States)

    Dinçer, S.; Tamerler, C.; Sarıkaya, M.; Pişkin, E.

    2008-05-01

    The aim of this study is to prepare photoresponsive peptide-azobenzene compounds which interacts with platinum surfaces specifically, in order to create smart surfaces for further novel applications in design of smart biosensors and array platforms. Here, a water-soluble azobenzene molecule, 4-hydroxyazo benzene,4-sulfonic acid was synthesized by diazo coupling reaction. A platinum-specific peptide, originally selected by a phage display technique was chemically synthesized/purchased, and conjugated with the azobenzene compound activated with carbonyldiimidazole. Both azobenzene and its conjugate were characterized (including photoresponsive properties) by FTIR, NMR, and UV-spectrophotometer. The yield of conjugation reaction estimated by ninhydrin assay was about 65%. Peptide incorporation did not restrict the light-sensitivity of azobenzene. Adsorption of both the peptide and its azobenzene conjugate was followed by Quartz Crystal Microbalance (QCM) system. The kinetic evaluations exhibited that both molecules interact platinum surfaces, quite rapidly and strongly.

  16. Conductance switching in a molecular device: The role of side groups and intermolecular interactions

    DEFF Research Database (Denmark)

    Taylor, Jeremy Philip; Brandbyge, Mads; Stokbro, Kurt

    2003-01-01

    flow through the monolayer. However, functionalization has a significant effect on the interactions within the monolayer, so that monolayers with NO2 side groups exhibit local minima associated with twisted conformations of the molecules. We use our results to interpret observations of negative......We report first-principles studies of electronic transport in monolayers of Tour wires functionalized with different side groups. An analysis of the scattering states and transmission eigenchannels suggests that the functionalization does not strongly affect the resonances responsible for current...... differential resistance and molecular memory in monolayers of NO2 functionalized molecules in terms of a twisting of the central ring induced by an applied bias potential....

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

    Science.gov (United States)

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

    2014-12-01

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

  18. 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.

  19. 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.

  20. Phase Behavior of Pyrene and Vinyl Polymers with Aromatic Side Groups

    Energy Technology Data Exchange (ETDEWEB)

    Kangovi, Gagan N.; Lee, Sangwoo (Rensselaer)

    2017-10-17

    The phase behavior and thermodynamic properties of mixtures of pyrene and model vinyl polymers with and without aromatic side groups are investigated using differential scanning calorimetry (DSC) measurements. The melting temperature and associated heat of melting of the pyrene crystals in the mixtures are utilized to extract the effective interaction parameters χ and the composition of polymer-rich phases, respectively. The χ of pyrene mixed with polymers with aromatic side groups investigated in this study, polystyrene, poly(2-vinylpyridine), and poly(3-vinylanisole), is less than 0.5 at the melting point of the pyrene crystals, suggesting that pyrene and the polymers with aromatic sides groups are enthalpically compatible, likely due to aromatic π–π interactions. In contrast, the χ of pyrene mixed with poly(1,4-isoprene) or poly(ethylene-alt-propylene) is larger than 0.5. The DSC measurements also enable characterization of the composition of polymer-rich phases. Interestingly, the polymers with aromatic side groups are found to have more pronounced miscibility with pyrene at symmetric compositions.

  1. Synthesis and photoisomerization study of new aza-crown macrocyclic tweezer tethered through an azobenzene linker: The first report on supramolecular interaction of azobenzene moiety with C60

    Science.gov (United States)

    Ghanbari, Bahram; Mahdavian, Mahsa; García-Deibe, A. M.

    2017-09-01

    In the present communication, three bimacrocyclic tweezers linked through azobenzene moiety, Ln (n = 1-3) were synthesized in a multistep route and characterized by x-ray crystallography, IR, 1H and 13C NMR, UV-vis spectroscopy as well as CHN microanalysis. UV-visible spectroscopy established that the irradiation of L1 and L3 with UV light promoted the trans to cis isomerization. Irradiating the reaction mixtures with Hg lamp, significant supramolecular interactions between L1 and L3 with C60 were also found in terms of the association constants calculated by UV-visible spectroscopy, denoting on more pronounced interaction with C60 that in the absence of UV light. The molecular structures of L1-L3 calculated by using DFT method suggested a novel unprecedented interaction between the HOMO's of azobenzene moiety on the tweezer instead of the aromatic groups with C60.

  2. UV/Vis Spectroscopy Studies of the Photoisomerization Kinetics in Self-Assembled Azobenzene-Containing Adlayers.

    Science.gov (United States)

    Krekiehn, N R; Müller, M; Jung, U; Ulrich, S; Herges, R; Magnussen, O M

    2015-08-04

    Direct comparative studies of the photoisomerization of azobenzene derivatives in self-assembled adlayers on Au and as free molecules in dichloromethane solution were performed using UV/vis spectroscopy. For all studied systems a highly reversible trans-cis isomerization in the adlayer is observed. Quantitative studies of the absorbance changes and photoisomerization kinetics reveal that in azobenzenes mounted as freestanding vertical groups on the surface via triazatriangulene-based molecular platforms photoswitching is nearly uninhibited by the local environment in the adlayer. The blue-shift of the π-π* transition in adlayers of these molecules is in good agreement with theoretical studies of the effect of excitonic coupling between the molecules. In contrast, in azobenzene-containing thiol self-assembled monolayers the fraction of photoswitching molecules and the photoisomerization kinetics are significantly reduced compared to free molecules in solution.

  3. 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.

  4. [Isolation and study of azobenzene converting soil bacteria].

    Science.gov (United States)

    Vakkerov-Kouzova, N D

    2005-01-01

    Heterotrophic bacteria were isolated from soil and glass slides and classified as Bacillus cereus SNK12, Paenibacillus polymyxa SNK2, Azotobacter chroococcum ANKII, and Ochrobacterium intermedium ANKI. Their cultures could degrade azobenzene under the conditions of co-metabolism. A rapid test for the ability of bacteria to convert azobenzenes is proposed.

  5. Molecular Engineering of Azobenzene-Functionalized Polyimides to Enhance Both Photomechanical Work and Motion (POSTPRINT)

    Science.gov (United States)

    2014-09-01

    concentrations of azobenzene in both linear and cross-linked PIs, 30 mol % azobenzene diamine (4) and 20 mol % of azobenzene triamine (7) were added...AFRL-RX-WP-JA-2014-0204 MOLECULAR ENGINEERING OF AZOBENZENE - FUNCTIONALIZED POLYIMIDES TO ENHANCE BOTH PHOTOMECHANICAL WORK AND MOTION...August 2014 4. TITLE AND SUBTITLE MOLECULAR ENGINEERING OF AZOBENZENE - FUNCTIONALIZED POLYIMIDES TO ENHANCE BOTH PHOTOMECHANICAL WORK AND MOTION

  6. Synthesis of waterborne polyurethane containing alkoxysilane side groups and the properties of the hybrid coating films

    Energy Technology Data Exchange (ETDEWEB)

    Li, Qi; Guo, Longhai [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 (China); Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, Beijing University of Chemical Technology, Beijing 100029 (China); Qiu, Teng, E-mail: qiuteng@mail.buct.edu.cn [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 (China); Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, Beijing University of Chemical Technology, Beijing 100029 (China); Xiao, Weidong; Du, Dianxing [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 (China); Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, Beijing University of Chemical Technology, Beijing 100029 (China); Li, Xiaoyu, E-mail: lixy@mail.buct.edu.cn [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 (China); Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, Beijing University of Chemical Technology, Beijing 100029 (China)

    2016-07-30

    Highlights: • A diol with side-chain trimethoxysilane (DEA-Si) was synthesized using 3-(methacryloxypropyl)trimethoxysilane (MAPTS) and diethanolamine (DEA). • The crosslinking structure could in situ formed within the WPU matrix through sol-gel process. • The Si tends to shift to the polymer-air interface due to the flexible long alkyl-ester side chain. • The incorporation of DEA-Si enhanced mechanical and surface hydrophobic properties of WPU films. - Abstract: A series of waterborne polyurethane (WPU) containing alkoxysilane side groups were synthesized by using the dihydroxy functionalized alkoxysilane. The diol with trimethoxysilane groups at the side chains was synthesized via Michael addition between 3-(methacryloxypropyl)trimethoxysilane (MAPTS) and diethanolamine (DEA). The silane diol was applied as the chain extender for the NCO-endcapped prepolymer of isophorone diisocyanate, polycarbonate diol, 2,2-bis(hydroxymethyl) butyric acid and 1,4-butanediol. The products with the silane content varied from 1.2 to 16.5 wt% were dispersed in water after neutralization. The effect of the silane diol on the particle size and morphology of the WPU dispersion was studied by dynamic light scattering (DLS) and transmission electron microscopy (TEM), respectively. X-ray photoelectron spectroscopy (XPS) characterization was carried out on the coating film of the WPU, revealing that the long flexible side chain is favorable for the silane components to emigrate toward the film surface and crosslink during the film formation process. As a result, both the surface contact angle to water and water adsorption of the WPU coating films increased with the silane content. Furthermore, the mechanical properties including the modulus and tensile strength of the films were also improved by the incorporation of silane diol.

  7. Hydrogen bonds induced supramolecular self-assembly of azobenzene derivatives on the highly oriented pyrolytic graphite surface

    Science.gov (United States)

    Miao, Xinrui; Cheng, Zhiyu; Ren, Biye; Deng, Wenli

    2012-08-01

    The self-assembly of azobenzene derivatives (CnAzCOOH) with various lengths of peripheral alkyl chains (with carbon number of n = 8, 10, 12, 14, 16) were observed by scanning tunneling microscopy on highly oriented pyrolytic graphite (HOPG) surface. The effect of van der Waals interactions and the intermolecular hydrogen bonding on the two-dimensional self-assembly was systematically studied. No alkyl-chain length effect was observed according to the STM images. All kinds of CnAzCOOH adopting the same pattern self-assembled on the HOPG surface, suggesting the formation of the two-dimensional structures was dominated by the hydrogen bonding of the functional groups. It could be found that two CnAzCOOH molecules formed a hydrogen-bonded dimer with “head-to-head” fashion as expected; however, the dimers organized themselves in the form of relative complex lamellae. Three dimers as a group arranged side by side and formed a well-defined stripe with periodic dislocations due to the registry mechanism of the alkyl chain with the underlying HOPG surface. The hydrogen bonds between the adjacent dimers in one lamella were formed and dominated the self-assembled pattern.

  8. Ion-Exchange Membranes Based on Polynorbornenes with Fluorinated Imide Side Chain Groups

    Directory of Open Access Journals (Sweden)

    Arlette A. Santiago

    2012-01-01

    Full Text Available The electrochemical characteristics of cation-exchange membranes based on polynorbornenes with fluorinated and sulfonated dicarboximide side chain groups were reported. This study was extended to a block copolymer containing structural units with phenyl and 4-oxybenzenesulfonic acid, 2,3,5,6-tetrafluorophenyl moieties replacing the hydrogen atom of the dicarboximide group. A thorough study on the electrochemical characteristics of the membranes involving electromotive forces of concentration cells and proton conductivity is reported. The proton permselectivity of the membranes is also discussed.

  9. Molecular design of ¿super¿ hydrogelators: understanding the gelation process of azobenzene-based sugar derivatives in water

    NARCIS (Netherlands)

    Kobayashi, Hideki; Friggeri, A.; Koumoto, Kazuya; Amaike, Masato; Shinkai, Seiji; Reinhoudt, David

    2002-01-01

    As an attempt to rationally design aqueous organogelators, a bolaamphiphilic azobenzene derivative (1) bearing two sugar groups was synthesized. Compound 1 formed a gel in water even at concentrations as low as 0.05 wt % (0.65 mM). Spectroscopic studies and electron-micrographic observations have

  10. Gold Superparticles Functionalized with Azobenzene Derivatives: SERS Nanotags with Strong Signals.

    Science.gov (United States)

    Ma, Ying; Promthaveepong, Kittithat; Li, Nan

    2017-03-29

    The surface-enhanced Raman spectroscopy (SERS) nanotag was proposed as a substitute for fluorescent dye for imaging and biosensors several decades ago. However, its weak signal and poor reproducibility has hindered its application. Here, we report a new strategy to form Au superparticles (AuSPs) with high SERS enhancement via one-pot formation and self-assembly of Au nanoparticles (NPs). An azobenzene-carrying Raman reporter was synthesized to exhibit a large Raman cross-section and multiple bands. The self-assembly of the Raman reporter on AuSPs generated SERS nanotags with intense signals. A Raman reporter carrying boronic acid and azobenzene groups displayed six distinctive bands. Its corresponding SERS nanotag demonstrated a high sensing ability toward glycoprotein through aggregation-induced SERS enhancement or as a substitute for labeled antibodies in an immunoassay of the glycoprotein.

  11. 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.

  12. Interaction of Azobenzene and Benzalaniline with Strong Amido Bases.

    Science.gov (United States)

    Kornev, Alexander N; Sushev, Vyacheslav V; Zolotareva, Natalia V; Baranov, Evgenii V; Fukin, Georgy K; Abakumov, Gleb A

    2015-12-18

    The interaction of azobenzene with lithium dicyclohexylamide (Cy2NLi) in THF or Et2O afforded the ion-radical salt of azobenzene (1) structurally characterized for the first time and dicyclohexylaminyl radical, which begins a novel chain of transformations leading eventually to the imino-enamido lithium complex (3). Benzalaniline, being a relative of azobenzene, reacted with Cy2NLi without electron transfer by a proton-abstraction mechanism to form the dilithium salt of N(1),N(2),1,2-tetraphenylethene-1,2-diamine quantitatively.

  13. 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....

  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...... 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....

  15. Photoinduced Birefringent Pattern and Photoinactivation of Liquid-Crystalline Copolymer Films with Benzoic Acid and Phenylaldehyde Side Groups.

    Science.gov (United States)

    Kawatsuki, Nobuhiro; Inada, Shogo; Fujii, Ryosuke; Kondo, Mizuho

    2018-02-06

    In situ formation of N-benzylideneaniline (NBA) side groups achieved photoinduced cooperative reorientation of photoinactive copolymers with phenylaldehyde (PA) and benzoic acid (BA) side groups doped with 4-methoxyaniline (AN) molecules. Thermally stimulated molecular reorientation of the side groups was generated due to the axis-selective photoreaction of the NBA moieties. Selective coating with AN on the copolymer film formed NBA moieties in the desired region, resulting in a photoinduced birefringent pattern. Additionally, postannealing at an elevated temperature for a long time attained photoinactivation of the reoriented film, and recoating with AN to form NBA achieved the multiple birefringent patterns and repatterning of the reoriented structures. The slow thermal hydrolysis of NBA, which was 50 times slower than the thermally stimulated self-organization of the side groups due to the presence of BA side groups, contributed to the photodurability of the reoriented film and multiple birefringent patterns.

  16. A phylogenetic group of Escherichia coli associated with active left-sided inflammatory bowel disease

    DEFF Research Database (Denmark)

    Petersen, Andreas M; Nielsen, Eva M; Litrup, Eva

    2009-01-01

    BACKGROUND: Escherichia coli have been found in increased numbers in tissues from patients with Inflammatory Bowel Disease (IBD) and adherent-invasive E. coli have been found in resected ileum from patients with Crohn's disease. This study aimed to characterize possible differences in phylogenetic...... 10 healthy controls. Disease activity was evaluated by sigmoidoscopy. Interestingly, E. coli strains of the phylogenetic group B2 were cultured from 60% of patients with IBD compared to 11% of healthy controls (p coli B2 strains with at least one...... group (triplex PCR), extraintestinal pathogenic E. coli (ExPEC) genes and multilocus sequence type (MLST) between E. coli strains isolated from IBD patients with past or present involvement of the left side of the colon and from controls. RESULTS: Fecal samples were collected from 18 patients and from...

  17. Role of Solvent and Effect of Substituent on Azobenzene Isomerization by Using Room-Temperature Ionic Liquids as Reaction Media.

    Science.gov (United States)

    Angelini, Guido; Canilho, Nadia; Emo, Mélanie; Kingsley, Molly; Gasbarri, Carla

    2015-08-07

    The effects of a para substituent, as the electron-donating -OCH3 and -OtBu groups and the electron-withdrawing -Br and -F atoms, on azobenzene isomerization have been investigated in a series of imidazolium ionic liquids (BMIM PF6, BMIM BF4, BMIM Tf2N, EMIM Tf2N, BM2IM Tf2N, and HMIM Tf2N). The thermal cis-trans conversion tends to be improved in the presence of the substituent, as pointed out by the first-order rate constants measured at 25 °C. Both the rotation and the inversion mechanisms occur in BMIM Tf2N, EMIM Tf2N, and HMIM Tf2N, as highlighted by typical V-shape Hammett plots, but only rotation takes place in BMIM PF6, BMIM BF4, and BM2IM Tf2N. The possible interactions between the cation and the anion of the solvent and both the isomers of the azobenzene derivatives have been studied by small-wide-angle X-ray scattering (SWAXS). The calculated cis population in the photostationary state and the hardness parameter η of the trans isomer show that azobenzene and F-azobenzene are the less reactive molecules for the trans-cis conversion in all the investigated ionic liquids.

  18. Light and Temperature as Dual Stimuli Lead to Self-Assembly of Hyperbranched Azobenzene-Terminated Poly(N-isopropylacrylamide

    Directory of Open Access Journals (Sweden)

    Wenyan Huang

    2016-05-01

    Full Text Available Hyperbranched poly(N-isopropylacrylamides (HBPNIPAMs end-capped with different azobenzene chromophores (HBPNIPAM-Azo-OC3H7, HBPNIPAM-Azo-OCH3, HBPNIPAM-Azo, and HBPNIPAM-Azo-COOH were successfully synthesized by atom transfer radical polymerization (ATRP of N-isopropylacrylamide using different azobenzene-functional initiators. All HBPNIPAMs showed a similar highly branched structure, similar content of azobenzene chromophores, and similar absolute weight/average molecular weight. The different azobenzene structures at the end of the HBPNIPAMs exhibited reversible trans-cis-trans isomerization behavior under alternating UV and Vis irradiation, which lowered the critical solution temperature (LCST due to different self-assembling behaviors. The spherical aggregates of HBPNIPAM-Azo-OC3H7 and HBPNIPAM-Azo-OCH3 containing hydrophobic para substituents either changed to bigger nanorods or increased in number, leading to a change in LCST of −2.0 and −1.0 °C, respectively, after UV irradiation. However, the unimolecular aggregates of HBPNIPAM-Azo were unchanged, while the unstable multimolecular particles of HBPNIPAM-Azo-COOH end-capped with strongly polar carboxyl groups partly dissociated to form a greater number of unimolecular aggregates and led to an LCST increase of 1.0 °C.

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

    Science.gov (United States)

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

    2015-03-01

    The photocontrol of protein function like enzyme activity has been the subject of many investigations to enable reversible and spatiotemporally defined cascading biochemical reactions without the need for separation in miniaturized and parallelized assay setups for academic and industrial applications. A photoswitchable amidohydrolase variant from Bordetella/Alcaligenes with the longest reported half-life (approximately 30 h) for the cis-state of the attached azobenzene group was chosen as a model system to dissect the underlying mechanism and molecular interactions that caused the enormous deceleration of the thermal cis-to-trans relaxation of the azobenzene photoswitch. A systematic site-directed mutagenesis study on the basis of molecular dynamics simulation data was employed to investigate enzyme and thermal cis-to-trans relaxation kinetics in dependence on selected amino acid substitution, which revealed a prominent histidine and a hydrophobic cluster as molecular determinants for the stabilization of the cis-isomer of the attached azobenzene moiety on the protein surface. The nature of the involved interactions consists of polar, hydrophobic, and possibly aromatic Π-Π contributions. The elucidated principles behind the stabilization of the cis-state of azobenzene derivatives on a protein surface can be exploited to design improved biologically inspired photoswitches. Moreover, the findings open the door to highly long-lived cis-states of azobenzene groups yielding improved bistable photoswitches that can be controlled by single light-pulses rather than continuous irradiation with UV light that causes potential photodamage to the employed biomolecules. Copyright © 2015 John Wiley & Sons, Ltd.

  20. Effects of side group functionality and molecular weight on the activity of synthetic antimicrobial polypeptides.

    Science.gov (United States)

    Engler, Amanda C; Shukla, Anita; Puranam, Sravanthi; Buss, Hilda G; Jreige, Nina; Hammond, Paula T

    2011-05-09

    The rapid emergence of antibiotic-resistant bacteria along with increasing difficulty in biofilm treatment has caused an immediate need for the development of new classes of antimicrobial therapeutics. We have developed a library of antimicrobial polypeptides, prepared by the ring-opening polymerization of γ-propargyl-L-glutamate N-carboxyanhydride and the alkyne-azide cycloaddition click reaction, which mimic the favorable characteristics of naturally occurring antimicrobial peptides (AmPs). AmPs are known not to cause drug resistance as well as prevent bacteria attachment on surfaces. The ease and scale of synthesis of the antimicrobial polypeptides developed here are significantly improved over the traditional Merrifield synthetic peptide approaches needed for naturally occurring antimicrobial peptides and avoids the unique challenges of biosynthetic pathways. The polypeptides range in length from 30 to 140 repeat units and can have varied side group functionality, including primary, secondary, tertiary, and quaternary amines with hydrocarbon side chains ranging from 1 to 12 carbons long. Overall, we find these polypeptides to exhibit broad-spectrum activity against both Gram positive and Gram negative bacteria, namely, S. aureus and E. coli , while having very low hemolytic activity. Many of the polypeptides can also be used as surface coatings to prevent bacterial attachment. The polypeptide library developed in this work addresses the need for effective biocompatible therapeutics for drug delivery and medical device coatings.

  1. Polystyrene Backbone Polymers Consisting of Alkyl-Substituted Triazine Side Groups for Phosphorescent OLEDs

    Directory of Open Access Journals (Sweden)

    Beatrice Ch. D. Salert

    2012-01-01

    Full Text Available This paper describes the synthesis of new electron-transporting styrene monomers and their corresponding polystyrenes all with a 2,4,6-triphenyl-1,3,5-triazine basic structure in the side group. The monomers differ in the alkyl substitution and in the meta-/paralinkage of the triazine to the polymer backbone. The thermal and spectroscopic properties of the new electron-transporting polymers are discussed in regard to their chemical structures. Phosphorescent OLEDs were prepared using the obtained electron-transporting polymers as the emissive layer material in blend systems together with a green iridium-based emitter 13 and a small molecule as an additional cohost with wideband gap characteristics (CoH-001. The performance of the OLEDs was characterized and discussed in regard to the chemical structure of the new electron-transporting polymers.

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

    Science.gov (United States)

    Neukirch, Amanda J.; Park, Jinhee; Zobac, Vladmir; Wang, Hong; Jelinek, Pavel; Prezhdo, Oleg V.; Zhou, Hong-Cai; Lewis, James P.

    2015-04-01

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

  3. Unfolding of cytochrome C upon interaction with azobenzene-modified copolymers.

    Science.gov (United States)

    Sun, Jing; Ruchmann, Juliette; Pallier, A; Jullien, L; Desmadril, M; Tribet, Christophe

    2012-11-12

    Hydrophilic or amphiphilic macromolecules are common organic matrices used to encapsulate and protect fragile drugs such as proteins. Polymer cargoes are in addition designed for remote control of protein delivery, upon imparting the macromolecules with stimuli-responsive properties, such as light-triggered polarity switches. The effect of interaction between polymers and proteins on the stability of the proteins is, however, rarely investigated. Here we studied the unfolding/folding equilibrium of cytochrome c (cyt c) under its oxidized or reduced forms, in the presence of various amphiphilic copolymers (by circular dichroism and intrinsic fluorescence measurements). As models of stimuli-responsive amphiphilic chains, we considered poly(acrylic acid) derivatives, modified to contain hydrophobic, light-responsive azobenzene moieties. These copolymers are, thus, capable to develop both ionic (under their sodium forms at pH > 8) and hydrophobic associations with the basic protein cyt c (isoelectric point of 10.0). In aqueous buffer upon increasing urea concentrations, cyt c underwent unfolding, at [urea] of 9-10 M, which was analyzed under the framework of the equilibrium between two states (native-unfolded). In the presence of polymers, the native folding of cyt c was preserved at low concentrations of urea (typically azobenzene moieties in the copolymers and the disappearance of destabilization at ionic strength higher than 150 mM. In addition, stability was similar to that of an isolated cyt c, in the presence of a neutral chain bearing acryloyl(oligoethyleneoxide) units instead of the ionized sodium acrylate moieties. DSC measurements showed that in the presence of polymers, cyt c is thermally unfolded in aqueous buffer at temperatures lowered by >20 °C as compared to thermal unfolding in the absence of polymers. Upon exposure to UV light, properties of the polymers chains were perturbed in situ, upon cis/trans isomerization of the azobenzene groups. In polymers

  4. Azobenzene derivatives carrying a nitroxide radical.

    Science.gov (United States)

    Nakatsuji, Shin'ichi; Fujino, Masahiro; Hasegawa, Satoko; Akutsu, Hiroki; Yamada, Jun-ichi; Gurman, Vladimir S; Kh Vorobiev, Andrey

    2007-03-16

    Several trans-azobenzene derivatives carrying a nitroxide (aminoxyl) radical (2a, 6a-12a) were prepared, and their photoisomerization reactions to the corresponding cis-isomers were investigated. Although no fruitful results could be obtained for the photoisomerizations of the derivatives with para-subsituents (9a-12a), the unsubstututed derivatives at the para-position (2a, 6a, 7a, 8a) were found to show photoisomerizations by irradiation to give the corresponding cis-isomers (2b, 6b, 7b, 8b), being isolated as relatively stable solid materials, and the change of the intermolecular magnetic interactions was apparently observed by the structural change for each photochromic couple.

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

    Science.gov (United States)

    2014-10-01

    is a diamine containing two azobenzenes per molecule and synthesized according to our previous publica- tion. [ 25 ] The generic chemical structure...AFRL-RX-WP-JA-2015-0026 PHOTOPIEZOELECTRIC COMPOSITES OF AZOBENZENE -FUNCTIONALIZED POLYIMIDES AND POLYVINYLIDENE FLUORIDE (POSTPRINT...3. DATES COVERED (From – To) 24 December 2009 – 15 September 2014 4. TITLE AND SUBTITLE PHOTOPIEZOELECTRIC COMPOSITES OF AZOBENZENE - FUNCTIONALIZED

  6. Surface relief gratings in azobenzene supramolecular systems based on polyimides

    Science.gov (United States)

    Schab-Balcerzak, Ewa; Sobolewska, Anna; Stumpe, Joachim; Hamryszak, Lukasz; Bujak, Piotr

    2012-12-01

    The paper describes formation of new supramolecular azopolymers based on hydrogen bonds as perspective materials for laser induced surface relief gratings (SRGs) and for polarization gratings. Supramolecular films were built on the basis of hydrogen bonds between the functional groups of polymer and azobenzene derivatives, that is 4-[4-(3-hydroxypropyloxy)phenylazo]-pyridine and 4-[4-(6-hydroxyhexyloxy)phenylazo]pyridine. Polymers with imide rings, i.e., poly(esterimide)s and poly(etherimide)s, with phenolic hydroxyl or carboxylic groups were applied as matrixes for polymer-dye supramolecular systems. They revealed glass transition temperatures (Tg) in the range of 170-260 °C, whereas supramolecular systems exhibited lower Tg (88-187 °C). The polymers were easily soluble in aprotic polar solvents and exhibited remarkable good film forming properties. Moreover, new chromophore 4-[4-(3-hydroxypropyloxy)phenylazo]pyridine was synthesized and characterized. The light induced SRGs formation and simultaneous formation of the polarization gratings were explored in prepared polymer-chromophore assembles films using a holographic grating recording technique. First time to the best of our knowledge SRGs were formed in hydrogen-bonded supramolecular systems based on polyimides. The highest SRG amplitude and thus the highest diffraction efficiency were obtained in poly(esterimide)s with the hydroxyl functional group. Additionally, the thermal stability of the photoinduced surface gratings and polarization gratings were tested revealing in the case of the SRGs partial stability and almost complete erasure of the polarization gratings.

  7. 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

  8. Side Group Addition to the Polycyclic Aromatic Hydrocarbon Coronene by Proton Irradiation in Cosmic Ice Analogs

    Science.gov (United States)

    Bernstein, Max P.; Moore, Marla H.; Elsila, Jamie E.; Sandford, Scott A.; Allamandola, Louis J.; Zare, Richard N.

    2003-01-01

    Ices at ~15 K consisting of the polycyclic aromatic hydrocarbon coronene (C24H12) condensed either with H2O, CO2, or CO in the ratio of 1:100 or greater have been subjected to MeV proton bombardment from a Van de Graaff generator. The resulting reaction products have been examined by infrared transmission-reflection-transmission spectroscopy and by microprobe laser-desorption laser-ionization mass spectrometry. Just as in the case of UV photolysis, oxygen atoms are added to coronene, yielding, in the case of H2O ices, the addition of one or more alcohol (OH) and ketone (>CO) side chains to the coronene scaffolding. There are, however, significant differences between the products formed by proton irradiation and the products formed by UV photolysis of coronene containing CO and CO2 ices. The formation of a coronene carboxylic acid (COOH) by proton irradiation is facile in solid CO but not in CO2, the reverse of what was previously observed for UV photolysis under otherwise identical conditions. This work presents evidence that cosmic-ray irradiation of interstellar or cometary ices should have contributed to the formation of aromatics bearing ketone and carboxylic acid functional groups in primitive meteorites and interplanetary dust particles.

  9. A project by the SIDeMaST Immunopathology Group on cutaneous vasculitis.

    Science.gov (United States)

    Papini, M; Quaglino, P; La Placa, M; Marzano, A V

    2015-04-01

    Vasculitides are a challenge to the clinician, in terms of both diagnosis and therapy. Multiple classification systems have been implemented and the numerous classification schemes reflect the complexity of establishing a simple classification that could be functional for daily care. Although vasculitis classification has become increasingly elaborated, some areas remain ill defined. Some forms of vasculitis are still difficult to assign to a specific disease entity. Generally accepted operational criteria are available for many vasculitides, but for some entities there are no effective criteria. Moreover, diagnostic criteria for vasculitis with sufficient strength and/or confidence that can be universally accepted are not yet available. The need for diagnostic criteria validated and agreed upon is particularly relevant in the context of cutaneous vasculitis. The project of the SIDeMaST Italian Group of Immunopathology on cutaneous vasculitis is a national prospective observational study designed to develop and validate diagnostic criteria and to improve and validate classification criteria for cutaneous small vessel vasculitis also known as leukocytoclastic vasculitis (CLV). Primary objective of the study will also be that of developing the CUtaneous VAsculitis Severity Index (CUVASI). Secondary objectives of the project will be: 1) definition of the etiological agents that are most frequently associated with CLV; 2) search for possible correlations between causative agent and peculiar clinical and/or histopathological aspects; 3) evaluation of immunofluorescence pattern observed in this specific group of primitive cutaneous vasculitis in order to characterize the diagnostic sensitivity and specificity of this technique; 4) identification of a set of clinical investigations and laboratory tests to be performed for a correct CLV assessment. Actually 15 Italian dermatological clinics are contributing to the project and anticipated recruiting >100 patients with CLV

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

    Science.gov (United States)

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

    2015-11-05

    Photoresponsive molecularly imprinted polymers (PMIPs) containing azobenzene have received wide research attention in recent years and made notable achievements. This article reviews the recent developments on PMIPs containing azobenzene. Topics include the following: (i) brief introduction of azobenzene, molecularly imprinted polymers, and PMIPs containing azobenzene; (ii) progress in functional monomers, cross-linkers, and polymerization conditions; (iii) preparation methods, properties, applications, as well as advantages and disadvantages of conventional PMIPs; (iv) substrate, preparation method, and applications of photoresponsive surface molecularly imprinted polymers; and (v) some perspectives for further development of PMIPs containing azobenzene. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. ANTIPSYCHOTICS SIDE EFFECTS' INFLUENCE ON STIGMA OF MENTAL ILLNESS: FOCUS GROUP STUDY RESULTS

    OpenAIRE

    Novak, Lan; Švab, Vesna

    2009-01-01

    Background: Little research was done on the influence of antipsychotics’ side effects on stigma of mental illness. An overview of studies shows that people with mental illness state that because of medication side effects they feel discriminated in the field of employment, observe worsening of family relations and tend to skip or discontinue their regular medication. It is difficult to discriminate between stigmatizing effects of antipsychotics and other stigma related factors such as illness...

  12. A dynamic combinatorial approach for identifying side groups that stabilize DNA-templated supramolecular self-assemblies.

    Science.gov (United States)

    Paolantoni, Delphine; Cantel, Sonia; Dumy, Pascal; Ulrich, Sébastien

    2015-02-06

    DNA-templated self-assembly is an emerging strategy for generating functional supramolecular systems, which requires the identification of potent multi-point binding ligands. In this line, we recently showed that bis-functionalized guanidinium compounds can interact with ssDNA and generate a supramolecular complex through the recognition of the phosphodiester backbone of DNA. In order to probe the importance of secondary interactions and to identify side groups that stabilize these DNA-templated self-assemblies, we report herein the implementation of a dynamic combinatorial approach. We used an in situ fragment assembly process based on reductive amination and tested various side groups, including amino acids. The results reveal that aromatic and cationic side groups participate in secondary supramolecular interactions that stabilize the complexes formed with ssDNA.

  13. A Dynamic Combinatorial Approach for Identifying Side Groups that Stabilize DNA-Templated Supramolecular Self-Assemblies

    Directory of Open Access Journals (Sweden)

    Delphine Paolantoni

    2015-02-01

    Full Text Available DNA-templated self-assembly is an emerging strategy for generating functional supramolecular systems, which requires the identification of potent multi-point binding ligands. In this line, we recently showed that bis-functionalized guanidinium compounds can interact with ssDNA and generate a supramolecular complex through the recognition of the phosphodiester backbone of DNA. In order to probe the importance of secondary interactions and to identify side groups that stabilize these DNA-templated self-assemblies, we report herein the implementation of a dynamic combinatorial approach. We used an in situ fragment assembly process based on reductive amination and tested various side groups, including amino acids. The results reveal that aromatic and cationic side groups participate in secondary supramolecular interactions that stabilize the complexes formed with ssDNA.

  14. A photoresponsive Au25 nanocluster protected by azobenzene derivative thiolates

    Science.gov (United States)

    Negishi, Yuichi; Kamimura, Ukyo; Ide, Mao; Hirayama, Michiyo

    2012-06-01

    An Au25 cluster protected by azobenzene derivative thiolates (S-Az) ([Au25(S-Az)18]-) was synthesized with the aim of producing a photoresponsive Au25 cluster. The matrix-assisted laser desorption/ionization mass spectrum of the product revealed that [Au25(S-Az)18]- was synthesized in high purity. Optical absorption spectra of [Au25(S-Az)18]- obtained before and after photoirradiation suggest that the azobenzenes in the ligands of Au25(S-Az)18 isomerize with an efficiency of nearly 100%, both from the trans to cis conformation and from the cis to trans conformation. Furthermore, the redox potential and optical absorption of Au25(S-Az)18 were found to change reversibly due to photoisomerization of azobenzenes.An Au25 cluster protected by azobenzene derivative thiolates (S-Az) ([Au25(S-Az)18]-) was synthesized with the aim of producing a photoresponsive Au25 cluster. The matrix-assisted laser desorption/ionization mass spectrum of the product revealed that [Au25(S-Az)18]- was synthesized in high purity. Optical absorption spectra of [Au25(S-Az)18]- obtained before and after photoirradiation suggest that the azobenzenes in the ligands of Au25(S-Az)18 isomerize with an efficiency of nearly 100%, both from the trans to cis conformation and from the cis to trans conformation. Furthermore, the redox potential and optical absorption of Au25(S-Az)18 were found to change reversibly due to photoisomerization of azobenzenes. Electronic supplementary information (ESI) available: Details of the experimental procedure and characterization of the products. See DOI: 10.1039/c2nr30830d

  15. Optical patterning in azobenzene polymer films.

    Science.gov (United States)

    Stiller, B; Geue, T; Morawetz, K; Saphiannikova, M

    2005-09-01

    Thin azobenzene polymer films show a very unusual property, namely optically induced material transport. The underlying physics for this phenomenon has not yet been thoroughly explained. Nevertheless, this effect enables one to inscribe different patterns onto film surfaces, including one- and two-dimensional periodic structures. Typical sizes of such structures are of the order of micrometers, i.e. related to the interference pattern made by the laser used for optical excitation. In this study we have measured the mechanical properties of one- and two-dimensional gratings, with a high lateral resolution, using force-distance curves and pulse force mode of the atomic force microscope. We also report on the generation of considerably finer structures, with a typical size of 100 nm, which were inscribed onto the polymer surface by the tip of a scanning near-field optical microscope used as an optical pen. Such inscription not only opens new application possibilities but also gives deeper insight into the fundamentals physics underlying optically induced material transport.

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

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Sanchez, Carlos; Alcalá, Rafael

    2009-01-01

    Volume holographic data storage is one of the most promising techniques to improve both the storage capacity of devices and the transfer data rate. Among the materials proposed as storage data media, azobenzene containing polymers have received much attention. Some of their properties seem...... to be suitable for holographic storage applications. However, they still present several problems, mainly those related with light sensitivity, response time and stability of the stored information. In this article we review the work performed on volume holographic storage using azobenzene containing polymers...

  17. Porphyrin-Azobenzene-Bodipy Triads: Syntheses, Structures, and Photophysical Properties.

    Science.gov (United States)

    Yin, Bangshao; Kim, Taeyeon; Zhou, Mingbo; Huang, Weiming; Kim, Dongho; Song, Jianxin

    2017-05-19

    Cyclic and acyclic azobenzene bridged porphyrin-dipyrrin derivatives were successfully prepared via Suzuki-Miyaura coupling reaction of α,α'-diborylated dipyrromethane with bromoazophenyl porphyrin or reaction of borylated porphyrin with dibromoazophenyl dipyrrin, and the corresponding porphyrin-Bodipy derivatives were obtained by subsequent boron complexation. The cyclic porphyrin-dipyrrin compound 3Ni was confirmed by X-ray diffraction. The low fluorescence quantum yields of azobenzene bridged porphyrin-Bodipy can be ascribed to the presence of the intramolecular charge transfer state.

  18. 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).

  19. Synthesis and characterization of photoactive azobenzene-based chromophores containing a bulky cholesteryl moiety

    Science.gov (United States)

    Yang, Po-Chih; Lu, Ya-Ling; Li, Chung-Yuan

    2012-05-01

    This study describes the synthesis of a series of azobenzene-based chromophores bearing pendent bulky cholesteryl groups, using esterification reactions. The chromophores were composed of liquid crystalline mesophases with six or eleven methylene segments as spacers, and with electron-donating (sbnd OCH3) and electron-withdrawing (sbnd NO2) terminal groups. The target compounds were characterized by nuclear magnetic resonance spectroscopy, differential scanning calorimetry, polarizing optical microscopy, absorption, and photoluminescence spectroscopies. All the azobenzene derivatives with six or eleven methylene segments revealed chiral nematic phases. We investigated the effects of these photochromic compounds' structures on E/Z photoisomerization under UV irradiation. Chromophores containing the electron-withdrawing nitro-group (sbnd NO2) underwent a faster rate of Z to E isomerization in darkness than the electron-donating (sbnd OCH3) groups did; the isomerization process proceeded via a rotation mechanism. Self-assembled aggregates of C6 solution exhibited enhanced fluorescence in THF/water mixtures at 10% water fraction.

  20. Road–side herbaceous vegetation: life history groups and habitat preferences

    Czech Academy of Sciences Publication Activity Database

    Šerá, Božena

    2010-01-01

    Roč. 58, č. 1 (2010), s. 69-79 ISSN 1505-2249 R&D Projects: GA MŠk(CZ) OC 350.002 Institutional research plan: CEZ:AV0Z60870520 Keywords : road-side vegetation * road ecology * life form * life history * habitat preference * alien species Subject RIV: EH - Ecology, Behaviour Impact factor: 0.542, year: 2010

  1. 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.

  2. Influence of side groups on 90 degrees superexchange : A modification of the Goodenough-Kanamori-Anderson rules

    NARCIS (Netherlands)

    Geertsma, W; Khomskii, D

    1996-01-01

    A mechanism is suggested which can modify in certain cases the Goodenough-Kanamori-Anderson rules determining the character of superexchange in magnetic insulators; namely, side groups coupled to ligands, which are often present but are usually ignored, may contribute significantly, and may in

  3. The Side Effects of the Most Commonly Used Group of Antibiotics in Periodontal Treatments

    Directory of Open Access Journals (Sweden)

    Saimir Heta

    2018-01-01

    Full Text Available Antibiotic combinations are preferred for the treatment of periodontal diseases, with the aim of hitting the bacterial flora, according to its characteristics—aerobic, anaerobic, gram-negative, and gram-positive—with certain antibiotics that act on certain bacteria. The aim of this study is to analyze the side effects of the antibiotics used. Data on the side effects (preferably expressed in percentages of some antibiotics, the favorites in periodontal recipes, are gathered from the literature. These data are listed according to the antibiotic used. In the case of providing a periodontal prescription, the patient is at risk of allergy (5%, nephritis (3%, hematological problems (2–2.5%, gastrointestinal problems (5.5%, disturbance in the nervous system (2%, allergic signs on the skin (5.5%, and problems with electrolytes displayed in lower percentages. Interaction with different medications is present in almost all cases. The influence on the body systems is 4% in total, the maximum value of which is expressed on the skin, and the minimum value is expressed in the nervous system. Cross allergies are at a high value because of the expressed structural similarity of antibiotics. Given a recipe, we have a balance of the percentage of side effects, the percentage of bacterial resistance, and the percentage of the success of the recommended dose of antibiotics.

  4. Photo-orientation in azobenzene containing polybutadiene based polymer

    Czech Academy of Sciences Publication Activity Database

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

    2005-01-01

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

  5. A Fast, Visible-Light-Sensitive Azobenzene for Bioorthogonal Ligation

    NARCIS (Netherlands)

    Poloni, Claudia; Szymanski, Wiktor; Hou, Lili; Browne, Wesley R.; Feringa, Bernard

    2014-01-01

    Azobenzenes have been used as photoresponsive units for the control of numerous biological processes. Primary prerequisites for such applications are site-selective incorporation of photoswitchable units into biomolecules and the possibility of using non-destructive and deep-tissue-penetrating

  6. 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.

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

    DEFF Research Database (Denmark)

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

    1999-01-01

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

  8. An Analysis of Group-Oriented Contingencies and Associated Side Effects in Preschool Children

    Science.gov (United States)

    Payne, Steven W.; Dozier, Claudia L.; Briggs, Adam M.; Newquist, Matthew H.

    2017-01-01

    Group-oriented contingencies are arranged to target the behavior of a group of people simultaneously. Overall, group-oriented contingencies have been shown to be effective in both decreasing problem behavior and increasing appropriate behavior. However, results are mixed regarding which type(s) of group-oriented contingency is most effective for…

  9. 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

  10. Side chain dynamics of carboxyl and carbonyl groups in the catalytic function of Escherichia coli ribonuclease H

    Science.gov (United States)

    Stafford, Kate A.; Ferrage, Fabien; Cho, Jae-Hyun; Palmer, Arthur G.

    2014-01-01

    Many proteins use Asx and Glx (x = n, p, or u) side chains as key functional groups in enzymatic catalysis and molecular recognition. In this study, NMR spin relaxation experiments and molecular dynamics (MD) simulations are used to measure the dynamics of the side chain amide and carboxyl groups, 13Cγ/δ, in Escherichia coli ribonuclease HI (RNase H). Model-free analysis shows that the catalytic residues in RNase H are pre-organized on ps-ns timescales via a network of electrostatic interactions. However, chemical exchange line broadening shows that these residues display significant conformational dynamics on μs – ms timescales upon binding of Mg2+ ions. Two groups of catalytic residues exhibit differential linebroadening, implicating distinct reorganizational processes upon binding of metal ions. These results support the “mobile metal ion” hypothesis, which was inferred from structural studies of RNase H. PMID:24219366

  11. 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.

  12. Switching Process Consisting of Three Isomeric States of an Azobenzene Unit.

    Science.gov (United States)

    Adam, Abdulselam; Haberhauer, Gebhard

    2017-07-19

    Azobenzene and its derivatives are among the most commonly used switching units in organic chemistry. The switching process consists of two states, in which the trans isomer has a stretched and the cis isomer a compact form. Here, we have designed a system in which all isomeric states of an azobenzene moiety (trans → cis-(M) → cis-(P)) are passed step by step. The first step involves a change in the distance between the benzene units, which is common for azobenzene derivatives. In the second step an inversion of the helicity (M→P) of the cis azobenzene unit takes place. The third step leads back to the stretched trans isomer. This switching cycle is achieved by coupling the azobenzene unit with two chiral clamps and with a further azobenzene switching unit.

  13. The C8 side chain is one of the key functional group of Garcinol for its anti-cancer effects.

    Science.gov (United States)

    Zhou, Xin-Ying; Cao, Jing; Han, Chao-Ming; Li, Shu-Wen; Zhang, Chen; Du, Yin-Duan; Zhou, Qian-Qian; Zhang, Xin-Yan; Chen, Xin

    2017-04-01

    Garcinol from the fruit rind of Garcinia indica shows anti-carcinogenic and anti-inflammatory properties, but its mechanism and key functional groups were still need to be identified. Our previous computer modeling suggested that the C8 side chain of Garcinol is so large that it may influence the bioactivity of the compound. 8-Me Garcinol, a derivative of Garcinol in which the bulky side chain at the C8 position of Garcinol is replaced with a much smaller methyl group, was synthesized through a 12-step procedure starting from 1,3-cyclohexanedione. The antitumor activity of Garcinol and 8-Me Garcinol was evaluated in vitro by MTT, cell cycle and cell apoptosis assays. The results showed that 8-Me Garcinol had weaker inhibitory activity on cells proliferation, and little effects on cell cycle and apoptosis in oral cancer cell line SCC15 cells when compared with Garcinol. All of the results indicated 8-Me Garcinol exerts weaker antitumor activity than Garcinol, and the C8 side chain might be an important active site in Garcinol. Changing the C8 side chain will affect the inhibitory effect of Garcinol. Copyright © 2017 Elsevier Inc. All rights reserved.

  14. Are Student Groups Dysfunctional? Perspectives from Both Sides of the Classroom

    Science.gov (United States)

    Chapman, Kenneth J.; Meuter, Matthew L.; Toy, Daniel; Wright, Lauren K.

    2010-01-01

    In today's business world, the ability to work efficiently and effectively in a team is mandatory to a business student's success. Many employers rank "ability to work with a group" as one of the most important attributes for hiring business school graduates. Although an abundance of research has investigated group processes and dynamics during…

  15. Quantifying millisecond time-scale exchange in proteins by CPMG relaxation dispersion NMR spectroscopy of side-chain carbonyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, Alexandar L.; Kay, Lewis E., E-mail: kay@pound.med.utoronto.ca [University of Toronto, Departments of Molecular Genetics, Biochemistry and Chemistry (Canada)

    2011-08-15

    A new pulse sequence is presented for the measurement of relaxation dispersion profiles quantifying millisecond time-scale exchange dynamics of side-chain carbonyl groups in uniformly {sup 13}C labeled proteins. The methodology has been tested using the 87-residue colicin E7 immunity protein, Im7, which is known to fold via a partially structured low populated intermediate that interconverts with the folded, ground state on the millisecond time-scale. Comparison of exchange parameters extracted for this folding 'reaction' using the present methodology with those obtained from more 'traditional' {sup 15}N and backbone carbonyl probes establishes the utility of the approach. The extracted excited state side-chain carbonyl chemical shifts indicate that the Asx/Glx side-chains are predominantly unstructured in the Im7 folding intermediate. However, several crucial salt-bridges that exist in the native structure appear to be already formed in the excited state, either in part or in full. This information, in concert with that obtained from existing backbone and side-chain methyl relaxation dispersion experiments, will ultimately facilitate a detailed description of the structure of the Im7 folding intermediate.

  16. D-Side: A Facility and Workforce Planning Group Multi-criteria Decision Support System for Johnson Space Center

    Science.gov (United States)

    Tavana, Madjid

    2005-01-01

    "To understand and protect our home planet, to explore the universe and search for life, and to inspire the next generation of explorers" is NASA's mission. The Systems Management Office at Johnson Space Center (JSC) is searching for methods to effectively manage the Center's resources to meet NASA's mission. D-Side is a group multi-criteria decision support system (GMDSS) developed to support facility decisions at JSC. D-Side uses a series of sequential and structured processes to plot facilities in a three-dimensional (3-D) graph on the basis of each facility alignment with NASA's mission and goals, the extent to which other facilities are dependent on the facility, and the dollar value of capital investments that have been postponed at the facility relative to the facility replacement value. A similarity factor rank orders facilities based on their Euclidean distance from Ideal and Nadir points. These similarity factors are then used to allocate capital improvement resources across facilities. We also present a parallel model that can be used to support decisions concerning allocation of human resources investments across workforce units. Finally, we present results from a pilot study where 12 experienced facility managers from NASA used D-Side and the organization's current approach to rank order and allocate funds for capital improvement across 20 facilities. Users evaluated D-Side favorably in terms of ease of use, the quality of the decision-making process, decision quality, and overall value-added. Their evaluations of D-Side were significantly more favorable than their evaluations of the current approach. Keywords: NASA, Multi-Criteria Decision Making, Decision Support System, AHP, Euclidean Distance, 3-D Modeling, Facility Planning, Workforce Planning.

  17. 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.

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

    Science.gov (United States)

    Rezaee, Mohammadreza; Compton, Robert

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

  19. Azobenzene Modified Polymer Electrolyte Membrane for Ion Gating

    Science.gov (United States)

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

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

  20. Herstellung polarisationsholografischer optischer Elemente durch Laserbelichtung in Azobenzen-Polymeren

    OpenAIRE

    Fratz, Markus

    2010-01-01

    Polarisationshologramme sind optische Elemente, deren Wirkung auf der Beeinflussung des Polarisationszustandes elektromagnetischer Wellen beruht. Eine Möglichkeit der Herstellung von Polarisationshologrammen besteht darin, mit Hilfe kurzwelligen, linear polarisierten Lichts (Wellenlänge kleiner 550 nm) Anisotropie in Azobenzen-Polymeren zu erzeugen. Die erzeugte Anisotropie ist nach der Belichtung makroskopisch als Doppelbrechung beobachtbar. Durch hochaufgelöste räumliche Variation dieser Do...

  1. In situ Raman spectroelectrochemistry of azobenzene monolayers on glassy carbon.

    Science.gov (United States)

    Itoh, Takashi; McCreery, Richard L

    2007-05-01

    In situ Raman spectra of chemisorbed azobenzene (AB) monolayers on glassy carbon (GC) electrodes were observed under potentiostatic conditions in acetonitrile (ACN) with tetrabutyl-ammonium tetrafluoroborate (TBA-BF4). The Raman intensities of these spectra were high below -1000 mV, and this is attributed to the change in absorbance of AB on GC. In this paper, we describe chemisorbed AB molecules on GC electrode surfaces under potentiostatic conditions.

  2. 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.

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

    NARCIS (Netherlands)

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

    2012-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-02-15

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

  5. 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.

  6. Slower processes of the ultrafast photo-isomerization of an azobenzene observed by IR spectroscopy

    NARCIS (Netherlands)

    Koller, F.O.; Sobotta, C.; Schrader, T.E.; Cordes, T.; Schreier, W.J.; Sieg, A.; Gilch, P.

    2007-01-01

    The photo-induced trans–cis isomerization of the azobenzene derivative 4-nitro-4'-(dimethylamino)azobenzene in polar solution was studied by femtosecond UV/Vis and IR spectroscopy. The UV/Vis experiment reveals two excited state processes; the slower one (1 ps) is the internal conversion to the

  7. Photoinduced reorientation and polarization holography in a new photopolymer with 4-methoxy-N-benzylideneaniline side groups

    Directory of Open Access Journals (Sweden)

    Nobuhiro Kawatsuki

    2013-08-01

    Full Text Available The photoinduced reorientation and surface relief (SR formation behaviors of a novel photosensitive polymer, which was transparent in visible region, were investigated using linearly polarized-313-nm light and holographic exposure with a 325-nm He-Cd laser. The polymer was comprised of photosensitive 4-methoxy-N-benzylideneaniline side groups, and exhibited a sufficient photoinduced molecular reorientation with a birefringence of 0.11. Holographic exposure generated a SR structure, which had a periodical molecular reorientation that depended on the polarization of the interference beams. The generated SR height was ∼212 nm, and the inscription of a double holographic exposure yielded a two-dimensional SR structure.

  8. Coverage-driven dissociation of azobenzene on Cu(111): a route towards defined surface functionalization.

    Science.gov (United States)

    Willenbockel, Martin; Maurer, Reinhard J; Bronner, Christopher; Schulze, Michael; Stadtmüller, Benjamin; Soubatch, Serguei; Tegeder, Petra; Reuter, Karsten; Stefan Tautz, F

    2015-10-25

    We investigate the surface-catalyzed dissociation of the archetypal molecular switch azobenzene on the Cu(111) surface. Based on X-ray photoelectron spectroscopy, normal incidence X-ray standing waves and density functional theory calculations a detailed picture of the coverage-induced formation of phenyl nitrene from azobenzene is presented. Furthermore, a comparison to the azobenzene/Ag(111) interface provides insight into the driving force behind the dissociation on Cu(111). The quantitative decay of azobenzene paves the way for the creation of a defect free, covalently bonded monolayer. Our work suggests a route of surface functionalization via suitable azobenzene derivatives and the on surface synthesis concept, allowing for the creation of complex immobilized molecular systems.

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

    Energy Technology Data Exchange (ETDEWEB)

    Guang Shuaijiang [College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083 (China); Shi Anzhong, E-mail: zhongshian@yahoo.com.c [College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083 (China); Australian Institute for Bioengineering and Nanotechnology, University of Queensland, St. Lucia Qld 4702 (Australia); Chen Lan [Australian Institute for Bioengineering and Nanotechnology, University of Queensland, St. Lucia Qld 4702 (Australia); Blakey, Idriss, E-mail: i.blakey@ug.edu.a [Australian Institute for Bioengineering and Nanotechnology, University of Queensland, St. Lucia Qld 4702 (Australia); Whitaker, Andrew [Australian Institute for Bioengineering and Nanotechnology, University of Queensland, St. Lucia Qld 4702 (Australia)

    2011-02-15

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

  10. Theoretical design of visible light driven azobenzene-based photo-switching molecules

    Science.gov (United States)

    Pang, Juan; Tian, Ziqi; Ma, Jing

    2014-10-01

    The preparation of switchable azobenzene derivatives driven by visible light is desirable for applications in biomolecular systems. o-R-substituted 4,4‧-diacetamidoazobenzene derivatives (Rdbnd H, CH3, OCH3 or OH) were investigated by using both density functional theory (DFT) and reactive molecular dynamics simulations. DFT calculations demonstrated that the nonplanar azo trans geometric structure, which caused by bulky groups tetra substituted in the ortho-position, is the key factor to enable the trans → cis transition with visible light. Furthermore, 100 independent reactive MD simulations demonstrated that 71% trans isomers of tetra o-OCH3-substituted 4,4‧-diacetamidoazobenzene translated to cis, in good agreement with the experimental data.

  11. Charge transfer between the PO4- groups of DNA and the arginine + and lysine + side chains of proteins

    Science.gov (United States)

    Bende, A.; Bogár, F.; Ladik, J.

    2007-03-01

    Using the HF + MP2 methods with full geometry optimizations the charge transfer (CT) from the PO4- groups of DNA to the arginine or lysine side chains of the proteins forming the nuclohistone cores were calculated. (X-ray investigation shows that in the nucleohistone core there are eight histones which are wrapped around by a DNA superhelix). We have found 0.21e and 0.26e CT, respectively. Knowing the structure of nucleohistones one can estimate a charge transfer at every fourth base pair. Taking as average 0.10e CT (there are also other attractive interactions) one can compute the concentrations of holes in DNA. From these one can obtain the dc conductivity for polyguanilic acid (the mobilities are known).

  12. Side-chain liquid crystalline polyesters for optical information storage

    DEFF Research Database (Denmark)

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

    1996-01-01

    and holographic storage in one particular polyester are described in detail and polarized Fourier transform infrared spectroscopic data complementing the optical data are presented. Optical and atomic force microscope investigations point to a laser-induced aggregation as responsible for permanent optical storage.......Azobenzene side-chain liquid crystalline polyester structures suitable for permanent optical storage are described. The synthesis and characterization of the polyesters together with differential scanning calorimetry and X-ray investigations are discussed. Optical anisotropic investigations...

  13. Substituted group and side chain effects for the porphyrin and zinc(II)–porphyrin derivatives: A DFT and TD-DFT study

    International Nuclear Information System (INIS)

    Tai, Chin-Kuen; Chuang, Wen-Hua; Wang, Bo-Cheng

    2013-01-01

    The DFT/B3LYP/LANL2DZ and TD-DFT calculations have been performed to generate the optimized structures, electronic and photo-physical properties for the porphyrin and zinc(II)–porphyrin (metalloporphyrin) derivatives. The substituted group and side chain effects for these derivatives are discussed in this study. According to the calculation results, the side chain moiety extends the π-delocalization length from the porphyrin core to the side chain moiety. The substituted group with a stronger electron-donating ability increases the energy level of highest occupied molecular orbital (E HOMO ). The side chain moiety with a lower resonance energy decreases E HOMO , the energy level of the lowest unoccupied molecular orbital (E LUMO ), and the energy gap (E g ) between HOMO and LUMO in the porphyrin and zinc(II)–porphyrin derivatives. The natural bonding orbital (NBO) analysis determines the possible electron transfer mechanism from the electron-donating to -withdrawing groups (the side chain moiety) in these porphyrin derivatives. The projected density of state (PDOS) analysis shows that the electron-donating group affects the electron density distribution in both HOMO and LUMO, and the side chain moiety influence the electron density distribution in LUMO. The calculated photo-physical properties (absorption wavelengths and the related oscillator strength, f) in dichloromethane environment for porphyrin and zinc(II)–porphyrin derivatives have been simulated by using the TD-DFT method within the Polarizable Continuum Model (PCM). The present of both of the substituted group and the side chain moiety in these derivatives results in a red shift and broadening of the range of the absorption peaks of the Q/Soret band as compared to porphin. -- Highlights: • Side chain moiety extends the π-delocalization for the porphyrins. • Substituted group increases the energy of highest occupied molecular orbital. • Side chain moiety influences the Q/Soret band of

  14. Prevention of aggregation and renaturation of carbonic anhydrase via weak association with octadecyl- or azobenzene-modified poly(acrylate) derivatives.

    Science.gov (United States)

    Martin, Nicolas; Ruchmann, Juliette; Tribet, Christophe

    2015-01-01

    The prevention of aggregation during renaturation of urea-denatured carbonic anhydrase B (CAB) via hydrophobic and Coulomb association with anionic polymers was studied in mixed solutions of CAB and amphiphilic poly(acrylate) copolymers. The polymers were derivatives of a parent poly(acrylic acid) randomly grafted with hydrophobic side groups (either 3 mol % octadecyl group, or 1-5 mol % alkylamidoazobenzene photoresponsive groups). CAB:polymer complexes were characterized by light scattering and fluorescence correlation spectroscopy in aqueous buffers (pH 7.75 or 5.9). Circular dichroism and enzyme activity assays enabled us to study the kinetics of renaturation. All copolymers, including the hydrophilic PAA parent chain, provided a remarkable protective effect against CAB aggregation during renaturation, and most of them (but not the octadecyl-modified one) markedly enhanced the regain of activity as compared to CAB alone. The significant role of Coulomb binding in renaturation and comparatively the lack of efficacy of hydrophobic association was highlighted by measurements of activity regain before and after in situ dissociation of hydrophobic complexes (achieved by phototriggering the polarity of azobenzene-modified polymers under exposure to UV light). In the presence of polymers (CAB:polymer of 1:1 w/w ratio) at concentration ∼0.6 g L(-1), the radii of the largest complexes were similar to the radii of the copolymers alone, suggesting that the binding of CAB involves one or a few polymer chain(s). These complexes dissociated by dilution (0.01 g L(-1)). It is concluded that prevention of irreversible aggregation and activity recovery were achieved when marginally stable complexes are formed. Reaching a balanced stability of the complex plays the main role in CAB renaturation, irrespective of the nature of the binding (by Coulomb association, with or without contribution of hydrophobic association).

  15. Temperature and Recognition Dual Responsive Poly(N-Isopropylacrylamide) and Poly(N,N-Dimethylacrylamide) with Adamantyl Side Group.

    Science.gov (United States)

    Dong, Qiujing; Luo, Chunhua; Li, Na; Chi, Jiaxiang; Zhang, Qingqing

    2018-03-22

    A series of copolymers with an adamantyl side group (poly(NIPAM-co-AdMA) and poly(DMAM-co-AdMA)) were prepared by radical copolymerization of N -isopropylacrylamide (NIPAM) and N , N -dimethylacrylamide (DMAM) with a 2-methyl-2-adamantylmethacrylate (AdMA) monomer. The structure and composition of the as-synthesized copolymers were characterized by Fourier transform infrared (FT-IR) spectroscopy, proton nuclear magnetic resonance (¹H NMR) spectroscopy, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), and elemental analysis. Temperature and recognition dual responsivity of the copolymers was investigated by cloud point (T cp ) and dynamic light scattering (DLS), respectively. The results show that the as-synthesized copolymers are a kind of temperature-responsive polymer with a lower critical solution temperature (LCST). T cp was approximately consistent with the critical temperature of intermolecular copolymer association (T ass ) from DLS. For these copolymers, T cp decreases with increasing content of AdMA unit in the copolymers. After the addition of β-cyclodextrins (β-CD), T cp increases, and the increment of T cp values gradually became large with increasing content of AdMA in the copolymers. It is host-guest molecular recognition of β-CD and adamantyl groups that endows the as-synthesized copolymers with recognition-tunable thermosensitivity.

  16. Relaxation effect of stilbene azobenzene derivatives on their holographic properties

    Energy Technology Data Exchange (ETDEWEB)

    Saharov, D; Ozols, A; Kokars, V; Kampars, V; Mezinskis, G; Maleckis, A; Pludons, A; Jansone, M [Riga Technical University, Faculty of Material Science and Applied Chemistry, Azenes 14/24, LV-1048, Riga (Latvia)

    2007-12-15

    The material relaxation effect on holographic properties of stilbene azobenzene derivatives in the form of glassy films has been experimentally studied. Holographic grating recording with the period of 2 {mu}m was made by a He-Ne laser at 633 nm in the self-diffraction mode. The readout was made simultaneously in order to follow the fast self-diffraction efficiency changes. The existence of the optimal material storage time (6-51 day) is established enabling the most efficient recording. Material relaxation amplitude and the holographic recording efficiency increased when the chromophore concentration was increased, especially above the threshold of about 70 mass %. It is also found that 633 nm recording due to the modulation of refraction and absorption indices is accompanied by the formation of surface relief grating. The conclusion is made that holographic recording in stilbene azobenzene derivatives at 633 nm is due to the chromophore reorientation by linearly polarized light possibly including trans-cis-trans transformations.

  17. Preparing Patients and Partners for Recovery From the Side Effects of Prostate Cancer Surgery: A Group Approach.

    Science.gov (United States)

    Paich, Kellie; Dunn, Rodney; Skolarus, Ted; Montie, James; Hollenbeck, Brent; Palapattu, Ganesh; Wood, David; Mitchell, Staci; Hola, Victor; Erickson, Kim; Shifferd, Jennifer; Wittmann, Daniela

    2016-02-01

    To evaluate the acceptance and knowledge attained in a preoperative psychoeducational group seminar for patients and partners. Education before radical prostatectomy (RP) helps patients set appropriate expectations for functional recovery. We hypothesized that the seminar would be acceptable and would facilitate learning. Men scheduled for RP from March 1, 2012, to July 31, 2013, were eligible, and partners were invited. The 2.5-hour interactive seminar included multidisciplinary presentations about surgery-related urinary and sexual outcomes, rehabilitation, and couples' work toward recovering sexual intimacy. A satisfaction and knowledge survey was administered immediately afterward. We analyzed demographic and satisfaction data with descriptive statistics and evaluated congruence of patients' and partners' knowledge responses using nonparametric statistics. Of 618 patients scheduled, 426 patients and 342 partners attended; 323 couples provided complete data. Over 90% of participants found the seminar informative and 74% found a group setting comfortable; 84% found travel to the seminar burdensome. Most patients and partners (84% and 90%, respectively) expected some urinary incontinence and understood rehabilitation strategies to regain bladder control; 84% of patients and 78% of partners expected postsurgery sexual activity to be different and 73% of patients and 65% of partners expected surgery to make erections worse. Couples were incongruent regarding frequency of incontinence, likelihood of erectile dysfunction, and sex being different after surgery: patients were more realistic. A preoperative psychoeducational group seminar on the recovery from RP side effects promotes realistic expectations and is acceptable to patients and partners. Incongruent couples may need further instruction after surgery. Web-based methodology could improve access and should be studied in future research. Copyright © 2016 Elsevier Inc. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    Shohei Mori

    2015-03-01

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

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

    Science.gov (United States)

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

    2015-06-01

    Bilayer photomechanical films are fabricated by depositing one layer of molecular azobenzene chromophores onto flexible low-density polyethylene substrates. The photoinduced bending and unbending behavior of five azobenzene derivatives including azobenzene, 4-hydroxy-azobenzene, 4-((4-hydroxyphenyl)diazenyl)bezoitrile, 4-((4-methoxyph-enyl)diazenyl)phenol, and 4-(phenyldiazenyl)phenol is systematically studied by considering the incident light intensity and the thickness of the coated chromophore layers. Precise control of photoinduced curling of the bilayer film is successfully achieved upon irradiation with two beams of UV light, and the curled films can be recovered by thermal relaxation in the dark. The easily fabricated bilayer films show fast photomechanical response, strong photoinduced stress, and stability similar to crosslinked polymeric films. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    OpenAIRE

    Mori, Shohei; Morihiro, Kunihiko; Kasahara, Yuuya; Tsunoda, Shin-ichi; Obika, Satoshi

    2015-01-01

    Nucleic acids that change their properties upon photo-irradiation could be powerful materials for molecular sensing with high spatiotemporal resolution. Recently, we reported a photo-isomeric nucleoside bearing azobenzene at the C5 position of 2'-deoxyuridine (dUAz), whose hybridization ability could be reversibly controlled by the appropriate wavelength of light. In this paper, we synthesized and evaluated dUAz analogues that have various para-substitutions on the azobenzene moiety. Spectro...

  1. Regulation of supramolecular chirality in co-assembled polydiacetylene LB films with removable azobenzene derivatives.

    Science.gov (United States)

    Jiang, Hao; Chen, Xin; Pan, Xiujuan; Zou, Gang; Zhang, Qijin

    2012-05-14

    Herein, we report a novel model that combines supramolecular chemistry and the LB technique for the chirality regulation of the PDA films. The helical packing of PCDA molecules and the chiroptical properties of the resulting PDA LB films can be easily modulated by different azobenzene derivatives. Moreover, the effect of the photo-isomerization of azobenzene chromophores on the helical formation of PCDA assemblies is investigated in detail. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Surface-Relief Gratings in Halogen-Bonded Polymer–Azobenzene Complexes: A Concentration-Dependence Study

    OpenAIRE

    Stumpel, Jelle E.; Marco, Saccone; Valentina, Dichiarante; Ossi, Lehtonen; Matti, Virkki; Pierangelo, Metrangolo; Arri, Priimagi

    2017-01-01

    In recent years, supramolecular complexes comprising a poly(4-vinylpyridine) backbone and azobenzene-based halogen bond donors have emerged as a promising class of materials for the inscription of light-induced surface-relief gratings (SRGs). The studies up to date have focused on building supramolecular hierarchies, i.e., optimizing the polymer-azobenzene noncovalent interaction for efficient surface patterning. They have been conducted using systems with relatively low azobenzene content, a...

  3. 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

    2018-04-27

    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.

  4. CB 1/2 dual agonists with 3-carbamoyl 2-pyridone derivatives as antipruritics: reduction of CNS side effects by introducing polar functional groups.

    Science.gov (United States)

    Odan, Masahide; Ishizuka, Natsuki; Hiramatsu, Yoshiharu; Inagaki, Masanao; Hashizume, Hiroshi; Fujii, Yasuhiko; Mitsumori, Susumu; Morioka, Yasuhide; Soga, Masahiko; Deguchi, Masashi; Yasui, Kiyoshi; Arimura, Akinori

    2012-04-15

    Our lead compound 1 showed high affinity for both CB1 and CB2 receptors, suggesting the possibility of inducing psychoactive side effects through the CB1 receptor in the brain. To solve this issue, polar functional groups were introduced at the 3-position of the pyridone core of compound 1 to find CB1/2 dual agonists such as 17 and 20 which did not show any CNS side effects. Copyright © 2012 Elsevier Ltd. All rights reserved.

  5. Optical anisotropy of polyimide and polymethacrylate containing photocrosslinkable chalcone group in the side chain under irradiation of a linearly polarized UV light

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Dong Hoon; Cha, Young Kwan [Kyunghee Univ., Yongin (Korea, Republic of)

    2002-03-01

    Photocrosslinkable soluble polyimide and polymethacrylate compound were synthesized for studying the optically induced anisotropy of the thin films. Chalcone group was introduced into the side chain unit of two polymers. We observed a photodimerization behavior between the double bonds in the chalcone group and an optical anisotropy of these materials by irradiation of a linearly polarized UV light (LPL). Optical anisotropy of the thin film was also investigated by using polarized UV absorption spectroscopy.The dynamic property of optical anisotropy in photoreactive polyimide was compared to that in polymethacrylate containing chalcone group in the side chain.

  6. Optical anisotropy of polyimide and polymethacrylate containing photocrosslinkable chalcone group in the side chain under irradiation of a linearly polarized UV light

    CERN Document Server

    Choi, D H

    2002-01-01

    Photocrosslinkable soluble polyimide and polymethacrylate compound were synthesized for studying the optically induced anisotropy of the thin films. Chalcone group was introduced into the side chain unit of two polymers. We observed a photodimerization behavior between the double bonds in the chalcone group and an optical anisotropy of these materials by irradiation of a linearly polarized UV light (LPL). Optical anisotropy of the thin film was also investigated by using polarized UV absorption spectroscopy.The dynamic property of optical anisotropy in photoreactive polyimide was compared to that in polymethacrylate containing chalcone group in the side chain.

  7. The molecular mechanism of N-acetylglucosamine side-chain attachment to the Lancefield group A carbohydrate in Streptococcus pyogenes.

    Science.gov (United States)

    Rush, Jeffrey S; Edgar, Rebecca J; Deng, Pan; Chen, Jing; Zhu, Haining; van Sorge, Nina M; Morris, Andrew J; Korotkov, Konstantin V; Korotkova, Natalia

    2017-11-24

    In many Lactobacillales species ( i.e. lactic acid bacteria), peptidoglycan is decorated by polyrhamnose polysaccharides that are critical for cell envelope integrity and cell shape and also represent key antigenic determinants. Despite the biological importance of these polysaccharides, their biosynthetic pathways have received limited attention. The important human pathogen, Streptococcus pyogenes , synthesizes a key antigenic surface polymer, the Lancefield group A carbohydrate (GAC). GAC is covalently attached to peptidoglycan and consists of a polyrhamnose polymer, with N -acetylglucosamine (GlcNAc) side chains, which is an essential virulence determinant. The molecular details of the mechanism of polyrhamnose modification with GlcNAc are currently unknown. In this report, using molecular genetics, analytical chemistry, and mass spectrometry analysis, we demonstrated that GAC biosynthesis requires two distinct undecaprenol-linked GlcNAc-lipid intermediates: GlcNAc-pyrophosphoryl-undecaprenol (GlcNAc-P-P-Und) produced by the GlcNAc-phosphate transferase GacO and GlcNAc-phosphate-undecaprenol (GlcNAc-P-Und) produced by the glycosyltransferase GacI. Further investigations revealed that the GAC polyrhamnose backbone is assembled on GlcNAc-P-P-Und. Our results also suggested that a GT-C glycosyltransferase, GacL, transfers GlcNAc from GlcNAc-P-Und to polyrhamnose. Moreover, GacJ, a small membrane-associated protein, formed a complex with GacI and significantly stimulated its catalytic activity. Of note, we observed that GacI homologs perform a similar function in Streptococcus agalactiae and Enterococcus faecalis In conclusion, the elucidation of GAC biosynthesis in S. pyogenes reported here enhances our understanding of how other Gram-positive bacteria produce essential components of their cell wall. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  8. 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.

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

    Science.gov (United States)

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

    2016-06-01

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

  10. Small azobenzene derivatives active against bacteria and fungi.

    Science.gov (United States)

    Piotto, Stefano; Concilio, Simona; Sessa, Lucia; Porta, Amalia; Calabrese, Elena Concetta; Zanfardino, Anna; Varcamonti, Mario; Iannelli, Pio

    2013-10-01

    ATP synthase and protein kinase (PKs) are prime targets for drug discovery in a variety of diseases. It is well known that numerous stilbenes are capable to interact and inhibit ATP synthase and PKs. This work focuses on a series of azobenzene based molecules having high structural similarity with antimicrobial stilbenes. An investigation was carried out analyzing the potential toxicity of a large set of molecules by means of computational analysis. A small selection of potential low toxic molecules have been therefore synthesized, characterized and finally microbiologically tested. The synthesized compounds show potent bactericidal activity against Gram+ and a fungus, and are capable of inhibiting biofilm formation. Finally, the compounds demonstrated a thermal stability that makes them potential candidates for incorporation in polymer matrix for application as biomedical devices and food packaging. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

  11. Tracking of azobenzene isomerization by X-ray emission spectroscopy.

    Science.gov (United States)

    Ebadi, H

    2014-09-11

    Cis-trans isomerizations are among the fundamental processes in photochemistry. In azobenzene or its derivatives this dynamics is, due to its reversibility, one of the reactions widely used in photostimulation of molecular motors or in molecular electronics. Though intensively investigated in the optical regime, no detailed study exists in the X-ray regime so far. Because the X-ray emission spectroscopy echoes the electronic structure sensitive to the geometry, this theoretical report based on the density functional theory and its time-dependent version presents different nitrogen K-edge X-ray emission spectra for cis and trans isomers with close interrelation to their electron configuration. Considering the spectrum along the isomerization path, these structural signatures can be utilized to probe the isomerization dynamics in the excited molecule. The scheme can further be generalized to the element specific photoreactions.

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

    Science.gov (United States)

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

    2016-06-24

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

  13. Azobenzene-based supramolecular polymers for processing MWCNTs.

    Science.gov (United States)

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

    2013-01-21

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

  14. Photoisomerization of azobenzene derivatives confined in gold nanoparticle aggregates.

    Science.gov (United States)

    Yoon, Jun Hee; Yoon, Sangwoon

    2011-07-28

    Photoisomerization is an important reaction that confers photoresponsive functionality on nanoparticles. Although photoisomerization of molecules forming self-assembled monolayers on two-dimensional surfaces or three-dimensional clusters has been studied, a detailed picture of interactions of molecules undergoing isomerization with nanoparticles is not available. In this paper, we report on the photoisomerization of azobenzene derivatives spatially confined in gold nanoparticle (AuNP) aggregates. AuNP aggregates allow us to simultaneously probe the structural changes of molecules via surface-enhanced Raman spectroscopy (SERS) and the accompanying changes in interparticle interactions via surface plasmon couplings. AuNP aggregates are formed by the adsorption of synthesized azobenzene-derivatized sulfides (Az) onto the surfaces of AuNPs. The photoisomerization of the adsorbed Az from trans to cis by excitation at 365 nm causes the AuNPs to move close to each other in the aggregates, leading to a redshift of the surface plasmon coupling band in the UV-vis spectra and a concomitant rise in SERS intensity. SERS spectra reveal that the vibrational modes containing the N=N stretching character redshift upon irradiation, suggesting that the N=N bond is significantly weakened when Az is in the cis form in the AuNP aggregates. The weakening of the N=N bond is attributed to the interaction of the N=N bond, which is more exposed to the outside in the cis conformation, with the nearby AuNPs that have come closer by the isomerization of adsorbed Az. We find that backisomerization from cis to trans occurs much faster in the AuNP aggregates (k = 1.9 × 10(-2) min(-1)) than in solution (k = 1.3 × 10(-3) min(-1)) because of the reduced N=N bond order of cis-Az in the aggregates. This journal is © the Owner Societies 2011

  15. UV-Vis spectroscopy of tyrosine side-groups in studies of protein structure. Part 2: selected applications.

    Science.gov (United States)

    Antosiewicz, Jan M; Shugar, David

    2016-06-01

    In Part 2 we discuss application of several different types of UV-Vis spectroscopy, such as normal, difference, and second-derivative UV absorption spectroscopy, fluorescence spectroscopy, linear and circular dichroism spectroscopy, and Raman spectroscopy, of the side-chain of tyrosine residues in different molecular environments. We review the ways these spectroscopies can be used to probe complex protein structures.

  16. UV?Vis spectroscopy of tyrosine side-groups in studies of protein structure. Part 2: selected applications

    OpenAIRE

    Antosiewicz, Jan M.; Shugar, David

    2016-01-01

    In Part 2 we discuss application of several different types of UV?Vis spectroscopy, such as normal, difference, and second-derivative UV absorption spectroscopy, fluorescence spectroscopy, linear and circular dichroism spectroscopy, and Raman spectroscopy, of the side-chain of tyrosine residues in different molecular environments. We review the ways these spectroscopies can be used to probe complex protein structures.

  17. Self-assembly of azobenzene based side-chain liquid crystalline ...

    Indian Academy of Sciences (India)

    . Grimsdale A C and Müllen K 2005 Angew. Chem. Int. Ed. 44 5592. 20. Serpe M J and Craig S L 2007 Langmuir 23 1626. 21. Delphia Shalini Rosalyn P, Senthil S, Kannan P, Vinitha. G and Ramalingam A 2007 J. Phys. Chem. Solids 68. 1812.

  18. Self-assembly of azobenzene based side-chain liquid crystalline ...

    Indian Academy of Sciences (India)

    The polymeric complexes acquitted as undivided liquid crystalline properties exhibited stable and enantiotropic mesophases. The precursor, monomer and polymer were analysed by 1H-NMR and. 13C-NMR spectroscopy. The hydrogen bonding interaction in polymer complexes (P10-A7 to P10-A12) was investigated by ...

  19. 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...

  20. Photoresponsive SAMs on gold fabricated from azobenzene-functionalised asparagusic acid derivatives.

    Science.gov (United States)

    Siemeling, Ulrich; Bruhn, Clemens; Bretthauer, Frauke; Borg, Marta; Träger, Frank; Vogel, Florian; Azzam, Waleed; Badin, Mihaela; Strunskus, Thomas; Wöll, Christof

    2009-10-28

    We have prepared a range of azobenzene derivatives equipped with an asparagusic acid-based 1,2-dithiolane headgroup suitable for chemisorption on solid gold substrates. The formation of self-assembled monolayers (SAMs) of the amide cyclo-S2C3H5-4-C(O)NH-p-C6H4-N=N-Ph (1) and the ester cyclo-S2C3H5-4-C(O)O-p-C6H4-N=N-Ph (2) on gold was monitored in situ and in real time by optical second harmonic generation (SHG). The structure and composition of these SAMs was investigated by a range of ex situ methods, viz. ellipsometry, X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and Fourier transform infrared reflection absorption spectroscopy (FTIRRAS). Reversible, but moderate, photoswitchability was observed for these one-component SAMs by ellipsometry and dynamic contact angle measurements. Use of a second 1,2-dithiolane component for lateral dilution of the photoactive terminal groups resulted in a much more pronounced photoresponse.

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

    Science.gov (United States)

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

    2015-04-27

    A series of new photo-responsive amino acid-derived azobenzenedicarboxylic acid derivatives (S)-1 a-e were synthesized. Compound (S)-1 a in the trans form exhibited no circular dichroism (CD) signal in DMF under ambient conditions, whereas intense Cotton effects were observed upon UV irradiation, indicating the formation of a chiral supramolecular structure in the cis form. The CD signals disappeared when trifluoroacetic acid (TFA) was added to the solution. The ester counterpart [(S)-1 a'] showed no CD signal. Hydrogen bonding between the carboxy groups seemed necessary for constructing the supramolecular structure. The kinetic studies of cis to trans isomerization of (S)-1 a demonstrated that the formation of a chiral supramolecule enhances the stability of the cis-azobenzene structure. The ESI mass spectrum of stilbenedicarboxylic acid (S)-4, an analogue of (S)-1 b, confirmed the formation of a dimer. A theoretical CD study revealed that (S)-1 a in the cis form should be present as a cyclic chiral dimer. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. 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.

  3. Photoisomerization of amphiphilic azobenzene derivatives in Langmuir Blodgett films prepared as polyion complexes, using ionic polymers

    Energy Technology Data Exchange (ETDEWEB)

    Shembekar, Vishakha R. [Department of Chemistry, Indian Institute of Technology, Bombay, Mumbai-400 076 (India); Contractor, A.Q. [Department of Chemistry, Indian Institute of Technology, Bombay, Mumbai-400 076 (India); Major, S.S. [Department of Physics, Indian Institute of Technology, Bombay, Mumbai-400 076 (India); Talwar, S.S. [Department of Physics, Indian Institute of Technology, Bombay, Mumbai-400 076 (India)]. E-mail: chsstia@phy.iitb.ac.in.z

    2006-07-03

    Polyion complexation in mixed Langmuir and Langmuir Blodgett (LB) films of photochromic amphiphilic azobenzene carboxylic acids, 11-[4-(4-hexylphenyl)azo] phenoxyundecanoic acid, 11-(4-phenylazo)phenoxyundecanoic acid, and diamine grafted poly(methylmethaacrylate) polymers has been studied. Monolayer behaviour of the pure components and mixed films was studied through pressure-area isotherms and LB films were characterized by spectroscopic, X-ray diffraction and Atomic force microscopy techniques. Aggregation (H-type), often observed in LB films of pure amphiphilic azo acids, was partly avoided in the mixed LB films as indicated by absorption spectral studies. Photoisomerization of the polyion complexed LB films was also studied. The results altogether demonstrate that amine grafted polymer enter into a polyion complexation with azo acid carboxylate group. LB films could be obtained by transfer of the composite monolayers and these LB films exhibited different levels of aggregation of the azo acids. Reversible photoisomerization was observed in LB films with unaggregated azo acid.

  4. Multiresponsive hydrogel coassembled from phenylalanine and azobenzene derivatives as 3D scaffolds for photoguiding cell adhesion and release.

    Science.gov (United States)

    Liu, Guo-Feng; Ji, Wei; Wang, Wan-Lin; Feng, Chuan-Liang

    2015-01-14

    A multiresponsive hydrogel system coassembled from phenylalanine derivative gelator (LPF2) and azobenzene (Azo) derivative (PPI) is constructed, which can respond to temperature, pH, host-guest interaction, and photoirradiation. A set of techniques including circular dichroism, Fourier transform infrared spectroscopy, (1)H NMR, and X-ray powder diffraction confirm that the hydrogel is formed through hydrogen bonds between amide moieties/pyridine and carbonyl groups, enduing the coassembled hydrogel with multiresponsive properties that make it possible to control cell encapsulation and release in three-dimensional environments under multistimulus, for example, UV irradiation. This study brings a novel approach to develop multistimuli-responsive hydrogels by coassembly of various responsive components for biomedical interest, for example, the controlled delivery of various therapeutic biological agents.

  5. 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...... is small and thus a high excitation light intensity is required. We investigate the enhancement of the local energy density using periodically nanostructured surfaces in a high refractive index material. Such photonic crystals support quasi-guided modes visible as resonances in the reflection as well...... as in the transmission light spectrum. These guided modes have field contributions decaying exponentially in the near field of the photonic crystal. Azobenzene immobilized on the photonic crystal surface will experience a significantly increased light intensity compared to non-resonant surfaces. We performed finite...

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

    Science.gov (United States)

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

    2015-12-18

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

  7. Effects of high pressure on azobenzene and hydrazobenzene probed by Raman spectroscopy.

    Science.gov (United States)

    Dong, Zhaohui; Seemann, Natashia M; Lu, Ning; Song, Yang

    2011-12-22

    In this study, two hydrazine derivatives, azobenzene and hydrazobenzene, were compressed in a diamond anvil cell at room temperature up to 28 GPa followed by decompression. In situ Raman spectroscopy was employed to monitor the pressure-induced structural evolutions. Azobenzene was found to undergo a phase transition at ~10 GPa. Further compression to 18 GPa resulted in an irreversible breakdown of the molecular structure. Although hydrazobenzene exhibited a structural transition at a similar pressure of 10 GPa, it was found to sustain a compression pressure as high as 28 GPa without chemical reactions. The transition sequence of hydrazobenzene upon compression and decompression was thus entirely reversible in the pressure region studied, in strong contrast to that of azobenzene. The high-pressure structures of these two molecules were examined based on the spectroscopic data, and their drastically different high-pressure behaviors were analyzed and interpreted with the aid of ab initio molecular orbital calculations.

  8. Photoresponsive Amphiphilic Macrocycles Containing Main-Chain Azobenzene Polymers.

    Science.gov (United States)

    Sun, Yadong; Wang, Zhao; Li, Yiwen; Zhang, Zhengbiao; Zhang, Wei; Pan, Xiangqiang; Zhou, Nianchen; Zhu, Xiulin

    2015-07-01

    Herein, the first example of photosensitive cyclic amphiphilic homopolymers consisting of multiple biphenyl azobenzene chromophores in the cyclic main chain tethered with hydrophilic tetraethylene glycol monomethyl ether units is presented. The synthetic approach involves sequentially performed thermal catalyzed "click" step-growth polymerization in bulk, and Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) intramolecular cyclization from α-alkyne/ω-azide linear precursors. It is observed that such amphiphilic macrocycles exhibit increased glass transition temperatures (Tg ), slightly faster trans-cis-trans photoisomerization, and enhanced fluorescence emission intensity compared with the corresponding linear polymers. In addition, the cyclic amphiphilic homopolymers self-assemble into spherical nanoparticles with smaller sizes which possess slower photoresponsive behaviors in a tetrahydrofuran/water mixture compared with those of the linear ones. All these interesting observations suggest that the cyclic topology has a great influence on the physical properties and self-assembly behavior of these photoresponsive amphiphilic macrocycles in general. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. [Ochrobactrum intermedium ANKI, a nitrogen-fixing bacterium able to decolorize azobenzene].

    Science.gov (United States)

    Vakkerov-Kouzova, N D

    2007-01-01

    Morphological and biochemical properties of the nitrogen-fixing strain Ochrobactrum intermedium ANKI, intensely growing on media with azo compounds, and its resistance to various common xenobiotics were investigated. The kinetics of azobenzene conversion by O. intermedium ANKI was studied. Under cometabolism conditions, up to 40 mg of azobenzene per liter of medium were decolorized within one week. It was shown that the strain possessed molybdenum-dependent nitrogenase activity, and its nitrogenase system was sensitive to oxygen and fixed nitrogen in the medium.

  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. Anion-tunable control of thermal Z→E isomerisation in basic azobenzene receptors.

    Science.gov (United States)

    Dąbrowa, Kajetan; Niedbała, Patryk; Jurczak, Janusz

    2014-12-25

    Herein, we report that thermal Z→E isomerisation of simple azobenzene urea derivatives is selectively and predictably controlled by anion binding. The rate of this process depends strictly on the anion concentration and its binding affinity to the Z-isomer of the azobenzene host, i.e. increased rate constants are observed for higher anion concentration as well as for more strongly bound guests. The origin of this phenomenon is attributed to the electron density transfer from the anion to the host π-system, resulting in increased repulsion between the lone electron pairs in the N=N bond.

  12. Reversible photoswitching of azobenzene-based monolayers physisorbed on a mica surface.

    Science.gov (United States)

    El Garah, Mohamed; Palmino, Frank; Cherioux, Frederic

    2010-01-19

    The formation of compact and large-scale self-assembled monolayers (SAMs) adsorbed on a mica surface has been achieved by insertion of alkyl chains on azobenzene derivatives, leading to strong intermolecular van der Waals interactions and hydrogen bonding. The reversible photoswitching of monolayers was investigated by monitoring the variation of the thickness of the SAMs during the cis-trans isomerization of the azobenzene cores with an atomic force microscope (AFM). The absence of covalent bonds between molecules and substrate induces a molecular diffusion which leads to the complete isomerization of the molecules constituting the SAMs.

  13. Experimental and theoretical investigations of spectroscopic properties of azobenzene derivatives in solution.

    Science.gov (United States)

    Zaleśny, Robert; Matczyszyn, Katarzyna; Kaczmarek, Anna; Bartkowiak, Wojciech; Cysewski, Piotr

    2007-07-01

    The UV-Vis spectra of series of polymethylmethacrylate (PMMA) copolymers with attached trans-azobenzene derivatives were measured in 1,1,2-trichloroethane. In order to gain some insight into the recorded spectra, the quantum chemical calculations were performed for the substituted azobenzenes using both configuration interaction with single excitations method (CIS) as well as density functional theory (DFT) with B3LYP and PBE0 functionals. The calculations were performed in solvent. In particular, we found that the PBE0 excitation energies are in very good agreement with the experimental data.

  14. Supramolecular effects in dendritic systems containing photoactive groups

    Directory of Open Access Journals (Sweden)

    GIANLUCA CAMILLO AZZELLINI

    2000-03-01

    Full Text Available In this article are described dendritic structures containing photoactive groups at the surface or in the core. The observed supramolecular effects can be attributed to the nature of the photoactive group and their location in the dendritic architecture. The peripheric azobenzene groups in these dendrimeric compounds can be regarded as single residues that retain the spectroscopic and photochemical properties of free azobenzene moiety. The E and Z forms of higher generation dendrimer, functionalized with azobenzene groups, show different host ability towards eosin dye, suggesting the possibility of using such dendrimer in photocontrolled host-guest systems. The photophysical properties of many dendritic-bipyridine ruthenium complexes have been investigated. Particularly in aerated medium more intense emission and a longer excited-state lifetime are observed as compared to the parent unsubstituted bipyridine ruthenium complexes. These differences can be attributed to a shielding effect towards dioxygen quenching originated by the dendritic branches.

  15. Side Effects

    Science.gov (United States)

    Side effects are problems that occur when cancer treatment affects healthy tissues or organs. Learn about side effects caused by cancer treatment. Know what signs and symptoms to call your doctor about. Learn about treatments for side effects.

  16. Probing the effects of the ester functional group, alkyl side chain length and anions on the bulk nanostructure of ionic liquids: a computational study.

    Science.gov (United States)

    Fakhraee, Mostafa; Gholami, Mohammad Reza

    2016-04-14

    The effects of ester addition on nanostructural properties of biodegradable ILs composed of 1-alkoxycarbonyl-3-alkyl-imidazolium cations ([C1COOCnC1im](+), n = 1, 2, 4) combined with [Br](-), [NO3](-), [BF4](-), [PF6](-), [TfO](-), and [Tf2N](-) were explored by using the molecular dynamics (MD) simulations and quantum theory of atoms in molecules (QTAIM) analysis at 400 K. Various thermodynamic properties of these ILs were extensively computed in our earlier work (Ind. Eng. Chem. Res., 2015, 54, 11678-11700). Nano-scale segregation analysis demonstrates the formation of a small spherical island-like hydrocarbon within the continuous ionic domain for ILs with short alkyl side chain ([C1COOC1C1im]), and a sponge-like nanostructure for the compound with long alkyl side chain ([C1COOC4C1im]). Ester-functionalized ILs with ethyl side chain ([C1COOC2C1im]) are the turning point between two different morphologies. Non-polar channels were observed for [C1COOC4C1im] ILs composed of smaller anions such as [Br] and [NO3], whereas clustering organization was found for the other anions. Formation of the spherical micelle-like nanostructure was seen for lengthened cations. Finally, the incorporation of an ester group into the alkyl side chain of the cation leads to stronger segregation between charged and uncharged networks, which consequently increased the possibility of self-assembly and micelle formation.

  17. Effect of Side Chain Functional Group on Interactions in Ionic Liquid Systems: Insights from Infinite Dilution Thermodynamic Data.

    Science.gov (United States)

    Paduszyński, Kamil; Królikowska, Marta

    2017-11-02

    Measurements of infinite dilution activity coefficients of 48 molecular solutes (including alkanes, alkenes, alkynes, aromatics, ethers, alcohols, water, ketones, pyridine, thiophene, acetonitrile, and 1-nitropropane) in two ionic liquids (ILs), namely, 1-(2-hydroxyethyl)-3-methylimidazolium dicyanamide and 1-(2-chloroethyl)-3-methylimidazolium dicyanamide, are reported in the temperature range from T = 308.15 to 358.15 K. Comparative analysis of an effect of OH/Cl substitution of terminal carbon in side chains of imidazolium cations is presented and discussed in terms of different types of intermolecular forces acting between ILs and solutes. The new data also are confronted to those published previously for a "plain" counterpart of the studied ILs, namely, 1-ethyl-3-methylimidazolium dicyanamide. Infinite dilution capacity and selectivity of the studied ILs are presented to evaluate them as separating agents in extraction of aromatics from alkanes and sulfur compounds from alkanes. Three modeling approaches, namely, linear solvation energy relationship (LSER), regular solution theory, and conductor-like screening model for real solvents (COSMO-RS), are tested for their capabilities of capturing the substitution effects detected experimentally.

  18. Synthesis and characterization of thermosensitive poly(organophosphazenes) with methoxy-poly(ethylene glycol) and alkylamines as side groups

    International Nuclear Information System (INIS)

    Lee, Bae Hoon; Song, Soo Chang; Lee, Young Moo; Sohn, Youn Soo

    2002-01-01

    Thermosensitive poly(organophosphazenes) bearing methoxy-poly(ethylene glycon) (MPEG) and alkylamine as substituents have been synthesized and characterized by elemental analysis, NMR spectroscopy, GPC, and DSC. All the polymers exhibited crystallinity, which was probably induced by the MPEG side chain of the polymers. All the polymers exhibited the lower critical solution temperature (LCSTs) in the range of 28 to 94 .deg. C depending on several factors such as mole ratio of the substituents, kinds of PEG and alkylamines. The higher content of MPEG and shorter chain length of alkylamines of the polymers afforded the higher LCST. The LCSTs of the polymers exhibited almost concentration-independent behavior in the range of 3-30 wt % of the polymers in aqueous solutions. The polymers showed the higher LCSTs in the acidic solutions than in the neutral and basic solutions. The ionic strength of the polymer solution affected the LCST,which decreased with increased NaCl concentration. The polymer bearing almost equimolar substituents with the -N-P-N unit has shown the LCST more sensitive to NaCl and pH than that with the -N-P-O- unit. The polymers were found to degrade in acidic solution but be very stable in alkali solution as well as in the buffer solution of pH 7.4

  19. 10,000 optical write, read, and erase cycles in an azobenzene sidechain liquid-crystalline polyester

    DEFF Research Database (Denmark)

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

    1996-01-01

    We show far what is believed to he the first time that it is possible tu generate 10,000 rapid write, read, and erase cycles optically in an azobenzene sidechain liquid-crystalline polyester. We do this by exposing the film alternately to visible light from an argon laser at 488 nm and ultraviolet...... light from a krypton laser at 351 nm. The efficiency of the system shows several exponential decays, presumably associated ci with the azobenzene chromophores' aligning out of the plane of the film and the lifetime of the cis state of the azobenzene. A local temperature increase may also play a role...

  20. H-aggregation of azobenzene-substituted amphiphiles in vesicular membranes

    NARCIS (Netherlands)

    Kuiper, JM; Engberts, JBFN

    2004-01-01

    Photochemical switching has been studied of double-tailed phosphate amphiphiles containing azobenzene units in both tails in aqueous vesicular dispersions and in mixed vesicular systems with 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). Since the ease of switching depends on the strength of the

  1. Photosensitive Cationic Azobenzene Surfactants: Thermodynamics of Hydration and the Complex Formation with Poly(methacrylic acid).

    Science.gov (United States)

    Montagna, Maria; Guskova, Olga

    2018-01-09

    In this computational work, we investigate the photosensitive cationic surfactants with the trimethylammonium or polyamine hydrophilic head and the azobenzene-containing hydrophobic tail. The azobenzene-based molecules are known to undergo a reversible trans-cis-trans isomerization reaction when subjected to UV-visible light irradiation. Combining the density functional theory and the all-atom molecular dynamics simulations, the structural and the hydration properties of the trans- and the cis-isomers and their interaction with the oppositely charged poly(methacrylic acid) in aqueous solution are investigated. We establish and quantify the correlations of the molecular structure and the isomerization state of the surfactants and their hydrophilicity/hydrophobicity and the self-assembling altered by light. For this reason, we compare the hydration free energies of the trans- and the cis-isomers. Moreover, the investigations of the interaction strength between the azobenzene molecules and the polyanion provide additional elucidations of the recent experimental and theoretical studies on the light triggered reversible deformation behavior of the microgels and the polymer brushes loaded with azobenzene surfactants.

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

    Science.gov (United States)

    2017-12-06

    5) in acetic acid yielded 6, a protected precursor containing two azobenzene units. Finally, the azoCBODA monomer (7) was obtained by deprotection of...Bunsenges. Phys. Chem. 1980, 84, 680−690. (6) Eisenbach, C. D. Isomerization of aromatic azo chromophores in poly( ethyl acrylate) networks and

  3. Submolecular Plasticization Induced by Photons in Azobenzene Materials.

    Science.gov (United States)

    Vapaavuori, Jaana; Laventure, Audrey; Bazuin, C Geraldine; Lebel, Olivier; Pellerin, Christian

    2015-10-28

    We demonstrate experimentally for the first time that the illumination of azobenzene derivatives leads to changes in molecular environment similar to those observed on heating but that are highly heterogeneous at the submolecular scale. This localized photoplasticization, which can be associated with a free volume gradient, helps to understand the puzzling phenomenon of photoinduced macroscopic material flow and photoexpansion upon illumination far below the glass transition temperature (T(g)). The findings stem from the correlation of infrared (IR) spectral band shifts measured upon illumination with those measured at controlled temperatures for two amorphous DR1-functionalized azo derivatives, a polymer, pDR1A, and a molecular glass, gDR1. This new approach reveals that IR spectroscopy can be used as an efficient label-free molecular-scale thermometer that allows the assignment of an effective temperature (T(eff)) to each moiety in these compounds when irradiated. While no band shift is observed upon illumination for the vibrational modes assigned to backbone moieties of pDR1A and gDR1 and a small band shift is found for the spacer moiety, dramatic band shifts are recorded for the azo moiety, corresponding to an increase in T(eff) of up to nearly 200 °C and a molecular environment that is equivalent to thermal heating well above the bulk T(g) of the material. An irradiated azo-containing material thus combines characteristic properties of amorphous materials both below and above its bulk T(g). The direct measurement of T(eff) is a powerful probe of the local environment at the submolecular scale, paving the way toward better rationalization of photoexpansion and the athermal malleability of azo-containing materials upon illumination below their T(g).

  4. Synthesis of novel vitamin K derivatives with alkylated phenyl groups introduced at the ω-terminal side chain and evaluation of their neural differentiation activities.

    Science.gov (United States)

    Sakane, Rie; Kimura, Kimito; Hirota, Yoshihisa; Ishizawa, Michiyasu; Takagi, Yuta; Wada, Akimori; Kuwahara, Shigefumi; Makishima, Makoto; Suhara, Yoshitomo

    2017-11-01

    Vitamin K is an essential cofactor of γ-glutamylcarboxylase as related to blood coagulation and bone formation. Menaquinone-4, one of the vitamin K homologues, is biosynthesized in the body and has various biological activities such as being a ligand for steroid and xenobiotic receptors, protection of neuronal cells from oxidative stress, and so on. From this background, we focused on the role of menaquinone in the differentiation activity of progenitor cells into neuronal cells and we synthesized novel vitamin K derivatives with modification of the ω-terminal side chain. We report here new vitamin K analogues, which introduced an alkylated phenyl group at the ω-terminal side chain. These compounds exhibited potent differentiation activity as compared to control. Copyright © 2017 The Author(s). Published by Elsevier Ltd.. All rights reserved.

  5. Thermal properties of some small peptides (N-acetyl-amino acid-N′-methylamides) with non-polar side groups

    International Nuclear Information System (INIS)

    Badea, Elena; Della Gatta, Giuseppe; Pałecz, Bartłomiej

    2014-01-01

    Highlights: • T fus and Δ fus H m of methylamides of N-acetyl substituted non-polar amino acids were measured. • T fus and Δ fus H m increased as a function of the molar mass of the alkyl side chains. • DL racemates showed T fus of about 40 °C lower than those of the corresponding pure L enantiomers. • Ideal solubility of solids at T = 298.15 K was estimated based on their T fus and Δ fus S m . - Abstract: Temperatures and molar enthalpies of fusion of a series of uncharged small peptides, namely the methylamides of N-acetyl substituted glycine, α-amino-butyric acid, alanine, valine, norvaline, leucine, isoleucine, norleucine, and proline, were measured by differential scanning calorimetry (d.s.c.), and molar entropies of fusion were derived. Both L- and DL-compunds were taken into account for the chiral molecules. No solid-to-solid transitions were detected from room temperature to fusion except for N-acetyl-N′-methyl alaninamide. Comparisons were made with the values for the N-acetyl amides of the corresponding amino acids previously reported. Both L enantiomers and DL racemates of α-aminobutyric acid, alanine, valine and isoleucine methylamides displayed temperatures of fusion sharply increasing as a function of molar mass, whereas much lower values, in countertendency with their molar mass increase, were found for proline and leucine methylamides. The racemic DL crystals showed temperatures of fusion of about 40 °C lower than those of the corresponding pure L enantiomers, except for proline and leucine derivatives. The enthalpies and entropies of fusion also varied as a function of molar mass following a similar trend with that of temperatures of fusion, except for alanine derivatives which showed lower values than expected. The values of ideal solubility of solids at T = 298.15 K were estimated based on their temperatures and molar entropies of fusion. Results were discussed with reference to the packing patterns based on hydrogen bonding and

  6. 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.

  7. Preparation and Characterization of Binary Organogels via Some Azobenzene Amino Derivatives and Different Fatty Acids: Self-Assembly and Nanostructures

    OpenAIRE

    Haiying Guo; Tifeng Jiao; Xihai Shen; Qingrui Zhang; Adan Li; Faming Gao

    2014-01-01

    In present work the gelation behaviors of binary organogels composed of azobenzene amino derivatives and fatty acids with different alkyl chains in various organic solvents were designed and investigated. Their gelation behaviors in 20 solvents were tested as new binary organic gelators. It showed that the length of alkyl substituent chains and azobenzene segment have played a crucial role in the gelation behavior of all gelator mixtures in various organic solvents. Longer alkyl chains in mol...

  8. Photoreversible switching of the lower critical solution temperature in a photoresponsive host-guest system of pillar[6]arene with triethylene oxide substituents and an azobenzene derivative.

    Science.gov (United States)

    Ogoshi, Tomoki; Kida, Kanako; Yamagishi, Tada-aki

    2012-12-12

    A new water-soluble thermoresponsive pillar[6]arene with triethylene oxide groups was synthesized. The pillar[6]arene showed lower critical solution temperature behavior in aqueous solution. Its clouding point was photoreversibly switched based on a photoresponsive host-guest system. The trans form of an azobenzene guest formed a stable 1:1 complex with the pillar[6]arene. Complexation increased the clouding point. Irradiation with UV light induced a conformation change for the azobenzene guest from the trans to cis form, and dethreading occurred because of a size mismatch between the cis form and the pillar[6]arene cavity. This dethreading decreased the clouding point. The photoresponsive host-guest system was reversible, and the clouding point could be switched by alternating irradiation with UV or visible light. We demonstrated photoresponsive reversible clear-to-turbid and turbid-to-clear transitions for the solution based on the reversible switching of the clouding point using the photosensitive host-guest system.

  9. A DFT study on photoinduced surface catalytic coupling reactions on nanostructured silver: selective formation of azobenzene derivatives from para-substituted nitrobenzene and aniline.

    Science.gov (United States)

    Zhao, Liu-Bin; Huang, Yi-Fan; Liu, Xiu-Min; Anema, Jason R; Wu, De-Yin; Ren, Bin; Tian, Zhong-Qun

    2012-10-05

    We propose that aromatic nitro and amine compounds undergo photochemical reductive and oxidative coupling, respectively, to specifically produce azobenzene derivatives which exhibit characteristic Raman signals related to the azo group. A photoinduced charge transfer model is presented to explain the transformations observed in para-substituted ArNO(2) and ArNH(2) on nanostructured silver due to the surface plasmon resonance effect. Theoretical calculations show that the initial reaction takes place through excitation of an electron from the filled level of silver to the lowest unoccupied molecular orbital (LUMO) of an adsorbed ArNO(2) molecule, and from the highest occupied molecular orbital (HOMO) of an adsorbed ArNH(2) molecule to the unoccupied level of silver, during irradiation with visible light. The para-substituted ArNO(2)(-)˙ and ArNH(2)(+)˙ surface species react further to produce the azobenzene derivatives. Our results may provide a new strategy for the syntheses of aromatic azo dyes from aromatic nitro and amine compounds based on the use of nanostructured silver as a catalyst.

  10. 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.

  11. Virulence Role of the GlcNAc Side Chain of the Lancefield Cell Wall Carbohydrate Antigen in Non-M1-Serotype Group A Streptococcus

    Directory of Open Access Journals (Sweden)

    Anna Henningham

    2018-01-01

    Full Text Available Classification of streptococci is based upon expression of unique cell wall carbohydrate antigens. All serotypes of group A Streptococcus (GAS; Streptococcus pyogenes, a leading cause of infection-related mortality worldwide, express the group A carbohydrate (GAC. GAC, the classical Lancefield antigen, is comprised of a polyrhamnose backbone with N-acetylglucosamine (GlcNAc side chains. The immunodominant GlcNAc epitope of GAC is the basis of all rapid diagnostic testing for GAS infection. We previously identified the 12-gene GAC biosynthesis gene cluster and determined that the glycosyltransferase GacI was required for addition of the GlcNAc side chain to the polyrhamnose core. Loss of the GAC GlcNAc epitope in serotype M1 GAS resulted in attenuated virulence in two animal infection models and increased GAS sensitivity to killing by whole human blood, serum, neutrophils, and antimicrobial peptides. Here, we report that the GAC biosynthesis gene cluster is ubiquitous among 520 GAS isolates from global sources, representing 105 GAS emm serotypes. Isogenic ΔgacI mutants were constructed in M2, M3, M4, M28, and M89 backgrounds and displayed an array of phenotypes in susceptibility to killing by whole human blood, baby rabbit serum, human platelet releasate, human neutrophils, and antimicrobial peptide LL-37. The contribution of the GlcNAc side chain to GAS survival in vivo also varied by strain, demonstrating that it is not a prerequisite for virulence in the murine infection model. Thus, the relative contribution of GAC to virulence in non-M1 serotypes appears to depend on the quorum of other virulence factors that each strain possesses.

  12. Synthesis of MOF having hydroxyl functional side groups and optimization of activation process for the maximization of its BET surface area

    International Nuclear Information System (INIS)

    Kim, Jongsik; Kim, Dong Ok; Kim, Dong Wook; Sagong, Kil

    2013-01-01

    To accomplish the postsynthetic modification of MOF with organic-metal precursors (OMPs) described in our previous researches more efficiently, synthesis of MOF (HCC-2) possessing relatively larger pore size as well as higher number of hydroxyl functional side groups per its base unit than those of HCC-1 has been successfully conducted via adopting 1,4-di-(4-carboxy-2,6-dihydroxyphenyl)benzene as an organic ligand and Zn(NO 3 ) 2 ·6H 2 O as a metal source, respectively. Also, optimization about the Activation process of HCC-2 was performed to maximize its BET (Brunauer–Emmett–Teller) surface area which was proved to be proportional to the number of exposed active sites on which its postsynthetic modification occurred. However, Activation process having been validated to be so effective with the acquirement of highly-purified HCC-1 (CO 2 supercritical drying step followed by vacuum drying step) was less satisfactory with the case of HCC-2. This might be attributed to relatively higher hydrophilicity and bulkier molecular structure of organic ligand of HCC-2. However, it was readily settled by simple modification of above Activation process. Moreover, indispensable residues composed of both DMF and its thermally degraded derivatives which were chemically attached via coordination bond with hydroxyl functionalities even after Activation process III might enable their H 2 adsorption properties to be seriously debased compared to that of IRMOF-16 having no hydroxyl functionalities. - Graphical abstract: Synthesis of new-structured MOF (HCC-2) simultaneously possessing relatively larger pore size as well as higher number of hydroxyl functional side groups per its base unit at the same time than those of HCC-1 has been performed via adopting 1,4-di-(4-carboxy-2,6-dihydroxyphenyl)benzene as an organic ligand and Zn(NO 3 ) 2 ·6H 2 O as a metal source, respectively. Also, the optimization of activation process for HCC-2 was conducted to maximize its BET surface area

  13. 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.

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

    DEFF Research Database (Denmark)

    Nedelchev, L; Nikolova, L; Todorov, T

    2001-01-01

    We investigate light propagation through azobenzene-containing polymers with photoinduced chiral structures. The structures have large pitch but the Mauguin condition is not fulfilled. The eigenmodes are shown to be elliptical and their ellipticity is determined by the ellipticity e(o) of the exc......We investigate light propagation through azobenzene-containing polymers with photoinduced chiral structures. The structures have large pitch but the Mauguin condition is not fulfilled. The eigenmodes are shown to be elliptical and their ellipticity is determined by the ellipticity e......(o) of the exciting light. In amorphous azopolymers, light induces a macroscopic chiral structure comprising the whole illuminated region. The pitch depends on the value of e(o): no chirality is induced if e(o) = 1 (circular polarization). In liquid-crystalline azopolymers circularly polarized light induces...... the formation of many microscopic spirals, which makes the material equivalent to the classical optically active media....

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

    Science.gov (United States)

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

    2015-11-05

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

  16. Photo-Responsive Soft Ionic Crystals: Ion-Pairing Assemblies of Azobenzene Carboxylates.

    Science.gov (United States)

    Yamakado, Ryohei; Hara, Mitsuo; Nagano, Shusaku; Seki, Takahiro; Maeda, Hiromitsu

    2017-07-12

    This report delineates the design and synthesis of negatively charged azobenzene derivatives that form photo-responsive ion-pairing assemblies. The azobenzene carboxylates possessing aliphatic chains were prepared as photo-responsive anions that promote the formation of ion-pairing dimension-controlled assemblies, including mesophases, when used in conjunction with a tetrabutylammonium (TBA) cation. The photo-responsive properties of the ion pairs and the precursory carboxylic acids in the bulk state were examined by polarized optical microscopy (POM) and X-ray diffraction (XRD), demonstrating that liquid crystal (LC)-liquid and crystal-liquid phase transitions occurred, depending on the number and lengths of the aliphatic chains of each assembly. An ion pair exhibited photo-induced crystal-crystal phase transitions upon switching between two irradiation wavelengths (365/436 nm). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Interactions of Lysozyme and Azobenzene Derivatives in the Solution and on a Surface

    Science.gov (United States)

    Wei, Tao; Shing, Katherine

    2015-03-01

    The reversible isomerization of the azobenzene and its derivatives can control protein structure in an aqueous environment with the alternation of visible and UV lights for very promising applications in drug delivery. However, an atomistic description of Azo-molecules and protein amino acid residues is still lacking. In this study we performed atomistic molecular dynamics simulation to study the interactions between a lysozyme molecule and the Azobenzene derivative (in the bulk solution and grafted on the Silica surfaces). Protein structural arrangements (i.e., the shape and secondary structures) and its mobility, as a function of tran/cis ratio in the bulk solution and on the self-assembling monolayer surface's density and morphology, are systematically investigated.

  18. Collisions induced dissociation and Ab initio study of azobenzene derivatives bond structure and electronic configuration

    Science.gov (United States)

    Rezaee, Mohammadreza; Compton, Robert

    2015-05-01

    Collision induced dissociation (CID) and ab initio calculations were utilized to study a few derivatives of azobenzene molecule and their product ions. High level computational methods along with large basis set size yield values in close agreement with the experimental results. Möller-Plesset and coupled-cluster theory including perturbative triple excitations, CCSD(T), method were performed to obtain a high accuracy estimation of the bond dissociation energy value. The electron affinities have been studied experimentally using the photoelectron spectroscopy method as well as theoretically using ab inito calculations. For the trans-2,2',6,6' tetra-fluoro azobenzene the bond dissociation has been experimentally determined to be 1.88 eV and the vertical detachment energy is 1.78 eV.

  19. Photonic manipulation of topological defects in liquid-crystal emulsions doped with azobenzene derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Yamamoto, Takahiro [Nanotechnology Research Institute, National Institute of Advanced Industrial Science and Technology, 1-1-1 Umezono, Tsukuba 305-8568, Ibaraki (Japan) and Liquid-Crystal Nano-System Project, ERATO/SORST, Japan Science and Technology, Agency, 5-9-9 Tokodai, Tsukuba 300-2635, Ibaraki (Japan)]. E-mail: takahiro.yamamoto@aist.go.jp; Tabe, Yuka [Nanotechnology Research Institute, National Institute of Advanced Industrial Science and Technology, 1-1-1 Umezono, Tsukuba 305-8568, Ibaraki (Japan); Liquid-Crystal Nano-System Project, ERATO/SORST, Japan Science and Technology, Agency, 5-9-9 Tokodai, Tsukuba 300-2635, Ibaraki (Japan); Department of Applied Physics, School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjyuku, 169-8555, Tokyo (Japan); Yokoyama, Hiroshi [Nanotechnology Research Institute, National Institute of Advanced Industrial Science and Technology, 1-1-1 Umezono, Tsukuba 305-8568, Ibaraki (Japan); Liquid-Crystal Nano-System Project, ERATO/SORST, Japan Science and Technology, Agency, 5-9-9 Tokodai, Tsukuba 300-2635, Ibaraki (Japan)

    2006-06-19

    By modulating liquid-crystal alignment on a colloidal sphere, we successfully manipulated topological defects in glycerol-droplet/liquid-crystal emulsions doped with amphiphilic azobenzene derivatives. At an initial state, a disclination loop (Saturn ring) could be observed around the droplet, in which the azobenzene molecules should adsorb onto the droplet and liquid crystal molecules align normally to the surface of the droplet. On irradiation with ultra-violet light ({lambda} = 365 nm), the disclination loop was unfastened and transformed into two point defects called boojums. This should be attributed to the alignment change of the liquid crystal molecules from normal to planar arrangement triggered by trans-to-cis photoisomerization of the adsorbed azo-dyes. On irradiation with visible light causing cis-to-trans photoisomerization ({lambda} = 435 nm), the boojums went back to the Saturn ring reversibly.

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

    Science.gov (United States)

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

    2014-09-01

    The synthesis, supramolecular complexation, and switching of new bifunctional azobenzene-oligoglycerol conjugates in different environments is reported. Through the formation of host-guest complexes with surface immobilized β-cyclodextrin receptors, the bifunctional switches were coupled to gold surfaces. The isomerization of the amphiphilic azobenzene derivatives was examined in solution, on gold nanoparticles, and on planar gold surfaces. The wettability of functionalized gold surfaces can be reversibly switched under light-illumination with two different wavelengths. Besides the photoisomerization processes and concomitant effects on functionality, the thermal cis to trans isomerization of the conjugates and their complexes was monitored. Thermal half-lives of the cis isomers were calculated for different environments. Surprisingly, the half-lives on gold nanoparticles were significantly smaller compared to planar gold surfaces. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Synthesis, Self-Assembly and Photoresponsive Liquid Crystals Based on Azobenzene Derivatives.

    Science.gov (United States)

    Wang, Hongyan; Han, Yi; Yuan, Wei; Wu, Mengjiao; Chen, Yulan

    2018-02-17

    A new class of rod-coil-rod molecules with an azobenzene core were synthesized. They were found to form robust organogels in several kinds of organic solvents. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), FT-IR spectroscopy, UV-vis absorption spectroscopy, 1H NMR, and X-ray diffraction (XRD) revealed that in these organogels, the molecules self-assembled into nanofiber network with an H-type aggregation mode under the joint effect of Pi-Pi stacking, intermolecular hydrogen bonding, and van der Waals forces. Interestingly, the incorporation of the azobenzene mesogene into the rigid core led to photo-isomerizable liquid crystal materials, which exhibited fast responsiveness to light and temperature, along with the trans-cis transition stimulated by UV light and heating. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. The role of water and K + ion in the charge transfer between PO4- groups of DNA and the lysine + and arginine + side chains of histone proteins

    Science.gov (United States)

    Bende, A.; Bogár, F.; Ladik, J.

    2008-09-01

    We have calculated the charge transfer (CT) between the PO4- group of DNA and the lysine (Lys) and arginine (Arg) positive side chains of histones in presence of water and K + ions. The calculations were performed at the HF + MP2 level, using the TZVP basis set. The calculations were corrected for basis set superposition error and besides Mulliken's population analysis we have introduced the - for charged systems more reliable - natural population analysis. The results show that the bare PO4--Lys and the PO4--Arg interactions become weaker, mainly, due to the presence of the K + ion. We have found 0.067 e CT for Lys and 0.050 e for Arg.

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

    DEFF Research Database (Denmark)

    Bernardos, Andrea; Mondragón, Laura; Javakhishvili, Irakli

    2012-01-01

    The synthesis and characterisation of new capped silica mesoporous nanoparticles for on‐command delivery applications is reported. Functional capped hybrid systems consist of MCM‐41 nanoparticles functionalised on the external surface with polyesters bearing azobenzene derivatives and rhodamine B...... with the cytotoxic drug camptothecin (CPT‐PAzo6‐S). Following cell internalisation and lysosome resident enzyme‐dependent gate opening, CPT‐PAzo6‐S induced CPT‐dependent cell death in HeLa cells....

  4. Comparative analysis of cleavable azobenzene-based affinity tags for bioorthogonal chemical proteomics.

    Science.gov (United States)

    Yang, Yu-Ying; Grammel, Markus; Raghavan, Anuradha S; Charron, Guillaume; Hang, Howard C

    2010-11-24

    The advances in bioorthogonal ligation methods have provided new opportunities for proteomic analysis of newly synthesized proteins, posttranslational modifications, and specific enzyme families using azide/alkyne-functionalized chemical reporters and activity-based probes. Efficient enrichment and elution of azide/alkyne-labeled proteins with selectively cleavable affinity tags are essential for protein identification and quantification applications. Here, we report the synthesis and comparative analysis of Na₂S₂O₄-cleavable azobenzene-based affinity tags for bioorthogonal chemical proteomics. We demonstrated that ortho-hydroxyl substituent is required for efficient azobenzene-bond cleavage and show that these cleavable affinity tags can be used to identify newly synthesized proteins in bacteria targeted by amino acid chemical reporters as well as their sites of modification on endogenously expressed proteins. The azobenzene-based affinity tags are compatible with in-gel, in-solution, and on-bead enrichment strategies and should afford useful tools for diverse bioorthogonal proteomic applications. Copyright © 2010 Elsevier Ltd. All rights reserved.

  5. Smectites intercalated with azobenzene and aminoazobenzene: Structure changes at nanoscale induced by UV light

    Science.gov (United States)

    Koteja, Anna; Szczerba, Marek; Matusik, Jakub

    2017-12-01

    The photoactive azobenzenes were intercalated into montmorillonite and beidellite in order to obtain a functional material responsive to UV radiation. The smectite modification involved two steps: (1) intercalation with alkylammonium salts, differing in alkyl chain length, and (2) co-intercalation with azobenzene or aminoazobenzene. The structure and chemistry of the obtained materials were thoroughly characterize with the means of XRD, FTIR, DTA/TG, UV-Vis methods and CHN elemental analysis. The mechanisms interpretation was supported with the molecular dynamics simulations. Photoresponse of the obtained materials was monitored through the observation of the basal spacing shifts upon UV radiation. The results proved that both the type of alkylammonium salt and the host mineral influenced heavily the efficiency of subsequent azobenzene intercalation as well as its photoactive behaviour. The evident and regular photoinduced basal spacing shifts were visible when the density of intercalated salts was low. This was achieved in the BId derivatives due to the low layer charge of the mineral. Also the shorter alkyl chain of the co-intercalated salt promoted larger photoresponses.

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

    Science.gov (United States)

    Bronner, Christopher; Tegeder, Petra

    2014-05-01

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

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

    Science.gov (United States)

    Floß, Gereon; Granucci, Giovanni; Saalfrank, Peter

    2012-12-01

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

  8. Synthesis and characterization of dicyclopalladated complexes of azobenzene derivatives by experimental and computational methods.

    Science.gov (United States)

    Babić, Darko; Curić, Manda; Molcanov, Kresimir; Ilc, Gregor; Plavec, Janez

    2008-11-17

    A series of doubly cyclopalladated complexes of azobenzene and its unsymmetrical substituted derivatives, namely, {LPdCl(mu-AZB)LPdCl}, where AZB is azobenzene, 4-methylazobenzene, 4-aminoazobenzene, or 4-(dimethylamino)-4'-nitroazobenzene, while L is N,N-dimethylformamide, dimethylsulfoxide, or pyridine, have been prepared. Their structural and spectroscopic properties were determined by X-ray diffraction analysis as well as by (1)H NMR, IR, UV-vis, and fluorimetric studies. Experimental results were rationalized by quantum chemical calculations. Crystal structures of several complexes have been resolved, and for the first time, it was demonstrated that the cyclopalladation may take place at the azobenzene aromatic ring having the strong electron-withdrawing substituent at the para position. In all cases, the metalated carbon and N,N-dimethylformamide or dimethylsulfoxide ligands are mutually trans, whereas the pyridine ligands are in the cis arrangement. cis/trans isomerism in the isolated compounds is explained by comparing the calculated energies of isomeric structures. All of the complexes absorb strongly in the visible region, and according to time-dependent density functional theory calculations, most of the absorptions can be attributed to intraligand pi --> pi* or metal-to-ligand charge-transfer transitions. The fluorescence emission was observed for the complexes with 4-aminoazobenzene or 4-(dimethylamino)-4'-nitroazobenzene. The aromaticity of palladacycles is evaluated by several aromaticity indices and related to relevant experimental findings.

  9. Electro-optic side-chain polyimide system with large optical nonlinearity and high thermal stability

    Science.gov (United States)

    Sotoyama, Wataru; Tatsuura, Satoshi; Yoshimura, Tetsuzo

    1994-04-01

    We report electro-optic (EO) efficiency and thermal stability of a poled polyimide system with nonlinear optical dyes as side chains. The side-chain polyimide system is synthesized from a dianhydride containing azobenzene dye and a diamine. The dye in the polymer is chemically stable for temperatures below 250 °C. The polymer can be poled simultaneously with or after imidization of the polyamic acid. Our sample poled after imidization shows a large EO coefficient (r33=10.8 pm/V at λ=1.3 μm) and long-term thermal stability at 120 °C.

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

    DEFF Research Database (Denmark)

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

    2000-01-01

    Electronic excitation energies of 16 azobenzene dyes have been calculated by ab initio methods within the second-order polarization propagator approximation (SOPPA). Good agreement with expriment is found for the lowest singlet and triplet states for both the trans- and cis-azobenzene molecules. ...... candidates for azo components used in materials for data storage....

  11. Photoinduced Trans-to-cis Phase Transition of Polycrystalline Azobenzene at Low Irradiance Occurs in the Solid State.

    Science.gov (United States)

    Bhattacharjee, Ujjal; Freppon, Daniel; Men, Long; Vela, Javier; Smith, Emily A; Petrich, Jacob W

    2017-09-20

    The ability to produce large-scale, reversible structural changes in a variety of materials by photoexcitation of a wide variety of azobenzene derivatives has been recognized for almost two decades. Because photoexcitation of trans-azobenzene produces the cis-isomer in solution, it has generally been inferred that the macroscopic structural changes occurring in materials are also initiated by a similar large-amplitude trans-to-cis isomerization. This work provides the first demonstration that a trans-to-cis photoisomerization occurs in polycrystalline azobenzene, and is consistent with the previously hypothesized nature of the trigger in the photoactuated mechanisms of the materials in question. It is also demonstrated that under low irradiance, trans-to-cis isomerization occurs in the solid (not via a pre-melted phase); and the presence of the cis-isomer thus lowers the melting point of the sample, providing a liquid phase. A variety of experimental techniques were employed, including X-ray diffraction measurements of polycrystalline azobenzene during exposure to laser irradiation and fluorescence measurements of the solid sample. A practical consequence of this work is that it establishes trans-azobenzene as an easily obtainable and well-defined control for monitoring photoinduced structural changes in X-ray diffraction experiments, using easily accessible laser wavelengths. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. A novel branched side-chain-type sulfonated polyimide membrane with flexible sulfoalkyl pendants and trifluoromethyl groups for vanadium redox flow batteries

    Science.gov (United States)

    Li, Jinchao; Liu, Suqin; He, Zhen; Zhou, Zhi

    2017-04-01

    A novel branched side-chain-type sulfonated polyimide (6F-s-bSPI) membrane with accessible branching agents of melamine, hydrophobic trifluoromethyl groups (sbnd CF3), and flexible sulfoalkyl pendants is prepared by a high-temperature polycondensation and post-sulfonation method for use in vanadium redox flow batteries (VRFBs). The chemical structure of the 6F-s-bSPI membrane is confirmed by ATR-FTIR and 1H NMR spectra. The physico-chemical properties of the as-prepared 6F-s-bSPI membrane are systematically investigated and found to be strongly related to the specially designed structure. The 6F-s-bSPI membrane offers a reduced cost and possesses a significantly lowered vanadium ion permeability (1.18 × 10-7 cm2 min-1) compared to the linear SPI (2.25 × 10-7 cm2 min-1) and commercial Nafion 115 (1.36 × 10-6 cm2 min-1) membranes, prolonging the self-discharge duration of the VRFBs. In addition, the VRFB assembled with a 6F-s-bSPI membrane shows higher coulombic (98.3%-99.7%) and energy efficiencies (88.4%-66.12%) than that with a SPI or Nafion 115 membrane under current densities ranging from 20 to 100 mA cm-2. Moreover, the VRFB with a 6F-s-bSPI membrane delivers a stable cycling performance over 100 cycles with no decline in coulombic and energy efficiencies. These results show that the branched side-chain-type structure is a promising design to prepare excellent proton conductive membranes.

  13. 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.

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

    Science.gov (United States)

    Wershaw, R L; Rutherford, D W; Rostad, C E; Garbarino, J R; Ferrer, Imma; Kennedy, K R; Momplaisir, Georges-Marie; Grange, Andrew

    2003-05-01

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

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

    Science.gov (United States)

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

    2003-01-01

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

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

    Science.gov (United States)

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

    2015-04-17

    In the present study, we demonstrate photoregulation of gene expression in a cell-free translation system from a T7 promoter containing two azobenzene derivatives at specific positions. As photoswitches, we prepared azobenzene-4'-carboxlyic acid (Azo) and 2,6-dimethylazobenzene-4'-carboxylic acid (DM-Azo), which were isomerized from trans to cis upon irradiation with UV light (λ azobenzene-4'-carobxylic acid (S-DM-Azo), which were cis-isomerized by irradiation with 400 nm visible light. Expression of green fluorescent protein from a promoter modified with S-Azo or S-DM-Azo could be induced by harmless visible light whereas that from a promoter modified with Azo or DM-Azo was induced only by UV light (340-360 nm). Thus, efficient photoregulation of green fluorescent protein production was achieved in a cell-free translation system with visible light without photodamage.

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

    Science.gov (United States)

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

    2013-01-01

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

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

    Science.gov (United States)

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

    2013-01-01

    The phase transition of a nematic liquid crystal containing a push-pull azobenzene dye could be induced efficiently during irradiation with visible light. The dynamical disorganizing effect of the push-pull azobenzene dye on the liquid crystalline order through its trans-cis-trans photoisomerizaion cycle under visible light was contributed to the efficient phase transition. Then, the effects of light irradiation on the motion of small objects dispersed in the liquid crystals containing the push-pull azobenzene were explored, and the manipulation and assembly of those objects were successfully achieved in the nematic phase but also in the smectic phase. The combination of the photo-controlled dynamical change in the liquid crystalline order and the intrinsic self-assembly property of a liquid crystal is promising for use in technologies that require not only the organization of small objects but also the photo-driving of nano- and micro-sized mechanical materials. PMID:23835605

  19. Dynamics of photoinduced motions in azobenzene grafted polybutadienes

    Czech Academy of Sciences Publication Activity Database

    Mysliwiec, J.; Czajkowski, M.; Miniewicz, A.; Bartkiewicz, S.; Kochalska, Anna; Poláková, Lenka; Sedláková, Zdeňka; Nešpůrek, Stanislav

    2011-01-01

    Roč. 33, č. 9 (2011), s. 1398-1404 ISSN 0925-3467 R&D Projects: GA AV ČR KAN401770651 Institutional research plan: CEZ:AV0Z40500505 Keywords : side-chain liquid crystalline polymers * dynamic holography * photochromism Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 2.023, year: 2011

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

    Science.gov (United States)

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

    2016-06-01

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

  1. Tuning the collective switching behavior of azobenzene/Au hybrid materials: flexible versus rigid azobenzene backbones and Au(111) surfaces versus curved Au nanoparticles.

    Science.gov (United States)

    Liu, Chunyan; Zheng, Dong; Hu, Weigang; Zhu, Qiang; Tian, Ziqi; Zhao, Jun; Zhu, Yan; Ma, Jing

    2017-11-09

    The combination of photo-responsive azobenzene (AB) and biocompatible Au nanomaterials possesses potential applications in diverse fields such as biosensing and thermotherapy. To explore the influence of azobenzene moieties and Au substrates on the collective switching behavior, two different azobenzene derivatives (rigid biphenyl-controlled versus flexible alkoxyl chain-linked) and three different Au substrates (a planar Au(111) surface, curved Au 102 (SR) 44 and Au 25 (SR) 18 clusters) were chosen to form six Au@AB combinations. A reactive molecular dynamics (RMD) model considering both the torsion and inversion path was implemented to simulate the collective photo-induced cis-to-trans switching process of AB monolayers on Au substrates. The major driving force for isomerization is demonstrated to be the torsion of the C-N[double bond, length as m-dash]N-C dihedral angle, in addition to the minor contribution from an inversion pathway. The isomerization process can be divided into the preliminary conformation switching stage and the later relaxation stage, in which a gradual self-organization is observed for 40 ps. The Au substrate affects the packing structure of the AB monolayer, while the choice of different kinds of ABs tunes the intermolecular interaction in the monolayer. Flexible alkoxyl-linked F-AB may achieve much faster conversion on Au clusters than on the surface. For rigid biphenyl-based R-AB anchored on Au nanoparticles (AuNPs), a competitive torsion between the biphenyl and C-N[double bond, length as m-dash]N-C dihedral may delay the C-N[double bond, length as m-dash]N-C dihedral torsion and the following isomerization process. After the R-AB molecules were anchored on the Au(111) surface, the strong π-π stacking between biphenyl units accelerates the collective isomerization process. A curvature-dependent effect is observed for R-AB SAMs on different-sized substrates. The cooperation between functional AB monolayers and the Au substrate

  2. Photo-driven directional motion of droplets on the surface of a liquid crystal doped with photochromic azobenzene: theory

    Energy Technology Data Exchange (ETDEWEB)

    Seki, Kazuhiko; Tachiya, M [National Institute of Advanced Industrial Science and Technology (AIST), AIST Tsukuba Central 5, Higashi 1-1-1, Tsukuba, Ibaraki 305-8565 (Japan)

    2005-12-14

    Recently, photo-driven directional motion of glycerol droplets on the surface of a liquid crystal doped with photochromic azobenzene derivatives has been reported. We present a theoretical model for this phenomenon. The motion of droplets is induced by a gradient in surface tension, which is produced by the combined effect of photo-isomerization and diffusion of surface azobenzenes. The theoretical relation between the surface tension and the surface concentration of cis isomers is proposed. The experimentally observed depletion zone of droplets can be reasonably well explained in terms of diffusion of droplets in the presence of the gradient in the surface tension.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ozols, A; Saharov, D; Kokars, V; Kampars, V; Maleckis, A; Mezinskis, G; Pludons, A, E-mail: aozols@latnet.l [Faculty of Material Science and Applied Chemistry, Riga Technical University, Azenes iela 14/24, LV-1048, Riga (Latvia)

    2010-11-01

    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 {mu}m period and an amplitude of 130 nm have been recorded with 0.88 W/cm{sup 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{sup 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.

  4. Correlation between substituent constants and hyperpolarizabilities for di-substituted trans-azobenzenes.

    Science.gov (United States)

    Lin, Tsung-Yi; Chaudhari, Ajay; Lee, Shyi-Long

    2013-02-01

    Nonlinear optical properties of a series of disubstituted trans-azobenzenes were studied. The structures were fully optimized by B3LYP/6-31+G* and both static polarizabilities and hyperpolarizabilities were then calculated by the derivative method. In order to show the relationships between dipole moments, (hyper)polarizabilities and the structures, three kinds of substituent constants were applied to correlate with both ground state dipole moment and hyperpolarizabilities. Both physical properties have a satisfactory correlation with substituent constants Σσ(+/-) and bond length alternation. Overall, the electronic excitation contribution to the hyperpolarizabilities is rationalized in terms of the two-level model.

  5. Gel formation and photoactive properties of azobenzene-containing polymer in liquid crystal mixture

    Czech Academy of Sciences Publication Activity Database

    Bobrovsky, A.; Shibaev, V.; Hamplová, Věra; Kašpar, Miroslav; Glogarová, Milada

    2010-01-01

    Roč. 288, 14-15 (2010), 1375-1384 ISSN 0303-402X R&D Projects: GA AV ČR IAA100100911; GA AV ČR(CZ) GA202/09/0047; GA MŠk(CZ) OC10006 Grant - others:EU(XE) COST D35 WG 0013-05 Institutional research plan: CEZ:AV0Z10100520 Keywords : gel * azobenzene-containing polymer * photoisomerization * nematic phase Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.443, year: 2010

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

    Directory of Open Access Journals (Sweden)

    Takashi Fukuda

    2012-01-01

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

  7. Evidence of two distinct mechanisms driving photoinduced matter motion in thin films containing azobenzene derivatives.

    Science.gov (United States)

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

    2011-02-17

    Photoinduced matter motion in thin films containing azobenzene derivatives grafted to a polymer backbone is investigated by means of near-field probe microscopy. We evidence the existence of two different photomechanical processes which produce mass transport. One is governed by the light intensity pattern and the other by the light polarization pattern. The intensity-driven mechanism is found to critically depend on the polymer matrix while the polarization-driven mechanism occurs with almost the same efficiency in different materials. Depending on the relationship between the polarization and intensity patterns, the two processes may either compete or cooperate giving rise to a nontrivial directional mass transport process.

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

    Science.gov (United States)

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

    2016-10-01

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

  9. Island formation and manipulation of prochiral azobenzene derivatives on Au(111)

    Science.gov (United States)

    Selvanathan, Sofia; Peters, Maike V.; Hecht, Stefan; Grill, Leonhard

    2012-09-01

    Based on previous work with very similar azobenzene derivatives, this study of para-TBA (2,2‧,5,5‧-tetra-tert-butylazobenzene) molecules aims to identify single intact molecules and investigate their adsorption behavior on a Au(111) surface. The molecules are found to be mobile on the surface at the deposition temperature, leading to highly ordered and enantiomerically pure molecular islands. Voltage pulses between the surface and the tip of a scanning tunneling microscope are used to change the chirality of the adsorbate molecules. On the Cu(111) surface instead, single molecules are found on the terraces, which points to a stronger molecule-substrate interaction.

  10. 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

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

    Science.gov (United States)

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

    2015-10-01

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

  13. 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.

  14. A chemical approach for site-specific identification of NMR signals from protein side-chain NH₃⁺ groups forming intermolecular ion pairs in protein-nucleic acid complexes.

    Science.gov (United States)

    Anderson, Kurtis M; Nguyen, Dan; Esadze, Alexandre; Zandrashvili, Levani; Gorenstein, David G; Iwahara, Junji

    2015-05-01

    Protein-nucleic acid interactions involve intermolecular ion pairs of protein side-chain and DNA or RNA phosphate groups. Using three protein-DNA complexes, we demonstrate that site-specific oxygen-to-sulfur substitution in phosphate groups allows for identification of NMR signals from the protein side-chain NH3 (+) groups forming the intermolecular ion pairs. A characteristic change in their (1)H and (15)N resonances upon this modification (i.e., substitution of phosphate to phosphorodithioate) can represent a signature of an intermolecular ion pair. Hydrogen-bond scalar coupling between protein side-chain (15)N and DNA phosphorodithiaote (31)P nuclei provides direct confirmation of the intermolecular ion pair. The same approach is likely applicable to protein-RNA complexes as well.

  15. A chemical approach for site-specific identification of NMR signals from protein side-chain NH3+ groups forming intermolecular ion pairs in protein–nucleic acid complexes

    International Nuclear Information System (INIS)

    Anderson, Kurtis M.; Nguyen, Dan; Esadze, Alexandre; Zandrashvili, Levani; Gorenstein, David G.; Iwahara, Junji

    2015-01-01

    Protein–nucleic acid interactions involve intermolecular ion pairs of protein side-chain and DNA or RNA phosphate groups. Using three protein–DNA complexes, we demonstrate that site-specific oxygen-to-sulfur substitution in phosphate groups allows for identification of NMR signals from the protein side-chain NH 3 + groups forming the intermolecular ion pairs. A characteristic change in their 1 H and 15 N resonances upon this modification (i.e., substitution of phosphate to phosphorodithioate) can represent a signature of an intermolecular ion pair. Hydrogen-bond scalar coupling between protein side-chain 15 N and DNA phosphorodithiaote 31 P nuclei provides direct confirmation of the intermolecular ion pair. The same approach is likely applicable to protein–RNA complexes as well

  16. A chemical approach for site-specific identification of NMR signals from protein side-chain NH{sub 3}{sup +} groups forming intermolecular ion pairs in protein–nucleic acid complexes

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Kurtis M. [University of Texas Health Science Center at Houston, Department of NanoMedicine and Biomedical Engineering and Institute of Molecular Medicine (United States); Nguyen, Dan; Esadze, Alexandre; Zandrashvili, Levani [University of Texas Medical Branch, Department of Biochemistry and Molecular Biology, Sealy Center for Structural Biology and Molecular Biophysics (United States); Gorenstein, David G. [University of Texas Health Science Center at Houston, Department of NanoMedicine and Biomedical Engineering and Institute of Molecular Medicine (United States); Iwahara, Junji, E-mail: juiwahar@utmb.edu, E-mail: j.iwahara@utmb.edu [University of Texas Medical Branch, Department of Biochemistry and Molecular Biology, Sealy Center for Structural Biology and Molecular Biophysics (United States)

    2015-05-15

    Protein–nucleic acid interactions involve intermolecular ion pairs of protein side-chain and DNA or RNA phosphate groups. Using three protein–DNA complexes, we demonstrate that site-specific oxygen-to-sulfur substitution in phosphate groups allows for identification of NMR signals from the protein side-chain NH{sub 3}{sup +} groups forming the intermolecular ion pairs. A characteristic change in their {sup 1}H and {sup 15}N resonances upon this modification (i.e., substitution of phosphate to phosphorodithioate) can represent a signature of an intermolecular ion pair. Hydrogen-bond scalar coupling between protein side-chain {sup 15}N and DNA phosphorodithiaote {sup 31}P nuclei provides direct confirmation of the intermolecular ion pair. The same approach is likely applicable to protein–RNA complexes as well.

  17. Photo-Reversible Supramolecular Hydrogels Assembled by α-Cyclodextrin and Azobenzene Substituted Poly(acrylic acid)s

    NARCIS (Netherlands)

    Wang, Mingwei; Zhang, Xiaojun; Li, Li; Wang, Junyou; Wang, Jie; Ma, Jun; Yuan, Zhenyu; Lincoln, Stephen F.; Guo, Xuhong

    2016-01-01

    Photo-reversible supramolecular hydrogels based on the mixture of α-cyclodextrin (α-CD) and azobenzene (Azo) substituted poly(acrylic acid) s were prepared. Effects of substitution degree of Azo, polymer concentration and tethered chain length on the reversible sol-gel transition of these

  18. 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...

  19. 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.

  20. 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

  1. Two-dimensional networks of an azobenzene derivative: bi-pyridine mediation and photo regulation

    Science.gov (United States)

    Zhang, Xuemei; Wang, Shuai; Shen, Yongtao; Guo, Yuanyuan; Zeng, Qingdao; Wang, Chen

    2012-07-01

    Two-dimensional photosensitive supramolecular assemblies based on an azobenzene derivative and bi-pyridine are built up and investigated using scanning tunneling microscopy (STM). In order to probe the photo-induced self-assembled behavior of these two molecules, irradiation experiments with different wavelengths are designed and performed. Our STM results show that the constructed H-bonded networks can be reversibly regulated under irradiation with UV light and visible light.Two-dimensional photosensitive supramolecular assemblies based on an azobenzene derivative and bi-pyridine are built up and investigated using scanning tunneling microscopy (STM). In order to probe the photo-induced self-assembled behavior of these two molecules, irradiation experiments with different wavelengths are designed and performed. Our STM results show that the constructed H-bonded networks can be reversibly regulated under irradiation with UV light and visible light. Electronic supplementary information (ESI) available: UV-Vis spectra and additional STM images. See DOI: 10.1039/c2nr31186k

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

    Science.gov (United States)

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

    2016-02-01

    We have investigated the attachment of azobenzene photochromic switches on the modified surface of cadmium sulfide (CdS) quantum dots (QDs). The modification of CdS QDs is done by varying the concentration of the capping agent (mercaptoacetic acid) and NH 3 in order to control the size of the QDs. The X-ray diffraction studies revealed that the crystallite size of CdS QDs ranged from 6 to 10 nm. The azobenzene photochromic derivatives bis(4-hydroxybenzene-1-azo)4,4'(1,1' diphenylmethane) (I) and 4,4'-diazenyldibenzoic acid (II) were synthesized and attached with surface-modified CdS QDs to make fluorophore-photochrome CdS-(I) and CdS-(II) dyad assemblies. Upon UV irradiation, the photochromic compounds (I) and (II) undergo a reversible trans - cis isomerization. The photo-induced trans - cis transformation helps to transfer photo-excited electrons from the conduction band of the CdS QDs to the lowest unoccupied molecular orbital of cis isomer of photochromic compounds (I) and (II). As a result, the fluorescence of CdS-(I) and CdS-(II) dyads is suppressed approximately five times compared to bare CdS QDs. The fluorescence modulation in such systems could help to design luminescent probes for bioimaging applications.

  3. Self-Assembled Monolayers of an Azobenzene Derivative on Silica and Their Interactions with Lysozyme.

    Science.gov (United States)

    Wei, Tao; Sajib, Md Symon Jahan; Samieegohar, Mohammadreza; Ma, Heng; Shing, Katherine

    2015-12-22

    The capability of the photoresponsive isomerization of azobenzene derivatives in self-assembled monolayer (SAM) surfaces to control protein adsorption behavior has very promising applications in antifouling materials and biotechnology. In this study, we performed an atomistic molecular dynamics (MD) simulation in combination with free-energy calculations to study the morphology of azobenzene-terminated SAMs (Azo-SAMs) grafted on a silica substrate and their interactions with lysozyme. Results show that the Azo-SAM surface morphology and the terminal benzene rings' packing are highly correlated with the surface density and the isomer state. Higher surface coverage and the trans-isomer state lead to a more ordered polycrystalline backbone as well as more ordered local packing of benzene rings. On the Azo-SAM surface, water retains a high interfacial diffusivity, whereas the adsorbed lysozyme is found to have extremely low mobility but a relative stable secondary structure. The moderate desorption free energy (∼60 kT) from the trans-Azo-SAM surface was estimated by using both the nonequilibrium-theorem-based Jarzynski's equality and equilibrium umbrella sampling.

  4. 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)

  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. An improved method for separating the kinetics of anisotropic and topographic gratings in side-chain azobenzene polyesters

    DEFF Research Database (Denmark)

    Helgert, M.; Fleck, B.; Wenke, L.

    2000-01-01

    the polarization of the first-order diffracted beam. The main advantage of this method is that both parts can be determined simultaneously by only one measurement. Furthermore the displacement between both gratings can be determined in a similar manner. Experimental results obtained with two different polyesters...

  7. Double Hydrogen Bonding between Side Chain Carboxyl Groups in Aqueous Solutions of Poly (β-L-Malic Acid): Implication for the Evolutionary Origin of Nucleic Acids

    Science.gov (United States)

    Francis, Brian R.; Watkins, Kevin; Kubelka, Jan

    2017-01-01

    The RNA world hypothesis holds that in the evolutionary events that led to the emergence of life RNA preceded proteins and DNA and is supported by the ability of RNA to act as both a genetic polymer and a catalyst. On the other hand, biosynthesis of nucleic acids requires a large number of enzymes and chemical synthesis of RNA under presumed prebiotic conditions is complicated and requires many sequential steps. These observations suggest that biosynthesis of RNA is the end product of a long evolutionary process. If so, what was the original polymer from which RNA and DNA evolved? In most syntheses of simpler RNA or DNA analogs, the D-ribose phosphate polymer backbone is altered and the purine and pyrimidine bases are retained for hydrogen bonding between complementary base pairs. However, the bases are themselves products of complex biosynthetic pathways and hence they too may have evolved from simpler polymer side chains that had the ability to form hydrogen bonds. We hypothesize that the earliest evolutionary predecessor of nucleic acids was the simple linear polyester, poly (β-D-malic acid), for which the carboxyl side chains could form double hydrogen bonds. In this study, we show that in accord with this hypothesis a closely related polyester, poly (β-L-malic acid), uses carboxyl side chains to form robust intramolecular double hydrogen bonds in moderately acidic solution. PMID:29061955

  8. Pattern of liquid crystalline droplets induced by two beam interference in azobenzene derivative

    Science.gov (United States)

    Czajkowski, Maciej; Dradrach, Klaudia; Bartkiewicz, Stanislaw; Galewski, Zbigniew

    2013-10-01

    A pattern of liquid crystalline droplets dispersed in the isotropic liquid can be formed during illumination by two interfering laser beams in certain range of the temperature and the light intensity. Azobenzene derivative substituted by long alkyl and alkoxy chains exhibiting smectic phases has been used for the study. The pattern can be reversibly erased and rewritten by shutting down and opening of the interfering beams. Polarized microscope images have shown the formation of numerous liquid crystalline droplets at bright regions of the interference fringes. Influence of the temperature and the light intensity has been studied by measuring the diffraction efficiency dynamics. Photothermal and photoorientational mechanisms of the formation of liquid crystalline droplets pattern have been proposed and discussed.

  9. Building photoswitchable 3,4'-AMPB peptides: Probing chemical ligation methods with reducible azobenzene thioesters

    Directory of Open Access Journals (Sweden)

    Gehad Zeyat

    2012-06-01

    Full Text Available Photoswitchable peptides were synthesized by using cysteine- and auxiliary-based native chemical ligation reactions. For this purpose, the two regioisomeric azobenzene building blocks 3,4'-AMPB thioester 1b and 4,4'-AMPB thioester 2b were employed in the ligation reactions. While 4,4'-AMPB requires the 4,5,6-trimethoxy-2-mercaptobenzyl auxiliary to minimize reduction of the diazene unit, 3,4'-AMPB can be used in combination with the 4,5,6-trimethoxy-2-mercaptobenzyl auxiliary as well as the Nα-2-mercaptoethyl auxiliary. Thus, 3,4'-AMPB derivatives/peptides proved to be significantly less prone to reduction by aliphatic and aromatic thiols than were the 4,4'-AMPB compounds.

  10. Experimental and Computational study of azobenzene and 2,2',6,6'-tetrafluoroazobenzene cation.

    Science.gov (United States)

    Rezaee, Mohammadreza; Armentrout, Peter B.

    The electronic structure of the protonated azobenzene and it its derivative 2,2',6,6'-tetrafluoroazobenzene were studied using ab initio methods and the bond strength were measured utilizing the collision induced dissociation experiment. Several highly accurate multi-level schemes such as different variations of the Complete Basis Set (CBS) method and the Gaussian (G-n) theory along with DFT study employed to accurately compute the energies of the neutral and the parent cation as well as the fragment ions. The transition state were studied and the dissociation path was identified using B3LYP method along with aug-cc-pVTZ as the basis set. Thermochemical properties such as proton affinity, gas phase basicity and the bond dissociation energies were calculated. Molecular electrostatic potential analysis was performed to identify the charge distribution inside the molecule to study the effects of the protonation reaction. Newton HPC Program, University of Tennessee.

  11. Azobenzene-Based Gel Coated Fibre Bragg Grating Sensor for Moisture Measurement

    Directory of Open Access Journals (Sweden)

    Mohammed Moniruzzaman

    2016-01-01

    Full Text Available A fibre Bragg grating sensor is coated with a novel polymer gel in order to investigate its suitability for nondestructive measurement of moisture in materials that can potentially lose their integrity due to moisture ingress. Absorption and desorption of moisture lead to swelling/shrinkage of an azobenzene-based gel, which induces a strain in the Bragg grating resulting in wavelength shifts. The results demonstrated that the amount of wavelength shift is linearly dependent on the amount of water ingress by the gel. The performance of the proposed optical fibre moisture sensor was found to be repeatable with no detectable hysteresis and has the potential to offer a low-cost route for monitoring moisture content.

  12. Photo-responsive carbon nanomaterials functionalized by azobenzene moieties: structures, properties and application.

    Science.gov (United States)

    Feng, Wei; Luo, Wen; Feng, Yiyu

    2012-10-21

    The ability to tune the microstructures, bandgap, conductance, chemical environment and thermal storage of carbon nanomaterials such as carbon nanotubes, graphene and fullerenes by optical modulation or response is important to design and fabricate advanced optoelectronic nanodevices. This review is focused on optical control and regulation of structures, properties, interface and interaction of a new generation of photo-responsive carbon nanomaterials/azobenzene moieties (Carbon-AZO) hybrids. The optical switching properties of Carbon-AZO hybrids resulting from the photo-isomerization between trans and cis isomers are highlighted and discussed in terms of photo-energy conversion devices including switches, sensors, detectors, fuels and storage. A wide range of advanced energy conversion devices using Carbon-AZO hybrids can be developed in the future by the optimization of the chemical structure, steric conformation, electrostatic environment and functionalization of specific molecules.

  13. Molecular glasses of azobenzene for holographic data storage applications

    Science.gov (United States)

    Zarins, Elmars; Balodis, Karlis; Ruduss, Armands; Kokars, Valdis; Ozols, Andris; Augustovs, Peteris; Saharovs, Dmitrijs

    2018-05-01

    A series of D-N=N-A type molecular glasses where the electron acceptor part (A) contains several electron withdrawing substituents, but the electron donating part (D) of the glassy azochromophores contains amorphous phase promoting non-conjugated bulky triphenyl or hydroxyl groups have been synthesized and investigated. Results showed that the azodye physical properties depend not only on the incorporated electron withdrawing substituents but are also influenced by the bonding type of covalently attached bulky moieties. Synthesized glassy azocompounds showed glass transition temperatures up to 106 °C and thermal stability up to 312 °C. The ability to form holographic gratings in spin-cast thin films of the glassy azodyes was investigated using 532 nm and 633 nm lasers obtaining diffraction efficiency up to 57%, self-diffraction efficiency up to 15% and photosensitivity as high as 3.7 J/(cm2%). Surface relief grating (SRG) depths reached 1.1 μm and in some cases even exceeded the thickness of the films.

  14. Preparation and Characterization of Binary Organogels via Some Azobenzene Amino Derivatives and Different Fatty Acids: Self-Assembly and Nanostructures

    Directory of Open Access Journals (Sweden)

    Haiying Guo

    2014-01-01

    Full Text Available In present work the gelation behaviors of binary organogels composed of azobenzene amino derivatives and fatty acids with different alkyl chains in various organic solvents were designed and investigated. Their gelation behaviors in 20 solvents were tested as new binary organic gelators. It showed that the length of alkyl substituent chains and azobenzene segment have played a crucial role in the gelation behavior of all gelator mixtures in various organic solvents. Longer alkyl chains in molecular skeletons in present gelators are favorable for the gelation of organic solvents. Morphological studies revealed that the gelator molecules self-assemble into different aggregates from lamella, wrinkle, to belt with change of solvents. Spectral studies indicated that there existed different H-bond formation and hydrophobic force, depending on different substituent chains in molecular skeletons. The present work may also give new perspectives for designing new binary organogelators and soft materials.

  15. Photo-optical properties of amorphous and crystalline films of azobenzene-containing photochromes with bent-shaped molecular structure

    Czech Academy of Sciences Publication Activity Database

    Bobrovsky, A.; Shibaev, V.; Hamplová, Věra; Bubnov, A.; Novotná, V.; Kašpar, M.; Piryazev, A.; Anokhin, D.; Ivanov, D.

    2016-01-01

    Roč. 316, Feb (2016), s. 75-87 ISSN 1010-6030 R&D Projects: GA ČR GA13-14133S; GA MŠk(CZ) LD14007 Institutional support: RVO:68378271 Keywords : bent-shaped azobenzene-containing compounds * E–Z isomerization * thin films * photoinduced phase transition * photoorientation Subject RIV: CC - Organic Chemistry Impact factor: 2.625, year: 2016

  16. 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

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

    Science.gov (United States)

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

    2017-01-01

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

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

    Science.gov (United States)

    Kim, Yuna; Tamaoki, Nobuyuki

    2016-02-01

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

  19. Snowmass Cosmic Frontiers 6 (CF6) Working Group Summary --The Bright Side of the Cosmic Frontier: Cosmic Probes of Fundamental Physics

    CERN Document Server

    Beatty, J.J.; Olinto, A.; Sinnis, G.; Abeysekara, A.U.; Anchordoqui, L.A.; Aramaki, T.; Belz, J.; Buckley, J.H.; Byrum, K.; Cameron, R.; Chen, Mu-Chun; Clark, K.; Connolly, A.; Cowen, D.F.; DeYoung, T.; von Doetinchem, P.; Dumm, J.; Errando, M.; Farrar, G.; Ferrer, F.; Fortson, L.; Funk, S.; Grant, D.; Griffiths, S.; Gross, A.; Hailey, C.; Hogan, C.; Holder, J.; Humensky, B.; Kaaret, P.; Klein, S.R.; Krawczynski, H.; Krennrich, F.; Krings, K.; Krizmanic, J.; Kusenko, A.; Linnemann, J.T.; MacGibbon, J.H.; Matthews, J.; McCann, A.; Mitchell, J.; Mukherjee, R.; Nitz, D.; Ong, R.A.; Orr, M.; Otte, N.; Paul, T.; Resconi, E.; Sanchez-Conde, M.A.; Sokolsky, P.; Stecker, F.; Stump, D.; Taboada, I.; Thomson, G.B.; Tollefson, K.; Ukwatta, T.; Vandenbroucke, J.; Vasileiou, V.; Vassileiv, V.V.; Weiler, T.J.; Williams, D.A.; Weinstein, A.; Wood, M.; Zitzer, B.

    2013-01-01

    Report of the CF6 Working Group at Snowmass 2013. Topics addressed include ultra-high energy cosmic rays, neutrinos, gamma rays, baryogenesis, and experiments probing the fundamental nature of spacetime.

  20. On the other side of the fence: effects of social categorization and spatial grouping on memory and attention for own-race and other-race faces.

    Science.gov (United States)

    Kloth, Nadine; Shields, Susannah E; Rhodes, Gillian

    2014-01-01

    The term "own-race bias" refers to the phenomenon that humans are typically better at recognizing faces from their own than a different race. The perceptual expertise account assumes that our face perception system has adapted to the faces we are typically exposed to, equipping it poorly for the processing of other-race faces. Sociocognitive theories assume that other-race faces are initially categorized as out-group, decreasing motivation to individuate them. Supporting sociocognitive accounts, a recent study has reported improved recognition for other-race faces when these were categorized as belonging to the participants' in-group on a second social dimension, i.e., their university affiliation. Faces were studied in groups, containing both own-race and other-race faces, half of each labeled as in-group and out-group, respectively. When study faces were spatially grouped by race, participants showed a clear own-race bias. When faces were grouped by university affiliation, recognition of other-race faces from the social in-group was indistinguishable from own-race face recognition. The present study aimed at extending this singular finding to other races of faces and participants. Forty Asian and 40 European Australian participants studied Asian and European faces for a recognition test. Faces were presented in groups, containing an equal number of own-university and other-university Asian and European faces. Between participants, faces were grouped either according to race or university affiliation. Eye tracking was used to study the distribution of spatial attention to individual faces in the display. The race of the study faces significantly affected participants' memory, with better recognition of own-race than other-race faces. However, memory was unaffected by the university affiliation of the faces and by the criterion for their spatial grouping on the display. Eye tracking revealed strong looking biases towards both own-race and own-university faces

  1. Subsequent radical fragmentation reactions of N, N-diethylamino-substituted azobenzene derivatives in a Fourier transform ion cyclotron resonance mass spectrometer using collision-induced dissociation and photodissociation.

    Science.gov (United States)

    Clemen, Martin; Grotemeyer, Jürgen

    2017-12-01

    The fragmentation behavior of N, N-diethylamino-substituted azobenzene derivatives is investigated by high-resolving mass spectrometry using a Fourier transform ion cyclotron resonance mass spectrometer. Former investigations by photodissociation as well as collision-induced dissociation experiments used to induce a loss of C 3 H 8 from the diethylamino group. The position of the additional proton in [M + H] + ions is important due to the sequences of radical fragmentation reactions. Two possibilities arise. First, a charge is located at the azo group leading to a methyl radical loss. The second possibility is that the charge has been located on the aniline nitrogen of the molecule resulting in an ethyl radical loss. Only o-ethyl red has shown the overall loss of C 3 H 8 in a two-step radical reaction mechanism. Nevertheless, p-ethyl red and ethyl yellow have shown systematic fragmentation reactions as well. Loss of C 3 H 8 has not been likely regarding both these molecules. All experimental findings together with quantum chemical calculations as well as kinetic calculations support the proposed fragmentation mechanisms of the three azo dyes.

  2. Dual photo- and pH-responsive supramolecular nanocarriers based on water-soluble pillar[6]arene and different azobenzene derivatives for intracellular anticancer drug delivery.

    Science.gov (United States)

    Hu, Xiao-Yu; Jia, Keke; Cao, Yu; Li, Yan; Qin, Shan; Zhou, Fan; Lin, Chen; Zhang, Dongmei; Wang, Leyong

    2015-01-12

    Two novel types of supramolecular nanocarriers fabricated by the amphiphilic host-guest inclusion complex formed from water-soluble pillar[6]arene (WP6) and azobenzene derivatives G1 or G2 have been developed, in which G1 is structurally similar to G2 but has an extra phenoxy group in its hydrophobic region. Supramolecular micelles can be initially formed by WP6 with G1, which gradually transform into layered structures with liquid-crystalline properties, whereas stable supramolecular vesicles are obtained from WP6 and G2, which exhibit dual photo- and pH-responsiveness. Notably, the resulting WP6⊃G2 vesicles can efficiently encapsulate anticancer drug mitoxantrone (MTZ) to achieve MTZ-loaded vesicles, which maintain good stability in a simulated normal physiological environment, whereas in an acid environment similar to that of tumor cells or with external UV irradiation, the encapsulated drug is promptly released. More importantly, cytotoxicity assay indicates that such vesicles have good biocompatibility and the MTZ-loaded vesicles exhibit comparable anticancer activity to free MTZ, especially with additional UV stimulus, whereas its cytotoxicity for normal cells was remarkably reduced. Flow cytometric analysis further confirms that the cancer cell death caused by MTZ-loaded vesicles is associated with apoptosis. Therefore, the dual pH- and UV-responsive supramolecular vesicles are a potential platform for controlled release and targeted anticancer drug delivery. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Bioactive Steroids with Methyl Ester Group in the Side Chain from a Reef Soft Coral Sinularia brassica Cultured in a Tank

    Directory of Open Access Journals (Sweden)

    Chiung-Yao Huang

    2017-09-01

    Full Text Available A continuing chemical investigation of the ethyl acetate (EtOAc extract of a reef soft coral Sinularia brassica, which was cultured in a tank, afforded four new steroids with methyl ester groups, sinubrasones A–D (1–4 for the first time. In particular, 1 possesses a β-D-xylopyranose. The structures of the new compounds were elucidated on the basis of spectroscopic analyses. The cytotoxicities of compounds 1–4 against the proliferation of a limited panel of cancer cell lines were assayed. The anti-inflammatory activities of these new compounds 1–4 were also evaluated by measuring their ability to suppress superoxide anion generation and elastase release in N-formyl-methionyl-leucyl-phenylalanine/cytochalasin B (fMLP/CB-induced human neutrophils. Compounds 2 and 3 were shown to exhibit significant cytotoxicity, and compounds 3 and 4 were also found to display attracting anti-inflammatory activities.

  4. Azide-bridged one-dimensional Mn(III) polymers: effects of side group of Schiff base ligands on structure and magnetism.

    Science.gov (United States)

    Yuan, Mei; Zhao, Fei; Zhang, Wen; Wang, Zhe-Ming; Gao, Song

    2007-12-24

    By changing ancillary tetradentate Schiff base ligands (L), two new one-dimensional azide-bridged manganese(III) coordination complexes [MnIII(L)(mu1,3-N3)]n [L = 5-Fsalen (1), 5-OCH3 (2); salen = N,N'-bis(salicylidene)-1,2-diaminoethane] as well as a mononuclear complex [MnIII(salophen)(N3)] (3) [salophen = N,N'-bis(salicylidene)-o-phenylenediamine] have been successfully obtained. All of them have been structurally and magnetically characterized. In the structures of 1-3 each MnIII ion is in a distorted octahedral geometry with an obvious Jahn-Teller effect, where the tetradentate L ligands all bind in the equatorial mode, whereas in the axial direction, the N3- ion acts as an end-to-end bridge in 1 and 2 while a terminal group in 3 with a methanol molecule at the other end. Magnetic characterization shows that the mu1,3-bridging azide ion proves to mainly transmit antiferromagnetic interaction between MnIII ions, but these three complexes exhibit various magnetic behaviors at low temperatures. Noteworthily, complex 2 behaves as a weak ferromagnet with a relatively large coercive field of 2.3 kOe, much larger than the value reported previously.

  5. Electrochemical modification of gold electrodes with azobenzene derivatives by diazonium reduction.

    Science.gov (United States)

    Kibena, Elo; Marandi, Margus; Mäeorg, Uno; Venarusso, Luna B; Maia, Gilberto; Matisen, Leonard; Kasikov, Aarne; Sammelselg, Väino; Tammeveski, Kaido

    2013-04-02

    An electrochemical study of Au electrodes electrografted with azobenzene (AB), Fast Garnet GBC (GBC) and Fast Black K (FBK) diazonium compounds is presented. Electrochemical quartz crystal microbalance, ellipsometry and atomic force microscopy investigations reveal the formation of multilayer films. The elemental composition of the aryl layers is examined by X-ray photoelectron spectroscopy. The electrochemical measurements reveal a quasi-reversible voltammogram of the Fe(CN)6 (3-/4-) redox couple on bare Au and a sigmoidal shape for the GBC- and FBK-modified Au electrodes, thus demonstrating that electron transfer is blocked due to the surface modification. The electrografted AB layer results in strongest inhibition of the Fe(CN)6 (3-/4-) response compared with other aryl layers. The same tendencies are observed for oxygen reduction; however, the blocking effect is not as strong as in the Fe(CN)6 (3-/4-) redox system. The electrochemical impedance spectroscopy measurements allowed the calculation of low charge-transfer rates to the Fe(CN)6 (3-) probe for the GBC- and FBK-modified Au electrodes in relation to bare Au. From these measurements it can be concluded that the FBK film is less compact or presents more pinholes than the electrografted GBC layer. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    Rezaee, Mohammadreza; Compton, Robert

    2015-03-01

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

  7. J-aggregates in matrix stabilized two-dimensional azobenzene derivatives.

    Science.gov (United States)

    Shankar, B Vijai; Patnaik, Archita

    2006-10-01

    A two-component film technique at the air-water interface has been used for fabricating matrix stabilized azobenzene J-aggregates. Langmuir monolayers of (E)-1-(3-chloro-4-(alkyloxy)phenyl)-2-phenyldiazene (CnCD, n=8,10,12) have been prepared with stearic acid (STA) as the two-dimensional matrix. Miscibility studies at a molecular level, explored from the monolayer pressure-area isotherms revealed a phase separation of the CnCD from the stearic acid matrix at a compression pressure of 10 mN/m. A 43-nm strong red shift in the 350 nm pi-pi * absorption feature implied formation of highly ordered J-aggregates of CnCDs in conformity with atomic force microscopy and micro-Raman spectral characteristics. While a one-component CnCD failed to form a 2D monolayer, the STA supported CnCD binary system crossed a mixed monolayer phase followed by compression, leading to the formation of matrix stabilized CnCD J-aggregates.

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

    Science.gov (United States)

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

    2016-11-01

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

  9. 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.

  10. 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.

  11. Thermodynamics and mesoscopic organisation in Langmuir monolayers of an azobenzene derivative.

    Science.gov (United States)

    Ignés-Mullol, J

    2010-12-15

    We have carried out the analysis of liquid crystalline Langmuir monolayers at the air-water interface composed of the amphiphilic azobenzene derivative 8Az5COOH. By varying the temperature and the isomeric (trans-cis) composition, the monolayer behaviour has been studied in comparison with a shorter homologue, 8Az3COOH, by measuring the surface pressure-area isotherms along with Brewster angle microscopy (BAM). Our data with the pure trans isomer enable a posterior thermodynamic analysis, which was not feasible with the shorter homologue. For the mixed trans-cis monolayers, BAM observations reveal a phase segregation with trans enriched domains surrounded by a cis enriched matrix. Line tension between the two phases is lower than in the shorter homologue. The organisation of the rodlike molecules inside the trans domains results in highly symmetric textures that make the quantitative analysis of the BAM images possible, and a better understanding of the microscopic structure of the monolayer can be achieved. Copyright © 2010 Elsevier Inc. All rights reserved.

  12. 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.

  13. Impact of the molecular structure of an indandione fragment containing azobenzene derivatives on the morphology and electrical properties of thin films

    Energy Technology Data Exchange (ETDEWEB)

    Pudzs, Kaspars, E-mail: kaspars.pudzs@cfi.lu.lv [Institute of Solid State Physics, University of Latvia, 8 Kengaraga Street, Riga LV-1063 (Latvia); Vembris, Aivars; Grzibovskis, Raitis; Latvels, Janis [Institute of Solid State Physics, University of Latvia, 8 Kengaraga Street, Riga LV-1063 (Latvia); Zarins, Elmars [Institute of Applied Chemistry, Riga Technical University, 14/24 Azenes Street, Riga LV-1048 (Latvia)

    2016-04-15

    The solution casting method is low-cost processing method. Moreover, it is possible to prepare amorphous thin films by using this method, and thus, both optical quality and electrical properties could be improved in compare to polycrystalline films made by thermal evaporation in vacuum. Therefore, low-molecular-weight compounds that form amorphous structure from solution could be promising in organic electronics. In this work film morphology, molecule energy levels, and charge carrier mobility in thin films of indandione fragment containing azobenzene derivatives were studied. Deep charge carrier trapping states that drastically influenced charge carrier mobility were observed for polycrystalline films with the model compound 2-(4-((4-(dimethylamino)phenyl)diazenyl)benzylidene)-1H-indene-1, 3(2H)-dione. This issue was overcome by attaching bulky groups to the model compound. An amorphous thin film without deep trapping states was obtained. Electron and hole mobilities of these materials at electric field 160 to 600 kV/cm were between 10{sup −5} and 10{sup −6} cm{sup 2}V{sup −1}s{sup −1} and between 10{sup −6} to 10{sup −7} cm{sup 2}V{sup −1}s{sup −1}, respectively. Charge carrier mobility, molecular ionization energy, and electron affinity energy were influenced by bulky groups. - Highlights: • Deep charge carriers trapping states could be observed in polycrystalline films. • Amorphous thin film was obtained by attaching bulky groups to the chromophore. • Different bulky groups change molecule packaging in thin film. • Distance between molecules influence charge carrier mobility. • Distance between molecules influence energy levels of the molecule.

  14. Medications and Side Effects

    Science.gov (United States)

    ... to fully work. You might feel some side effects of your medication before your feel the benefits – ... as sleepiness, anxiety or headache) is a side effect or a symptom of your illness. Many side ...

  15. Probing highly efficient photoisomerization of a bridged azobenzene by a combination of CASPT2//CASSCF calculation with semiclassical dynamics simulation.

    Science.gov (United States)

    Liu, Lihong; Yuan, Shuai; Fang, Wei-Hai; Zhang, Yong

    2011-09-08

    Mechanism of phototriggered isomerization of azobenzene and its derivatives is of broad interest. In this paper, the S(0) and S(1) potential energy surfaces of the ethylene-bridged azobenzene (1) that was recently reported to have highly efficient photoisomerization were determined by ab initio electronic structure calculations at different levels and further investigated by a semiclassical dynamics simulation. Unlike azobenzene, the cis isomer of 1 was found to be more stable than the trans isomer, consistent with the experimental observation. The thermal isomerization between cis and trans isomers proceeds via an inversion mechanism with a high barrier. Interestingly, only one minimum-energy conical intersection was determined between the S(0) and S(1) states (CI) for both cis → trans and trans → cis photoisomerization processes and confirmed to act as the S(1) → S(0) decay funnel. The S(1) state lifetime is ∼30 fs for the trans isomer, while that for the cis isomer is much longer, due to a redistribution of the initial excitation energies. The S(1) relaxation dynamics investigated here provides a good account for the higher efficiency observed experimentally for the trans → cis photoisomerization than the reverse process. Once the system decays to the S(0) state via CI, formation of the trans product occurs as the downhill motion on the S(0) surface, while formation of the cis isomer needs to overcome small barriers on the pathways of the azo-moiety isomerization and rotation of the phenyl ring. These features support the larger experimental quantum yield for the cis → trans photoisomerization than the trans → cis process.

  16. 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

  17. 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

  18. Synthesis of 2-aryl-2H-benzotrizoles from azobenzenes and N-sulfonyl azides through sequential rhodium-catalyzed amidation and oxidation in one pot.

    Science.gov (United States)

    Ryu, Taekyu; Min, Jiae; Choi, Wonseok; Jeon, Woo Hyung; Lee, Phil Ho

    2014-06-06

    An efficient synthetic method of 2-aryl-2H-benzotriazoles from nonprefunctionalized azobenzenes and N-sulfonyl azides via sequential Rh-catalyzed amidation (C-N bond formation) and oxidation (N-N bond formation) with PhI(OAc)2 in one pot is reported.

  19. Electric bistability induced by incorporating self-assembled monolayers/aggregated clusters of azobenzene derivatives in pentacene-based thin-film transistors.

    Science.gov (United States)

    Tseng, Chiao-Wei; Huang, Ding-Chi; Tao, Yu-Tai

    2012-10-24

    Composite films of pentacene and a series of azobenzene derivatives are prepared and used as the active channel material in top-contact, bottom-gate field-effect transistors. The transistors exhibit high field-effect mobility as well as large I-V hysteresis as a function of the gate bias history. The azobenzene moieties, incorporated either in the form of self-assembled monolayer or discrete multilayer clusters at the dielectric surface, result in electric bistability of the pentacene-based transistor either by photoexcitation or gate biasing. The direction of threshold voltage shifts, size of hysteresis, response time, and retention characteristics all strongly depend on the substituent on the benzene ring. The results show that introducing a monolayer of azobenzene moieties results in formation of charge carrier traps responsible for slower switching between the bistable states and longer retention time. With clusters of azobenzene moieties as the trap sites, the switching is faster but the retention is shorter. Detailed film structure analyses and correlation with the transistor/memory properties of these devices are provided.

  20. An azobenzene-containing metal-organic framework as an efficient heterogeneous catalyst for direct amidation of benzoic acids: synthesis of bioactive compounds.

    Science.gov (United States)

    Hoang, Linh T M; Ngo, Long H; Nguyen, Ha L; Nguyen, Hanh T H; Nguyen, Chung K; Nguyen, Binh T; Ton, Quang T; Nguyen, Hong K D; Cordova, Kyle E; Truong, Thanh

    2015-12-14

    An azobenzene-containing zirconium metal-organic framework was demonstrated to be an effective heterogeneous catalyst for the direct amidation of benzoic acids in tetrahydrofuran at 70 °C. This finding was applied to the synthesis of several important, representative bioactive compounds.

  1. 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)

  2. 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.

  3. Azobenzene polyesters used as gate-like scaffolds in nanoscopic hybrid systems.

    Science.gov (United States)

    Bernardos, Andrea; Mondragón, Laura; Javakhishvili, Irakli; Mas, Núria; de la Torre, Cristina; Martínez-Máñez, Ramón; Sancenón, Félix; Barat, José M; Hvilsted, Søren; Orzaez, Mar; Pérez-Payá, Enríque; Amorós, Pedro

    2012-10-08

    The synthesis and characterisation of new capped silica mesoporous nanoparticles for on-command delivery applications is reported. Functional capped hybrid systems consist of MCM-41 nanoparticles functionalised on the external surface with polyesters bearing azobenzene derivatives and rhodamine B inside the mesopores. Two solid materials, Rh-PAzo8-S and Rh-PAzo6-S, containing two closely related polymers, PAzo8 and PAzo6, in the pore outlets have been prepared. Materials Rh-PAzo8-S and Rh-PAzo6-S showed an almost zero release in water due to steric hindrance imposed by the presence of anchored bulky polyesters, whereas a large delivery of the cargo was observed in the presence of an esterase enzyme due to the progressive hydrolysis of polyester chains. Moreover, nanoparticles Rh-PAzo8-S and Rh-PAzo6-S were used to study the controlled release of the dye in intracellular media. Nanoparticles were not toxic for HeLa cells and endocytosis-mediated cell internalisation was confirmed by confocal microscopy. Furthermore, the possible use of capped materials as a drug-delivery system was demonstrated by the preparation of a new mesoporous silica nanoparticle functionalised with PAzo6 and loaded with the cytotoxic drug camptothecin (CPT-PAzo6-S). Following cell internalisation and lysosome resident enzyme-dependent gate opening, CPT-PAzo6-S induced CPT-dependent cell death in HeLa cells. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Threshold collision-induced dissociation and theoretical study of protonated azobenzene

    Science.gov (United States)

    Rezaee, Mohammadreza; McNary, Christopher P.; Armentrout, P. B.

    2017-10-01

    Protonated azobenzene (AB), H+(C6H5N2C6H5), has been studied using threshold collision-induced dissociation in a guided ion beam tandem mass spectrometer. Product channels observed are C6H5N2+ + C6H6 and C6H5+ + N2 + C6H6. The experimental kinetic energy-dependent cross sections were analyzed using a statistical model that accounts for internal and kinetic energy distributions of the reactants, multiple collisions, and kinetic shifts. From this analysis, the activation energy barrier height of 2.02 ± 0.11 eV for benzene loss is measured. To identify the transition states (TSs) and intermediates (IMs) for these dissociations, relaxed potential energy surface (PES) scans were performed at the B3LYP/aug-cc-pVTZ level of theory. The PES indicates that there is a substantial activation energy along the dissociation reaction coordinate that is the rate-limiting step for benzene loss and at some levels of theory, for subsequent N2 loss as well. Relative energies of the reactant, TSs, IMs, and products were calculated at B3LYP, wB97XD, M06, PBEPBE, and MP2(full) levels of theory using both 6-311++G(2d,2p) and aug-cc-pVTZ basis sets. Comparison of the experimental results with theoretical values from various computational methods indicates how well these theoretical methods can predict thermochemical properties. In addition to these density functional theory and MP2 methods, several high accuracy multi-level calculations such as CBS-QB3, G3, G3MP2, G3B3MP2, G4, and G4MP2 were performed to determine the thermochemical properties of AB including the proton affinity and gas-phase basicity, and to compare the performance of different theoretical methods.

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

    Science.gov (United States)

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

    2017-01-04

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

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

    Science.gov (United States)

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

    2017-01-01

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

  7. Using scanning near-field microscopy to study photo-induced mass motions in azobenzene containing thin films

    Science.gov (United States)

    Vu, A. D.; Fabbri, F.; Desboeufs, N.; Boilot, J.-P.; Gacoin, T.; Lahlil, K.; Lassailly, Y.; Martinelli, L.; Peretti, J.

    2014-10-01

    Scanning near-field optical microscopy (SNOM) is used to study the photo-induced deformation of layered structures containing azobenzene derivatives. This approach is particularly relevant since it allows detecting in real-time, with the same probe the surface topography and the optical field distribution at the nanoscale. The correlation between the local light pattern and the ongoing photo-induced deformation in azobenzene-containing thin films is directly evidenced for different light polarization configurations. This unveils several fundamental photodeformation mechanisms, depending not only on the light field properties, but also on the nature of the material. Controlling the projected electromagnetic field distribution allows inscription of various patterns with a resolution at the diffraction limit, i.e. of a few hundreds of nm. Surface relief patterns with characteristic sizes beyond the diffraction limit can also be produced by using the nearfield probe to locally control the photo-mechanical process. Finally, the photo-mechanical properties of azo-materials are exploited to optically patterned metal/dielectric hybrid structures. Gratings are inscribed this way on thin gold films. The characteristic features (enhancement and localization) of the surface plasmons supported by these noble metal structures are studied by near-field optical microscopy.

  8. 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.

  9. Unusual Photo-Induced Behaviour in a Side Chain Liquid Crystalline Azo-Polyester

    DEFF Research Database (Denmark)

    López, D; Rodríguez, F.J.; Sánchez, C.

    2006-01-01

    An unusual behaviour has been observed in the photo-indueed response of an azobenzene side chain liquid erystalline polyester (P6d4). Room temperature irradiation with linearly polarised 488 nm light does not induce any birefringence (An) in films of this polymer that have been quenehed from...... the isotropie state. However, using the same irradiation conditions An is indueed in quenehed films that have been kept in darkness for a few minutes. Besides, no photo-induced An is observed in films irradiated with 488 nm light that have been previously irradiated with UV light. In this ease, An can...... be reeorded if the UV irradiated films have been kept in darkness for several hours. In another set of experiments performed with the P6d4 polymer, irradiation with high intensity linearly polarised 488 nm light induces an initial increase of An and then it goes back to zero. Subsequent irradiation...

  10. Association between the frequency of meals combining "Shushoku, Shusai, and Hukusai" (Staple food, main dish, and side dish) and intake of nutrients and food groups among Japanese young adults aged 18-24 years: a cross-sectional study.

    Science.gov (United States)

    Kakutani, Yuya; Kamiya, Saori; Omi, Naomi

    2015-01-01

    "Shushoku," "Shusai," and "Hukusai" are staple food, main dish, and side dish, respectively. The recommended meal in Japan is a combination of "Shushoku," "Shusai," and "Hukusai"; however, it remains unclear whether there is an association between the frequency of these meals and intake of nutrients and food groups. This cross-sectional study examined the association between the frequency of meals combining "Shushoku, Shusai, and Hukusai" and intake of nutrients and food groups among 664 Japanese young adults aged 18-24 y. The dietary habits of the subjects during the preceding month were assessed using a validated brief-type self-administered diet history questionnaire. The frequency of meals combining "Shushoku, Shusai, and Hukusai" was self-reported according to four categories: "less than 1 d or 1 d/wk," "2 or 3 d/wk," "4 or 5 d/wk," and "every day." In both women and men, there was an association between the higher frequency of these meals and higher intake of the following food groups: pulses, green and yellow vegetables, other vegetables, mushrooms, seaweeds, fish and shellfish, and eggs. Moreover, there was an association with higher intake of protein, polyunsaturated fat, n-6 and n-3 polyunsaturated fat, total dietary fiber, soluble and insoluble dietary fiber, β-carotene, α-tocopherol, vitamin K, thiamin, riboflavin, folate, pantothenic acid, vitamin C, potassium, calcium, magnesium, iron, and copper, and lower intake of carbohydrate in both women and men. Our findings support the hypothesis that the meals combining "Shushoku, Shusai, and Hukusai" may be associated with intake of many food groups and nutrients among Japanese young adults.

  11. Side Effects (Management)

    Science.gov (United States)

    ... cancer care is relieving side effects, called symptom management, palliative care, or supportive care. It is important ... treat them. To learn about the symptoms and management of the long-term side effects of cancer ...

  12. 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

  13. Structure and Reactivity of Half-Sandwich Rh(+3) and Ir(+3) Carbene Complexes. Catalytic Metathesis of Azobenzene Derivatives.

    Science.gov (United States)

    Tindall, Daniel J; Werlé, Christophe; Goddard, Richard; Philipps, Petra; Farès, Christophe; Fürstner, Alois

    2018-02-07

    Traditional rhodium carbene chemistry relies on the controlled decomposition of diazo derivatives with [Rh 2 (OAc) 4 ] or related dinuclear Rh(+2) complexes, whereas the use of other rhodium sources is much less developed. It is now shown that half-sandwich carbene species derived from [Cp*MX 2 ] 2 (M = Rh, Ir; X = Cl, Br, I, Cp* = pentamethylcyclopentadienyl) also exhibit favorable application profiles. Interestingly, the anionic ligand X proved to be a critical determinant of reactivity in the case of cyclopropanation, epoxide formation and the previously unknown catalytic metathesis of azobenzene derivatives, whereas the nature of X does not play any significant role in -OH insertion reactions. This perplexing disparity can be explained on the basis of spectral and crystallographic data of a representative set of carbene complexes of this type, which could be isolated despite their pronounced electrophilicity. Specifically, the donor/acceptor carbene 10a derived from ArC(═N 2 )COOMe and [Cp*RhCl 2 ] 2 undergoes spontaneous 1,2-migratory insertion of the emerging carbene unit into the Rh-Cl bond with formation of the C-metalated rhodium enolate 11. In contrast, the analogous complexes 10b,c derived from [Cp*RhX 2 ] 2 (X = Br, I) as well as the iridium species 13 and 14 derived from [Cp*IrCl 2 ] 2 are sufficiently stable and allow true carbene reactivity to be harnessed. These complexes are competent intermediates for the catalytic metathesis of azobenzene derivatives, which provides access to α-imino esters that would be difficult to make otherwise. Rather than involving metal nitrenes, the reaction proceeds via aza-ylides that evolve into diaziridines; a metastable compound of this type has been fully characterized.

  14. 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.

  15. 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

    2018-03-09

    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

  16. Quantum chemical investigation of thermal cis-to-trans isomerization of azobenzene derivatives: substituent effects, solvent effects, and comparison to experimental data.

    Science.gov (United States)

    Dokić, Jadranka; Gothe, Marcel; Wirth, Jonas; Peters, Maike V; Schwarz, Jutta; Hecht, Stefan; Saalfrank, Peter

    2009-06-18

    Quantum chemical calculations of various azobenzene (AB) derivatives have been carried out with the goal to describe the energetics and kinetics of their thermal cis --> trans isomerization. The effects of substituents, in particular their type, number, and positioning, on activation energies have been systematically studied with the ultimate goal to tailor the switching process. Trends observed for mono- and disubstituted species are discussed. A polarizable continuum model is used to study, in an approximate fashion, the cis --> trans isomerization of azobenzenes in solution. The nature of the transition state(s) and its dependence on substituents and the environment is discussed. In particular for push-pull azobenzenes, the reaction mechanism is found to change from inversion in nonpolar solvents to rotation in polar solvents. Concerning kinetics, calculations based on the Eyring transition state theory give usually reliable activation energies and enthalpies when compared to experimentally determined values. Also, trends in the resulting rate constants are correct. Other computed properties such as activation entropies and thus preexponential rate factors are in only moderate agreement with experiment.

  17. Azobenzene-functionalized gold nanoparticles as hybrid double-floating-gate in pentacene thin-film transistors/memories with enhanced response, retention, and memory windows.

    Science.gov (United States)

    Tseng, Chiao-Wei; Huang, Ding-Chi; Tao, Yu-Tai

    2013-10-09

    Gold nanoparticles (Au-NPs) with surfaces covered with a self-assembled monolayer of azobenzene derivatives were prepared at the interface of dielectric insulator SiO2 and pentacene thin film. Transistors constructed with these composite channel materials exhibited electric bistability upon different gate biases, with the monolayer serving as a barrier layer, a work function modulator, as well as additional charge trapping sites at the Au-NPs/semiconductor interface at the same time. In comparison with simple alkanethiol monolayer-covered Au-NPs, the CH3-substituted azobenzene-functionalized Au-NPs result in a transistor memory device with about 70% more charges trapped, much faster response time as well as higher retention time. Besides, depending on the substituent on the azobenzene moieties (CH3, H, or CF3) and the tethering alkyl chain length, the speed at which the carriers are trapped (affecting switching response) and the stability of the carriers that are trapped (affecting memory retention) can be modulated to improve the device performance. The structural characterization and electronic characteristics of these devices will be detailed.

  18. Hardwood siding performance.

    Science.gov (United States)

    Glenn A. Cooper

    1967-01-01

    A 6-year exposure test of three styles of siding made from nine hardwoods and given three treatments showed that full-length yellow-poplar vertical tongue-and-groove siding dip-treated in a water-repellent preservative performed best.

  19. Single-sided NMR

    CERN Document Server

    Casanova, Federico; Blümich, Bernhard

    2011-01-01

    Single-Sided NMR describes the design of the first functioning single-sided tomograph, the related measurement methods, and a number of applications. One of the key advantages to this method is the speed at which the images are obtained.

  20. Side Effects: Appetite Loss

    Science.gov (United States)

    Cancer treatments may lower your appetite. Side effects such as nausea, fatigue, or mouth sores can also making eating difficult. Learn how to eat well to avoid losing weight or becoming dehydrated, so you stay strong during treatment.

  1. Side Effects: Fatigue

    Science.gov (United States)

    Fatigue is a common side effect of many cancer treatments such as chemotherapy, radiation therapy, immunotherapy, and surgery. Anemia and pain can also cause fatigue. Learn about symptoms and way to manage fatigue.

  2. Side Effects: Sleep Problems

    Science.gov (United States)

    Sleep problems are a common side effect during cancer treatment. Learn how a polysomnogram can assess sleep problems. Learn about the benefits of managing sleep disorders in men and women with cancer.

  3. Side Effects: Pain

    Science.gov (United States)

    Controlling pain is an important part of your cancer treatment plan. Learn how to track levels of pain. Find out how pain, a side effect of cancer treatment, is treated using acupuncture, biofeedback, and physical therapy.

  4. Side Effects: Diarrhea

    Science.gov (United States)

    Diarrhea, a side effect of cancer treatment, may cause symptoms such as loose, watery stools. Diarrhea can lead to dehydration and malnutrition in cancer patients. Learn about ways to treat and manage diarrhea during cancer treatment.

  5. Side Effects: Anemia

    Science.gov (United States)

    Anemia is a side effect of cancer treatments, including chemotherapy and radiation therapy. It can make women and men feel fatigued, dizzy, and short of breath. Learn how to manage fatigue caused by anemia during cancer treatment.

  6. [Psychoanalysis and Side Effect].

    Science.gov (United States)

    Shirahase, Joichiro

    2015-01-01

    A study of psychoanalysis from the perspective of side effects reveals that its history was a succession of measures to deal with its own side effects. This, however, does not merely suggest that, as a treatment method, psychoanalysis is incomplete and weak: rather, its history is a record of the growth and development of psychoanalysis that discovered therapeutic significance from phenomena that were initially regarded as side effects, made use of these discoveries, and elaborated them as a treatment method. The approach of research seen during the course of these developments is linked to the basic therapeutic approach of psychoanalysis. A therapist therefore does not draw conclusions about a patient's words and behaviors from a single aspect, but continues to make efforts to actively discover a variety of meanings and values from them, and to make the patient's life richer and more productive. This therapeutic approach is undoubtedly one of the unique aspects of psychoanalysis. I discuss the issue of psychoanalysis and side effects with the aim of clarifying this unique characteristic of psychoanalysis. The phenomenon called resistance inevitably emerges during the process of psychoanalytic treatment. Resistance can not only obstruct the progress of therapy; it also carries the risk of causing a variety of disadvantages to the patient. It can therefore be seen as an adverse effect. However, if we re-examine this phenomenon from the perspective of transference, we find that resistance is in fact a crucial tool in psychoanalysis, and included in its main effect, rather than a side effect. From the perspective of minimizing the character of resistance as a side effect and maximizing its character as a main effect, I have reviewed logical organization, dynamic evaluation, the structuring of treatment, the therapist's attitudes, and the training of therapists. I conclude by stating that psychoanalysis has aspects that do not match the perspective known as a side

  7. 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).

  8. 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.

  9. Ultrafast photoisomerization and its single-shot pump pulse efficiency of trans-azobenzene derivative: Compound for photosensitive DNA

    Science.gov (United States)

    Chen, Tao; Yamaguchi, Atsushi; Igarashi, Kazumasa; Nakagawa, Naoya; Nishioka, Hidenori; Asanuma, Hiroyuki; Yamashita, Mikio

    2012-03-01

    The femtosecond photoisomerization processes of trans (T) 4-carboxy-2',6'-dimethylazobenzen, which has been employed recently as an efficient photoregulator of DNA hybridization, were clarified by the rate equation analysis of measured transient absorbance changes with (350 nm) and without (380 nm) ground-state absorption of both the reactant (T) and photoproduct ( cis: C) isomers under S 2T-band excitation (360 nm, 150 fs pump): after excitation to the S 2T state with a 450-fs lifetime, ~ 1.5% of the T-molecules in the S 2T state are isomerized to the C-form within ~ 6 ps through the intermediate state (so called bottleneck state), but most of those return back to the T ground-state S 2T via the internal conversion processes with an ultrafast kinetic rate of 2.2 × 10 12 s - 1 . Moreover, the rate equation analysis enables us to determine the T-to-C photoisomerization rate ηT,C per pump pulse to be 0.0011 at the pump energy of 80 nJ from the amplitude A3,350 of the offset component in the 350-nm probe signal, and to obtain the photoisomerization quantum yield Φ T,C = 0.094. The latter value is slightly lower than that of T-azobenzene, and well agrees with that (Φ T,C = 0.097) measured by the conventional CW irradiation method using a photostationary state.

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

    Science.gov (United States)

    Komitov, Lachezar; Ruslim, Christian; Ichimura, Kunihiro

    2000-05-01

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

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

    Science.gov (United States)

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

    2013-11-19

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

  12. Four Sided Seal Tester

    Science.gov (United States)

    2009-07-01

    The Center for Advanced Food Technology School of Enviromental and Biological Sciences New Brunswick, NJ 08903 FTR 216 Defense Logistics Agency...specification for four sided seal tester as function of confinement plate distance” The following modifications were issued :  Jul 18, 2007 0013/01

  13. Forskningens personlige side

    DEFF Research Database (Denmark)

    Hansen, Finn Thorbjørn

    2008-01-01

    Artiklen omhandler den ontologiske vending inden for universitetspædagogisk forskning, og redegør for hvorfor en mere personlig og eksistentiel side ved forskningen må medtænkes i universitetspædagogikken og -vejledningen. Udgivelsesdato: 24.11.08...

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

    Science.gov (United States)

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

    2012-12-11

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

  15. Conoscopic evidence of the UV light-induced flexoelectric effect in homeotropic layers of nematic liquid crystal doped with azobenzene derivatives

    Science.gov (United States)

    Marinov, Y. G.; Hadjichristov, G. B.; Petrov, A. G.; Sridevi, S.; Hiremath, U. S.; Yelamaggad, C. V.; Prasad, S. K.

    2010-11-01

    A digitalized version of the standard method of conoscopy was employed to register the bend deformation of molecular orientation in homeotropic nematic layers caused by an in-plane applied DC electric field, and influenced by UV light illumination. Two guest-host systems prepared by mixing of a nematic liquid crystal and an azobenzene-containing photochromic liquid crystalline material featuring a longitudinal molecular asymmetry, were studied. Upon continuous UV irradiation, a photo-isomerization of the photochromic molecules occurs resulting in an enhanced flexoelectric response of the guest-host mixtures. The dependence of the photoflexoeffect on the field strength and UV light intensity was also examined.

  16. Conoscopic evidence of the UV light-induced flexoelectric effect in homeotropic layers of nematic liquid crystal doped with azobenzene derivatives

    International Nuclear Information System (INIS)

    Marinov, Y G; Hadjichristov, G B; Petrov, A G; Sridevi, S; Hiremath, U S; Yelamaggad, C V; Prasad, S K

    2010-01-01

    A digitalized version of the standard method of conoscopy was employed to register the bend deformation of molecular orientation in homeotropic nematic layers caused by an in-plane applied DC electric field, and influenced by UV light illumination. Two guest-host systems prepared by mixing of a nematic liquid crystal and an azobenzene-containing photochromic liquid crystalline material featuring a longitudinal molecular asymmetry, were studied. Upon continuous UV irradiation, a photo-isomerization of the photochromic molecules occurs resulting in an enhanced flexoelectric response of the guest-host mixtures. The dependence of the photoflexoeffect on the field strength and UV light intensity was also examined.

  17. Computer-mediated communication as a channel for social resistance : The strategic side of SIDE

    NARCIS (Netherlands)

    Spears, R; Lea, M; Corneliussen, RA; Postmes, T; Ter Haar, W

    2002-01-01

    In two studies, the authors tested predictions derived from the social identity model of deindividuation effects (SIDE) concerning the potential of computer-mediated communication (CMC) to serve as a means to resist powerful out-groups. Earlier research using the SIDE model indicates that the

  18. Working the Dark Side

    DEFF Research Database (Denmark)

    Bjering, Jens Christian Borrebye

    A few days after the terror attacks of 9/11, then Vice President Dick Cheney appeared on television with a call for “working the dark side.” While still unclear what this expression entailed at the time, Cheney's comment appears in retrospect to almost have been prophetic for the years to come...... – years where parts of the U.S. Army and intelligence community set up a rampant torture regime all across the world. Yet, the connection between a so-called “dark side,” “working” this “dark side,” and the torture that followed is not a given, but, instead, a consequence of a set of very specific legal......, political, and personal choices in the early years after 9/11. This dissertation is an investigation into how the notion of a “dark side” took form, and of how and why the specific make-up of this“dark side” ended up creating a torture regime which already today seems almost unreal. The dissertation's first...

  19. Superior Z→E and E→Z photoswitching dynamics of dihydrodibenzodiazocine, a bridged azobenzene, by S1(nπ*) excitation at λ = 387 and 490 nm.

    Science.gov (United States)

    Siewertsen, Ron; Schönborn, Jan Boyke; Hartke, Bernd; Renth, Falk; Temps, Friedrich

    2011-01-21

    The ultrafast Z→E and E→Z photoisomerisation dynamics of 5,6-dihydrodibenzo[c,g][1,2]diazocine (1), the parent compound of a class of bridged azobenzene-based photochromic molecular switches with a severely constrained eight-membered heterocyclic ring as central unit, have been studied by femtosecond time-resolved spectroscopy in n-hexane as solvent and by quantum chemical calculations. The diazocine contrasts with azobenzene (AB) in that its Z rather than E isomer is the energetically more stable form. Moreover, it stands out compared to AB for the spectrally well separated S(1)(nπ*) absorption bands of its two isomers. The Z isomer absorbs at around λ = 404 nm, the E form has its absorption maximum around λ = 490 nm. The observed transient spectra following S(1)(nπ*) photoexcitation show ultrafast excited-state decays with time constants τ(1) = 70 fs for the Z and derivatives constitute outstanding candidates for photoswitchable molecular tweezers and other applications.

  20. Broadcasting with side information

    OpenAIRE

    Alon, Noga; Hasidim, Avinatan; Lubetzky, Eyal; Stav, Uri; Weinstein, Amit

    2008-01-01

    A sender holds a word x consisting of n blocks x_i, each of t bits, and wishes to broadcast a codeword to m receivers, R_1,...,R_m. Each receiver R_i is interested in one block, and has prior side information consisting of some subset of the other blocks. Let \\beta_t be the minimum number of bits that has to be transmitted when each block is of length t, and let \\beta be the limit \\beta = \\lim_{t \\to \\infty} \\beta_t/t. In words, \\beta is the average communication cost per bit in each block (f...

  1. Flapping propulsion with side-by-side pitching foils

    Science.gov (United States)

    Huera-Huarte, Francisco

    2016-11-01

    Fish schools are one of the most common types of collective behaviour observed in nature. One of the reasons why fish swim in groups, is to reduce the cost of transport of the school. In this work we explore the propulsive performance of two foils flapping in a symmetric configuration, i.e. with an out-of-phase flapping motion. Direct thrust measurements and Particle Image Velocimetry (PIV) allowed a detailed examination of the forces and the wake generated by the system, for different kinematics (swept angles and frequencies) and shaft separations. For certain specific cases, volumetric PIV shows major differences on how the different structures in the wake of the system evolve, depending on the imposed kinematics and the side-by-side separation between the foils. Results obtained will be compared against data produced with isolated flapping foils with similar imposed kinematics, with the aim to better understand the interactions between both and the performance of the system as a whole. The author would like to acknowledge the financial support provided by the Spanish Ministerio de Economia y competitividad (MINECO) through Grant DPI2015-71645-P.

  2. Organocatalytic asymmetric arylation of indoles enabled by azo groups

    Science.gov (United States)

    Qi, Liang-Wen; Mao, Jian-Hui; Zhang, Jian; Tan, Bin

    2018-01-01

    Arylation is a fundamental reaction that can be mostly fulfilled by electrophilic aromatic substitution and transition-metal-catalysed aryl functionalization. Although the azo group has been used as a directing group for many transformations via transition-metal-catalysed aryl carbon-hydrogen (C-H) bond activation, there remain significant unmet challenges in organocatalytic arylation. Here, we show that the azo group can effectively act as both a directing and activating group for organocatalytic asymmetric arylation of indoles via formal nucleophilic aromatic substitution of azobenzene derivatives. Thus, a wide range of axially chiral arylindoles have been achieved in good yields with excellent enantioselectivities by utilizing chiral phosphoric acid as catalyst. Furthermore, highly enantioenriched pyrroloindoles bearing two contiguous quaternary chiral centres have also been obtained via a cascade enantioselective formal nucleophilic aromatic substitution-cyclization process. This strategy should be useful in other related research fields and will open new avenues for organocatalytic asymmetric aryl functionalization.

  3. Probiotics: Safety and Side Effects

    Science.gov (United States)

    ... turn JavaScript on. Feature: Probiotics Safety and Side Effects Past Issues / Winter 2016 Table of Contents What the Science Says About the Safety and Side Effects of Probiotics Whether probiotics are likely to be ...

  4. HIV Medicines and Side Effects

    Science.gov (United States)

    ... Apps skip to content Side Effects of HIV Medicines Home Understanding HIV/AIDS Fact Sheets HIV Medicines ... p.m. ET) Send us an email HIV Medicines and Side Effects Last Reviewed: October 9, 2017 ...

  5. Running away from side effects

    DEFF Research Database (Denmark)

    Casla, S; Hojman, P; Márquez-Rodas, I

    2015-01-01

    The number of breast cancer survivors increases every year, thanks to the development of new treatments and screening techniques. However, patients present with numerous side effects that may affect their quality of life. Exercise has been demonstrated to reduce some of these side effects, but in...... of how to design exercise interventions in patients with different side effects....

  6. Side-View Face Recognition

    NARCIS (Netherlands)

    Santemiz, P.; Spreeuwers, Lieuwe Jan; Veldhuis, Raymond N.J.

    2010-01-01

    Side-view face recognition is a challenging problem with many applications. Especially in real-life scenarios where the environment is uncontrolled, coping with pose variations up to side-view positions is an important task for face recognition. In this paper we discuss the use of side view face

  7. Azobenzene-containing LC polymethacrylates highly photosensitive in broad spectral range

    Czech Academy of Sciences Publication Activity Database

    Bobrovsky, A.; Shibaev, V.; Cigl, Martin; Hamplová, Věra; Pociecha, D.; Bubnov, Alexej

    2016-01-01

    Roč. 54, č. 18 (2016), s. 2962-2970 ISSN 0887-624X R&D Projects: GA ČR GA16-12150S; GA MŠk(CZ) LH15305 Institutional support: RVO:68378271 Keywords : liquid crystals * polymethacrylate * photosensitive * azo group * smectic A * photo-optical properties Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.952, year: 2016

  8. Side effects of ambulatory blood pressure monitoring.

    NARCIS (Netherlands)

    Steen, M.S. van der; Lenders, J.W.M.; Thien, Th.

    2005-01-01

    OBJECTIVE: To study the experiences and complaints of patients who underwent 24 h blood pressure monitoring. METHODS: Two groups of hypertensive patients of a tertiary outpatient clinic were asked to fill in a nine-item questionnaire about the side effects of ambulatory blood pressure monitoring

  9. Side Chain Engineering in Solution-Processable Conjugated Polymers

    KAUST Repository

    Mei, Jianguo

    2014-01-14

    Side chains in conjugated polymers have been primarily utilized as solubilizing groups. However, these side chains have roles that are far beyond. We advocate using side chain engineering to tune a polymer\\'s physical properties, including absorption, emission, energy level, molecular packing, and charge transport. To date, numerous flexible substituents suitable for constructing side chains have been reported. In this Perspective article, we advocate that the side chain engineering approach can advance better designs for next-generation conjugated polymers. © 2013 American Chemical Society.

  10. One-Sided Logic in Two-Sided Markets

    OpenAIRE

    Wright, Julian

    2003-01-01

    In this paper the author considers eight basic fallacies that can arise from using conventional wisdom from one-sided markets in two-sided market settings. These fallacies are illustrated using statements made in the context of regulatory investigations into credit card schemes in Australia and the United Kingdom. The author also discusses how these fallacies may be reconciled by proper use of a two-sided market analysis, making reference to the relevant economics literature where applicable....

  11. Contributions of the Histidine Side Chain and the N-terminal α-Amino Group to the Binding Thermodynamics of Oligopeptides to Nucleic Acids as a Function of pH

    Science.gov (United States)

    Ballin, Jeff D.; Prevas, James P.; Ross, Christina R.; Toth, Eric A.; Wilson, Gerald M.; Record, M. Thomas

    2010-01-01

    Interactions of histidine with nucleic acid phosphates and histidine pKa shifts make important contributions to many protein-nucleic acid binding processes. To characterize these phenomena in simplified systems, we quantified binding of a histidine-containing model peptide HWKK (+NH3-His-Trp-Lys-Lys-NH2) and its lysine analog KWKK (+NH3-Lys-Trp-Lys-Lys-NH2) to a single-stranded RNA model, polyuridylate (polyU), by changes in tryptophan fluorescence as a function of salt concentration and pH. For both HWKK and KWKK, equilibrium binding constants, Kobs, and magnitudes of log-log salt derivatives SKobs ≡ (∂logKobs/∂log[Na+]), decreased with increasing pH in the manner expected for a titration curve model in which deprotonation of the histidine and α-amino groups weakens binding and reduces its salt-dependence. Fully protonated HWKK and KWKK exhibit the same Kobs and SKobs within uncertainty, and these SKobs values are consistent with limiting-law polyelectrolyte theory for +4 cationic oligopeptides binding to single-stranded nucleic acids. The pH-dependence of HWKK binding to polyU provides no evidence for pKa shifts nor any requirement for histidine protonation, in stark contrast to the thermodynamics of coupled protonation often seen for these cationic residues in the context of native protein structure where histidine protonation satisfies specific interactions (e.g., salt-bridge formation) within highly complementary binding interfaces. The absence of pKa shifts in our studies indicates that additional Coulombic interactions across the nonspecific-binding interface between RNA and protonated histidine or the α-amino group are not sufficient to promote proton uptake for these oligopeptides. We present our findings in the context of hydration models for specific versus nonspecific nucleic acid binding. PMID:20108951

  12. High Energy Density in Azobenzene-based Materials for Photo-Thermal Batteries via Controlled Polymer Architecture and Polymer-Solvent Interactions.

    Science.gov (United States)

    Jeong, Seung Pyo; Renna, Lawrence A; Boyle, Connor J; Kwak, Hyunwook S; Harder, Edward; Damm, Wolfgang; Venkataraman, Dhandapani

    2017-12-19

    Energy densities of ~510 J/g (max: 698 J/g) have been achieved in azobenzene-based syndiotactic-rich poly(methacrylate) polymers. The processing solvent and polymer-solvent interactions are important to achieve morphologically optimal structures for high-energy density materials. This work shows that morphological changes of solid-state syndiotactic polymers, driven by different solvent processings play an important role in controlling the activation energy of Z-E isomerization as well as the shape of the DSC exotherm. Thus, this study shows the crucial role of processing solvents and thin film structure in achieving higher energy densities.

  13. Increased efficiency of light-emitting diodes incorporating anodes functionalized with fluorinated azobenzene monolayers and a green-emitting polyfluorene derivative

    Science.gov (United States)

    Lazzerini, G. M.; Mian, S.; Di Stasio, F.; Merari Masillamani, A.; Crivillers, N.; Reinders, F.; Mayor, M.; Samorı, P.; Cacialli, F.

    2012-10-01

    We investigate the functionalization of gold anodes with azobenzene-based self-assembled monolayers (AZO-SAM) and the influence of such functionalization on the external quantum efficiency (EQE) of polyfluorene-based light-emitting diodes (LEDs). Photoluminescence and electroluminescence measurements show that the AZO-SAMs do not modify the shape of the emission spectrum of the active layer. Instead, AZO-SAMs enhance the EQE of LEDs by an order of magnitude (from 0.018% to 0.18%) and decrease the turn-on voltage from 7.9 V to 6.2 V by reducing the injection barrier at the anode, thus promoting a better balance between hole and electron populations in the active layer.

  14. Growth of isotropic domains as a mechanism of dynamic diffraction grating recording in low molecular liquid-crystalline derivatives of azobenzene.

    Science.gov (United States)

    Czajkowski, Maciej; Bartkiewicz, Stanislaw; Mysliwiec, Jaroslaw

    2012-03-15

    In this paper, we propose and explain the mechanism of dynamic molecular motions and isotropic domain formation during the diffraction grating recording in low molecular liquid-crystalline azobenzene derivatives. The photochromic molecules of 4-heptyl-4'-methoxyazobenzene, showing nematic liquid-crystalline properties close to the room temperature (from T = 34 °C), are used. A one-dimensional model of the grating formation is formulated based on in vivo polarized microscope observations. Formation and growth of the isotropic domains induced by the sinusoidally modulated Gaussian light intensity distribution is proposed as the mechanism and is used for experimental data fitting. The influence of the recording light intensity, grating period, and temperature on the domain growth rate factor is checked. © 2012 American Chemical Society

  15. The first 3-fold interpenetrating framework containing both azobenzene-3,3′-dicarboxylicate and 1,2-bis(4-pyridylethylene

    Directory of Open Access Journals (Sweden)

    Yaping Duan

    2014-12-01

    Full Text Available The reactions of Co II or Ni II acetate with azobenzene-3,3′-dicarboxylic acid (3,3′-H2AZDB and 1,2-bis(4-pyridylethylene (bpe afforded two isomorphic compounds [M 2(3,3′-AZDB2(bpe2]n (M=Co (1 and Ni (2 under hydrothermal conditions. They were characterized by elemental analysis, IR spectra, thermogravimetric analysis and single-crystal X-ray diffraction technique. The structures of compounds 1 and 2 have similar 3-D 3-fold interpenetrating structures in which each 3-D net displayed a 6-connected pcu network consisting of M 2+-AZDB2− layers and bpe pillars. Variable-temperature magnetic-susceptibility measurements revealed the occurrence of weak antiferromagnetic interactions between the Co(II atoms in 1.

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

    Directory of Open Access Journals (Sweden)

    Belén Fernández

    2016-02-01

    Full Text Available We report the in situ formation of two novel metal-organic frameworks based on terbium and dysprosium ions using azobenzene-4,4′-dicarboxylic acid (H2abd as ligand, synthesized by soft hydrothermal routes. Both materials show isostructural three-dimensional networks with channels along a axis and display intense photoluminescence properties in the solid state at room temperature. Textural properties of the metal-organic frameworks (MOFs have been fully characterized although no appreciable porosity was obtained. Magnetic properties of these materials were studied, highlighting the dysprosium material displays slightly frequency-dependent out of phase signals when measured under zero external field and under an applied field of 1000 Oe.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-09-30

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

  18. Reversible light-controlled conductance switching of azobenzene-based metal/polymer nanocomposites

    International Nuclear Information System (INIS)

    Pakula, Christina; Zaporojtchenko, Vladimir; Strunskus, Thomas; Faupel, Franz; Zargarani, Dordaneh; Herges, Rainer

    2010-01-01

    We present a new concept of light-controlled conductance switching based on metal/polymer nanocomposites with dissolved chromophores that do not have intrinsic current switching ability. Photoswitchable metal/PMMA nanocomposites were prepared by physical vapor deposition of Au and Pt clusters, respectively, onto spin-coated thin poly(methylmethacrylate) films doped with azo-dye molecules. High dye concentrations were achieved by functionalizing the azo groups with tails and branches, thus enhancing solubility. The composites show completely reversible optical switching of the absorption bands upon alternating irradiation with UV and blue light. We also demonstrate reversible light-controlled conductance switching. This is attributed to changes in the metal cluster separation upon isomerization based on model experiments where analogous conductance changes were induced by swelling of the composite films in organic vapors and by tensile stress.

  19. Systemic side effects of locally used oxymetazoline

    OpenAIRE

    Dokuyucu, Recep; Gokce, Hasan; Sahan, Mustafa; Sefil, Fatih; Tas, Zeynel Abidin; Tutuk, Okan; Ozturk, Atakan; Tumer, Cemil; Cevik, Cengiz

    2015-01-01

    Objectives: The object of the study is to experimentally investigate the possible systemic side effects of Oxymetazoline including its nasal spray which has been in use for a long time both by the physicians and patients. There is no study in the literature to address the damages of oxymetazoline on the end organ. Materials and methods: The study conducted on 2 groups of rat. Group 1 (n = 8): Control; and Group 2 (n = 8): Oxymetazoline. During 4 week, the control group was applied with 2 drop...

  20. Tertiary amine derivatives of chlorochalcone as acetylcholinesterase (AChE) and buthylcholinesterase (BuChE) inhibitors: the influence of chlorine, alkyl amine side chain and α,β-unsaturated ketone group.

    Science.gov (United States)

    Gao, Xiao-Hui; Zhou, Chao; Liu, Hao-Ran; Liu, Lin-Bo; Tang, Jing-Jing; Xia, Xin-Hua

    2017-12-01

    A new series of tertiary amine derivatives of chlorochalcone (4a∼4l) were designed, synthesized and evaluated for the effect on acetylcholinesterase (AChE) and buthylcholinesterase (BuChE). The results indicated that all compounds revealed moderate or potent inhibitory activity against AChE, and some possessed high selectivity for AChE over BuChE. The structure-activity investigation showed that the substituted position of chlorine significantly influenced the activity and selectivity. The alteration of tertiary amine group also leads to obvious change in bioactivity. Among them, IC 50 of compound 4l against AChE was 0.17 ± 0.06 µmol/L, and the selectivity was 667.2 fold for AChE over BuChE. Molecular docking and enzyme kinetic study on compound 4l suggested that it simultaneously binds to the catalytic active site (CAS) and peripheral anionic site (PAS) of AChE. Further study showed that the pyrazoline derivatives synthesized from chlorochalcones had weaker activity and lower selectivity in inhibiting AChE compared to that of chlorochalcone derivatives.

  1. One-sided dichotomies versus two-sided dichotomies: arbitrary ...

    African Journals Online (AJOL)

    ... two- sided nonuniform exponential dichotomies with arbitrary growth rates in terms of the existence of one-sided nonuniform exponential dichotomies on the past and on the future. We consider both linear nonautonomous dynamics with discrete and continuous time, on an arbitrary Banach space. Keywords: Growth rates ...

  2. Side effects after ambulatory lumbar iohexol myelography

    International Nuclear Information System (INIS)

    Sand, T.; Myhr, G.; Stovner, L.J.; Dale, L.G.; Tangerud, A.

    1989-01-01

    Side effect incidences after ambulatory (22G needle and two h bed rest) and after non-ambulatory (22 and 20G needles and 20 h bed rest) lumbar iohexol myelography have been estimated and compared. Headache incidence was significantly greater in ambulatory (50%, n=107) as compared to nonambulatory myelography (26%, n=58). Headaches in the ambulatory group tended to be of shorter duration and the difference between severe headaches in ambulatory and non-ambulatory groups was not significant. Serious adverse reactions did not occur and none of the ambulatory patients required readmission because of side effects. The headache was predominantly postural and occurred significantly earlier in the ambulatory group. Headache incidence was significantly greater after 20G needle myelography (44%, n=97) as compared to 22G needle iohexol myelography (26%, n=58). The results support the hypothesis that CSF leakage is a major cause of headache after lumbar iohexol myelography. (orig.)

  3. Comparative molecular analyses of left-sided colon, right-sided colon, and rectal cancers.

    Science.gov (United States)

    Salem, Mohamed E; Weinberg, Benjamin A; Xiu, Joanne; El-Deiry, Wafik S; Hwang, Jimmy J; Gatalica, Zoran; Philip, Philip A; Shields, Anthony F; Lenz, Heinz-Josef; Marshall, John L

    2017-10-17

    Tumor sidedness has emerged as an important prognostic and predictive factor in the treatment of colorectal cancer. Recent studies demonstrate that patients with advanced right-sided colon cancers have a worse prognosis than those with left-sided colon or rectal cancers, and these patient subgroups respond differently to biological therapies. Historically, management of patients with metastatic colon and rectal cancers has been similar, and colon and rectal cancer patients have been grouped together in large clinical trials. Clearly, the differences in molecular biology among right-sided colon, left-sided colon, and rectal cancers should be further studied in order to account for disparities in clinical outcomes. We profiled 10,570 colorectal tumors (of which 2,413 were identified as arising from the left colon, right colon, or rectum) using next-generation sequencing, immunohistochemistry, chromogenic in-situ hybridization, and fragment analysis (Caris Life Sciences, Phoenix, AZ). Right-sided colon cancers had higher rates of microsatellite instability, more frequent aberrant activation of the EGFR pathway including higher BRAF and PIK3CA mutation rates, and increased mutational burden compared to left-sided colon and rectal cancers. Rectal cancers had higher rates of TOPO1 expression and Her2/neu amplification compared to both left- and right-sided colon cancers. Molecular variations among right-sided colon, left-sided colon, and rectal tumors may contribute to differences in clinical behavior. The site of tumor origin (left colon, right colon, or rectum) should certainly be considered when selecting treatment regimens and stratifying patients for future clinical trials.

  4. Analysis of side writing asymmetry

    NARCIS (Netherlands)

    Hozoi, A.; Groenland, J.P.J.; Albertini, J.B.; Lodder, J.C.

    2003-01-01

    The side writing asymmetry of a recording head was investigated using an overwrite configuration that enhances the edge effects. The track profiles of the overwrite patterns were measured for analyzing the side writing performance of the head. Magnetic force microscope (MFM) images of the overwrite

  5. Comparing Demand Side Management approaches

    NARCIS (Netherlands)

    Molderink, Albert; Bakker, Vincent; Hurink, Johann L.; Smit, Gerardus Johannes Maria

    2012-01-01

    Due to increasing energy prices and the greenhouse effect, a more efficient energy supply is desirable, preferably based on renewable sources. To cope with the decrease of flexibility due to the introduction of renewables in production side of the supply chain, a more flexible consumer side is

  6. Propargyloxycarbonyl as a protecting group for the side chains of ...

    Indian Academy of Sciences (India)

    WINTEC

    obtained was isolated by filtration. The crystalline solid was washed with isopropyl alcohol (25 mL × 2), ether (25 mL × 4) and dried under vacuum to get brick red crystals of ammonium tetrathiomolybdate. (13⋅4–14⋅2 g, 92%). A solution of benzyltriethylammonium chloride. (23⋅31 g, 102⋅5 mmol) in distilled water (60 mL).

  7. Propargyloxycarbonyl as a protecting group for the side chains of ...

    Indian Academy of Sciences (India)

    WINTEC

    100–200 mesh) using a solution of ethyl acetate. (10–20%) in petroleum ether as eluent. 2.4a Boc–Ser(Poc)–OMe, 4a: Colourless oil;. Yield: 90%; [α]D: +34 (c = 1, MeOH); FTIR (Neat):. 3289 (br), 2130 (w), 1754 (s), 1713 (s); δH. (300 MHz, CDCl3): 5⋅39 (bd, J = 7⋅8 Hz, 1H), 4⋅73. (d, J = 1⋅8 Hz, 2H), 4⋅52–4⋅60 (m, 2H), ...

  8. The DarkSide project

    Energy Technology Data Exchange (ETDEWEB)

    Agnes, P.; Agostino, L.; Albuquerque, Ivone Freire Da Mota; Alexander, Thomas R.; Alton, A.; Arisaka, K.; Back, Henning O.; Baldin, B.; Biery, K.; Bonfini, G.; Bossa, M.; Bottino, Bianca; Brigatti, A.; Brodsky, J.; Budano, F.; Bussino, Severino; Cadeddu, Matteo; Cadonati, L.; Cadoni, M.; Calaprice, F.; Canci, N.; Candela, A.; Cao, H.; Cariello, M.; Carlini, Macro; Catalanotti, Sergio; Cavalcante, P.; Chepurnov, A.; Cocco, A. G.; Covone, G.; Crippa, L.; D' Angelo, D.; D' Incecco, M.; Davini, S.; De Cecco, Sandro; De Deo, M.; De Vincenzi, Mario; Derbin, A.; Devoto, A.; Di Eusanio, F.; Di Pietro, Giuseppe; Edkins, E.; Empl, Anton; Fan, A.; Fiorillo, G.; Fomenko, K.; Forster, G.; Franco, D.; Gabriele, F.; Galbiati, C.; Giganti, C.; Goretti, A.; Granato, Francesco; Grandi, L.; Gromov, M.; Guan, M. Y.; Guardincerri, Y.; Hackett, B.; Herner, K.; Hungerford, Edward; Ianni, Al.; Ianni, An.; James, I.; Jollet, C.; Keeter, K.; Kendziora, C.; Kobychev, V.; Koh, G.; Korablev, D.; Korga, G.; Kubankin, Alexander; Li, X.; Lissia, M.; Lombardi, P.; Luitz, S.; Ma, Y. Q.; Machulin, I.; Mandarano, A.; Mari, S. M.; Maricic, J.; Marini, L.; Martoff, J.; Meregaglia, A.; Meyers, P. D.; Miletic, T.; Milincic, R.; Montanari, D.; Monte, Alissa; Montuschi, M.; Monzani, M. E.; Mosteiro, P.; Mount, B.; Muratova, V.; Musico, P.; Napolitano, James; Nelson, A.; Odrowski, S.; Orsini, M.; Ortica, F.; Pagani, L.; Pallavicini, Marco; Pantic, E.; Parmeggiano, S.; Pelczar, K.; Pelliccia, N.; Perasso, S.; Pocar, A.; Pordes, S.; Pugachev, D.; Qian, H.; Randle, K.; Ranucci, Gioacchino; Razeto, A.; Reinhold, B.; Renshaw, Andrew; Romani, A.; Rossi, B.; Rossi, N.; Rountree, S. D.; Sablone, D.; Saggese, P.; Saldanha, R.; Sands, W.; Sangiorgio, Samuele; Savarese, Claudio; Segreto, E.; Semenov, D.; Shields, E.; Singh, Parth; Skorokhvatov, Mikhail; Smirnov, Oleg; Sotnikov, Albert; Stanford, Chris; Suvorov, Yura; Tartaglia, Roberto; Tatarowicz, John; Testera, Gemma; Tonazzo, Alessandra; Trinchese, P.; Unzhakov, Eugenii; Vishneva, Alina; Vogelaar, R. B.; Wada, Masayuki; Walker, Susan E.; Wang, H.; Wang, Y.; Watson, A. W.; Westerdale, S.; Wilhelmi, James; Wojcik, M.; Xiang, Xin; Xu, Jingke; Yang, C. G.; Yoo, J.; Zavatarelli, Sandra; Zec, Adam; Zhong, W. L.; Zhu, Chengliang; Zuzel, G.

    2016-02-01

    DarkSide is a graded experimental project based on radiopure argon, and is now, and will be, used in direct dark matter searches. The present DarkSide-50 detector, operating at the Gran Sasso National Laboratory, is a dual-phase, 50 kg, liquid argon time-projection-chamber surrounded by an active liquid scintillator veto. It is designed to be background free in 3 years of operation. DS-50 performances, when filled with atmospheric argon, are reported. However DS-50 filled with underground argon, shows impressive reduction of the 39Ar isotope. The application of this powerful technology in a future generation of the DarkSide program is discussed.

  9. Side effects of retinoid therapy on the quality of vision

    Directory of Open Access Journals (Sweden)

    Bergler-Czop Beata

    2016-12-01

    Full Text Available Retinoids are compounds chemically related to vitamin A, which are frequently used in dermatological practice (1. They are characterized by numerous mechanisms of action leading to normalization of keratinocyte proliferation and maturation. They have anti-seborrhoeic, immunomodulatory and anti-inflammatory effects (1, 2. A number of side effects to retinoid treatment have been recorded; one group of such side effects relates to eyes and vision. Dry eye syndrome and blepharoconjunctivitis are the most common side effects, appearing in 20-50 % of patients treated with retinoids. They often contribute to the occurrence of other side-effects such as eye discomfort and contact lens intolerance. Due to the widespread use in clinical practice, the adverse effects, including ocular side effects, should be studied. To confirm the variety of adverse effects of retinoids, several case reports of rare side-effects are presented.

  10. Side Effects of Hormone Therapy

    Science.gov (United States)

    ... for PCF: Many vs Cancer Contact Us Side Effects of Hormone Therapy Testosterone is the primary male ... processes in the body. The list of potential effects of testosterone loss is long: hot flashes, decreased ...

  11. Side Effects: Nausea and Vomiting

    Science.gov (United States)

    Types of nausea and vomiting caused by cancer treatment include: anticipatory, acute, and delayed. Controlling these side effects will help to prevent serious problems such as malnutrition and dehydration in people with cancer.

  12. Coping – Late Side Effects

    Science.gov (United States)

    Cancer treatment can cause late side effects that may not show up for months or years after treatment. These late effects may include heart and lung problems, bone loss, eye and hearing changes, lymphedema, and other problems

  13. Side Effects: Infection and Neutropenia

    Science.gov (United States)

    Infection and neutropenia can be serious side effects during cancer treatment. Chemotherapy can increase your risk. Learn how to prevent infection during treatment. Find out what signs and symptoms to call the doctor about.

  14. Side Effects: Hair Loss (Alopecia)

    Science.gov (United States)

    Hair loss, also called alopecia, is a side effect of cancer treatments, such as chemotherapy and radiation therapy. Learn how to cope with and manage hair loss. Listen to tips from others who have experienced hair loss.

  15. Side Effects and Their Management

    Science.gov (United States)

    ... tumors. Donate Now Subscribe for e-updates Please leave this field empty ... tumors and their treatments bring an array of possible side effects in to a patient’s life. Fatigue, cognitive changes, and mood changes are ...

  16. The Moon's near side megabasin and far side bulge

    CERN Document Server

    Byrne, Charles

    2013-01-01

    Since Luna and Lunar Orbiter photographed the far side of the Moon, the mysterious dichotomy between the face of the Moon as we see it from Earth and the side of the Moon that is hidden has puzzled lunar scientists. As we learned more from the Apollo sample return missions and later robotic satellites, the puzzle literally deepened, showing asymmetry of the crust and mantle, all the way to the core of the Moon. This book summarizes the author’s successful search for an ancient impact feature, the Near Side Megabasin of the Moon and the extensions to impact theory needed to find it. The implications of this ancient event are developed to answer many of the questions about the history of the Moon.

  17. Orientation control of photo-immobilized antibodies on the surface of azobenzene-containing polymers by the introduction of functional groups.

    Science.gov (United States)

    Mouri, Makoto; Ikawa, Taiji; Narita, Mamiko; Hoshino, Fumihiko; Watanabe, Osamu

    2010-06-11

    In our photo-induced immobilization technique for an antibody (IgG) using azopolymers, the introduction of COOH and NMe(2) into the azopolymers, which can introduce surface charges, strongly affected the immobilization properties such as the efficiency of immobilization and the activity of the immobilized IgG (i.e., the orientation of the immobilized IgG). The introduction of COOH promoted a more active orientation of the immobilized IgG. The orientation was determined during the adsorption process onto the azopolymer surface in solution before photo-immobilization, and was maintained during the photo-immobilization. The surface charge of the azopolymer appears to be an important factor for IgG orientation, which involves electrostatic interactions between its Fab and the azopolymer surface.

  18. Side effects after lumbar iohexol myelography

    International Nuclear Information System (INIS)

    Sand, T.; Stovner, L.J.; Myhr, G.; Dale, L.G.

    1990-01-01

    Side effects of iohexol lumbar myelography have been analyzed with respect to the influence of the type of radiological abnormality, sex and age in a group of 200 patients. Headache, postural headache, nausea and back/leg pain were significantly more frequent in patients without definite radiological abnormalities. Postural headache, nausea, dizziness and mental symptoms were more frequent in women, while headache, postural headache, nausea, dizziness, minor mental symptoms (i.e. anxiety or depression) and pain became less frequent with age. This pattern is similar to that reported after lumbar puncture. Young women without definite clinical signs of nerve root lesions probably have the greatest risk of experiencing side effects after iohexol lumbar myelography. (orig.)

  19. Side effects of external tooth bleaching

    DEFF Research Database (Denmark)

    Bruzell, E.M.; Pallesen, Ulla; Thoresen, N.R.

    2013-01-01

    Objective The study was performed to assess the risk of at-home and in-office bleaching procedures, and to recognise potential predictors for side effects. Design Multi-centre, questionnaire-based prospective study with follow-ups at around 14 days and around one year post-treatment. Setting......-office = 39.3% [n = 28]; p >0.05; 95% CI [OR]: 0.198‑1.102) whereas prevalence of gingival irritation was higher after in-office treatment (at-home = 14.0%; in-office = 35.7%; p effects...... attributed to the bleaching treatment in the at-home and in-office groups, respectively. Predictors for side effects were tooth sensitivity, surface loss and gingivitis when observed at inclusion. Treatment-related predictors were bleaching concentration and contact between tray and gingiva. Conclusions...

  20. Systemic side effects of locally used oxymetazoline.

    Science.gov (United States)

    Dokuyucu, Recep; Gokce, Hasan; Sahan, Mustafa; Sefil, Fatih; Tas, Zeynel Abidin; Tutuk, Okan; Ozturk, Atakan; Tumer, Cemil; Cevik, Cengiz

    2015-01-01

    The object of the study is to experimentally investigate the possible systemic side effects of Oxymetazoline including its nasal spray which has been in use for a long time both by the physicians and patients. There is no study in the literature to address the damages of oxymetazoline on the end organ. The study conducted on 2 groups of rat. Group 1 (n = 8): Control; and Group 2 (n = 8): Oxymetazoline. During 4 week, the control group was applied with 2 drops of saline water on each nasal cavity 3 times a day and the other group was applied with 2 drops of oxymetazoline HCl 3 times a day. At the end of experiment, samples from mandible, parotid and tails of the rats were taken in 10% formalin for histopathological investigations. In histopathological experiments, when compared with the control group, the oxymetazoline group showed significant increase in many of the histopathological parameters (ischemic changes: P = 0.0001; congestion: P = 0.0006; arterial thrombosis: P = Ns; PNL accumulations: P = 0.001; necrosis: P = 0.0001; and ulceration: P = 0.014). The results of histopathologic tests on the samples taken from mandible and parotid gland, in comparison with the control group, showed no significant increase (focal inflammation: P = Ns; and lymphocyte aggregation: P = Ns). Due to the damage that the long-term use of nasal spray including oxymetazoline, it may cause injury on the end organ, which we revealed in our histopathological experiments. We believe that it's essential for the physicians to provide information on the side effects of the medicine to their patients who use for a long term.

  1. Social identity performance : Extending the strategic side of SIDE

    NARCIS (Netherlands)

    Klein, Olivier; Spears, Russell; Reicher, Stephen

    This article extends the social identity model of deindividuation effects (SIDE) by considering the various ways in which relations of visibility to an audience can affect the public expression of identity-relevant norms (identity performance). It is suggested that social identity performance can

  2. EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF); Scientific Opinion on Flavouring Group Evaluation 13, Revision 2 (FGE.13 Rev2) Furfuryl and furan derivatives with and without additional side-chain substituents and heteroatoms from chemical group 14

    DEFF Research Database (Denmark)

    Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister

    The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to evaluate 27 flavouring substances in the Flavouring Group Evaluation 13, Revision 2, using the Procedure in Commission Regulation (EC) No 1565/2000. Three...

  3. Dark Side of the Universe

    CERN Document Server

    2016-01-01

    The Dark Side of the Universe (DSU) workshops bring together a wide range of theorists and experimentalists to discuss current ideas on models of the dark side, and relate them to current and future experiments. This year's DSU will take place in the colorful Norwegian city of Bergen. Topics include dark matter, dark energy, cosmology, and physics beyond the standard model. One of the goals of the workshop is to expose in particular students and young researchers to the fascinating topics of dark matter and dark energy, and to provide them with the opportunity to meet some of the best researchers in these areas .

  4. 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

    2018-03-01

    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 266 nm. Additionally, simultaneous irradiation with 266 and 532 nm laser pulses increased the trans-to-cis isomerization yield (Υt → c) by 27%. It was concluded that the increase in Υt → c was caused by the occurrence of trans-to-cis isomerization in the higher-energy singlet state (Sn), which was reached by S1 → Sn transition induced by laser pulse excitation at 532 nm. The results of this study are potentially applicable in light-driven applications such as micromachining and chemical biology tools.

  5. A multireference perturbation study of the NN stretching frequency of trans-azobenzene in nπ* excitation and an implication for the photoisomerization mechanism.

    Science.gov (United States)

    Harabuchi, Yu; Ishii, Moe; Nakayama, Akira; Noro, Takeshi; Taketsugu, Tetsuya

    2013-02-14

    A multireference second-order perturbation theory is applied to calculate equilibrium structures and vibrational frequencies of trans-azobenzene in the ground and nπ* excited states, as well as the reaction pathways for rotation and inversion mechanism in the nπ* excited state. It is found that the NN stretching frequency exhibits a slight increase at the minimum energy structure in the nπ* state, which is explained by the mixing of the NN stretching mode with the CN symmetric stretching mode. We also calculate the NN stretching frequency at several selected structures along the rotation and inversion pathways in the nπ* state, and show that the frequency decreases gradually along the rotation pathway while it increases by ca. 300 cm(-1) along the inversion pathway. The frequencies and energy variations along the respective pathways indicate that the rotation pathway is more consistent with the experimental observation of the NN stretching frequency in nπ* excitation.

  6. 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.

  7. Not all side effects associated with tricyclic antidepressant therapy are true side effects.

    Science.gov (United States)

    Thiwan, Syed; Drossman, Douglas A; Morris, Carolyn B; Dalton, Chris; Toner, Brenda B; Diamant, Nicholas E; Hu, J B; Whitehead, William E; Leserman, Jane; Bangdiwala, Shrikant I

    2009-04-01

    Patients with functional gastrointestinal disorders treated with tricyclic antidepressants sometimes report nongastrointestinal symptoms; it is unclear whether these are drug side effects or reflect a behavioral tendency to report symptoms. We evaluated whether symptoms reported before treatment with a tricyclic antidepressant (desipramine) increased in number or worsened in severity after 2 weeks of treatment and assessed the baseline factors that predispose patients to report symptoms. Female patients in a multicenter National Institutes of Health trial for functional bowel disorders completed a 15-item symptom questionnaire at baseline (before randomization), 2 weeks after they were given desipramine (n = 81) or placebo (n = 40), and at study completion (12 weeks). Patients were asked about the severity and frequency of 15 symptoms. Results were analyzed from 57 patients given desipramine who completed the questionnaires. Symptoms reported as side effects to have occurred more frequently and also worsened at week 2 in the group given desipramine included dizziness, dry mouth/thirstiness, lightheadedness, jittery feelings/tremors, and flushing. Symptoms that did not change in severity or showed improvement at week 2 in the group given desipramine included morning tiredness, nausea, blurred vision, headaches, appetite reduction, and trouble sleeping. Psychologic distress but not desipramine blood level correlated with symptom reporting. Most symptoms often attributed to side effects of desipramine were present before treatment; only a few, related to anticholinergic effects, worsened 2 weeks after treatment, suggesting that most so-called side effects were not associated specifically with desipramine use. Such symptoms might instead be associated with psychologic distress.

  8. Managing Chemotherapy Side Effects: Constipation

    Science.gov (United States)

    ... Raw or cooked vegetables, such as broccoli, corn, green beans, peas, and spinach Snacks ••Granola ••Nuts ••Popcorn •• ... gov/livehelp NCI has a series of 18 Chemotherapy Side Effects Sheets at: www.cancer.gov/chemo- ...

  9. The Dark Side of Management

    DEFF Research Database (Denmark)

    Hanlon, Gerard; Dunne, Stephen; Johnsen, Christian Garmann

    2017-01-01

    Towards the end of 2015, the ephemera collective organised, chaired and participated within two separate Q+A panels celebrating the launch of Gerard Hanlon’s The dark side of management: A secret history of management theory. The events took place in The University of Leicester’s School...

  10. The Human Side of Libraries.

    Science.gov (United States)

    Surace, Cecily J.

    This paper discusses current trends in personnel management, with emphasis on performance standards and employee evaluation. Advances in personnel management from the scientific management theory to the application of the "human side of enterprise" approach should be reflected in how library managers review personnel and operate their libraries.…

  11. The DarkSide Program

    Directory of Open Access Journals (Sweden)

    Rossi B.

    2016-01-01

    Full Text Available DarkSide-50 at Gran Sasso underground laboratory (LNGS, Italy, is a direct dark matter search experiment based on a liquid argon TPC. DS-50 has completed its first dark matter run using atmospheric argon as target. The detector performances and the results of the first physics run are presented in this proceeding.

  12. Side-View Face Recognition

    NARCIS (Netherlands)

    Santemiz, P.; Spreeuwers, Lieuwe Jan; Veldhuis, Raymond N.J.; van den Biggelaar, Olivier

    As a widely used biometrics, face recognition has many advantages such as being non-intrusive, natural and passive. On the other hand, in real-life scenarios with uncontrolled environment, pose variation up to side-view positions makes face recognition a challenging work. In this paper we discuss

  13. Finasteride and sexual side effects

    Directory of Open Access Journals (Sweden)

    Venkataram Mysore

    2012-01-01

    Full Text Available Finasteride, a 5-alpha reductase inhibitor, widely used in the medical management of male pattern hairloss, has been reported to cause sexual side effects. This article critically examines the evidence available and makes recommendations as to how a physician should counsel a patient while prescribing the drug.

  14. Side-to-side aorto-Gore-Tex central shunt.

    Science.gov (United States)

    Gates, R N; Laks, H; Johnson, K

    1998-02-01

    This report details our experience in 13 patients with a technical modification of the standard central shunt. The study was performed using a retrospective chart review approach. In our operation, the aorto-Gore-Tex (W.L. Gore & Assoc, Flagstaff, AZ) anastomosis is created in a side-to-side fashion with the free end of the Gore-Tex shunt being oversewn. All patients had echocardiographic evidence of shunt patency in the immediate postoperative period, and there have been no cases of late shunt occlusion at a mean follow-up period of 10 months. We believe this approach will yield patency rates equivalent to or better than those of the standard central shunt. The technique has the advantage of creating a short, straight-lying shunt that is less likely to kink or be injured on repeated sternotomy and in which flow may be more reliable.

  15. Side-by-side intruders within a granular flow

    Science.gov (United States)

    Caballero-Robledo, Gabriel; Cuellar-Galan, Eli A.; Clemente-Lopez, Cesar L.; Malaga, Carlos; Mandujano Sanchez, Francisco J.; Acevedo-Escalante, Manuel F.

    Lift and drag forces on side-by-side intruders within a granular flow are studied using experiments, numerical simulations and a hydrodynamic model. Regimes of attractive and repulsive lift forces are found as a function of the separation of the intruders and flow velocity. The origin of such forces is investigated by correlating them to differences in the mean value and fluctuations of flow velocity in the regions around the intruders. Numerically, our three dimensional system is studied through Discrete Element Particle simulations adapted to use a Graphics Processing Unit (GPU). The hydrodynamic model that we apply to describe the system is kinetic theory extended for dense granular flow. This work has been supported by Conacyt, Mexico, under Grant Fronteras de la Ciencia 2015-02-1178.

  16. 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

    Science.gov (United States)

    Cao, Jun; Liu, Li-Hong; Fang, Wei-Hai; Xie, Zhi-Zhong; Zhang, Yong

    2013-04-01

    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 CH3OH 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 S1 relaxation of the photo-induced E → Z process is only mildly affected by the solvent effect, the relatively slower S1 relaxation of the reverse reaction becomes even slower in the solution compared to the gas phase. The subsequent S0 dynamics from the conical intersection between S1 and S0 (CI_E) to Z is accelerated in solution compared to the gas phase because of avoided re-crossing to the S1 state, while the S0 dynamics from the conical intersection between S1 and S0 (CI_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.

  17. Finishing and polishing of the ceromer material Targis. Lab-side and chair-side methods.

    Science.gov (United States)

    Behr, M; Rosentritt, M; Leibrock, A; Schneider-Feyrer, S; Handel, G

    1999-01-01

    The aim of the study was to check four lab-side and four chair-side methods for finishing and polishing the ceromer material Targis. Eighty bar-shaped specimens (20 mm x 10 mm x 2 mm) of Vectris were produced; 72 were covered with a 2 mm (thickness) layer of the Ceromer Targis and eight samples with the composite Tetric. All specimens were ground plane parallel with 320 Silicium carbide grit sandpaper in order to start with the same level of roughness. Then the specimens were finished and polished using the following methods: (1) Artglass toolkit, (2) pumice-stone and brushes/linen brush and polishing paste P3, (3) Robinson brush/Ivoclar Universal paste and wool brush, (4) Silicone wheel and rag wheel, (5) Shofu Rainbow set, (6) Sof-Lex discs, (7) Vivadent Politip set and (8) Nupro-pastes and brushes. The surface roughness was determined with a profilometer. The arithmetical roughness value Ra was calculated. From each group one specimen was randomly chosen and sputtered with gold in order to observe the surface with a scanning electron microscope to evaluate its smoothness. The methods were ranked as followed: 2, 3 and 5 with the lowest roughness, then 8, 6, 7, 4, 1. The best ranked chair-side method (5) and the best ranked lab-side methods (2, 3) did not differ significantly between the Ra values. No difference was observed between the composite Tetric and the ceromer Targis when these materials were polished using the same method. the lab-side-methods 2 and 3 and the chair-side-method 5 can be recommended for finishing and polishing the new ceromer material Targis.

  18. Controversy over nuclear power. Behavior of two sides and media from the point of communication

    International Nuclear Information System (INIS)

    Sata, Tsutomu

    2006-01-01

    The interaction process among the four groups such as the affirmative side, the reverse side, mass media and the people for nuclear power is analyzed from the point of communication. A definition of four groups, safety of the sites and economic induction, the affirmative side aims at persuasion, the reverse side appeals to feelings, mass media takes up news to amusement, articles dramatized on the basis of the fact, persuasion with threatening has the opposite effect, personal attitude is affected by the group criterion, media brings people's interaction into focus, people have a hatred for a one-sided information, and information with sincerity touches the heart are reported. (S.Y.)

  19. Cost benefit analysis of the demand side management programs

    International Nuclear Information System (INIS)

    Schechtman, R.; Baum, M.

    1989-01-01

    The several cost and benefit components of the demand side management programs for the society groups, including the concessionaire, consumers and society as a whole are studied. The rule evaluations of management programs by demand side, used by North American concessionaire are also discussed. Finally, the numerical examples, that consolidating the concepts and rules evaluation are presented. (C.G.C.). 5 refs, 1 fig, 3 tabs

  20. 49 CFR 229.69 - Side bearings.

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 4 2010-10-01 2010-10-01 false Side bearings. 229.69 Section 229.69....69 Side bearings. (a) Friction side bearings with springs designed to carry weight may not have more than 25 percent of the springs in any one nest broken. (b) Friction side bearings may not be run in...

  1. Metabolic Side Effects of Lithium

    Directory of Open Access Journals (Sweden)

    M. Cagdas Eker

    2010-04-01

    Full Text Available Lithium is an alkaline ion being used since 19th century. After its widespread use in psychiatric disorders, observed side effects caused skepticism about its therapeutic efficacy. Despite several disadvantages, lithium is one of the indispensible drugs used in affective disorders, especially in bipolar disorder. It became a necessity for physicians to recognize its side effects since lithium is still accepted as a gold standard in the treatment of bipolar disorder. Adverse effects of chronic administration of lithium on several organ systems are widely known. In this article metabolic effects of lithium on thyroid and parathyroid glands, body mass index and kidneys will be discussed along with their mechanisms, clinical findings, possible risk factors and treatment. One of the most common side effect of lithium is hypothyroidism. It has the same clinical and biochemical properties as primary hypothyroidism and observed as subclinical hypothyroidism in the first place. Hypothyroidism, even its subclinical form, may be associated with non-response or inadequate response and is indicated as a risk factor for development of rapid cycling bipolar disorder. Therefore, hypothyroidism should be screened no matter how severe it is and should be treated with thyroid hormone in the presence of clinical hypothyroidism. Weight gain due to lithium administration disturbs the compliance to treatment and negatively affects the course of the illness. Increased risk for diabetes, hypertension, ischemic heart disease and stroke because of weight gain constitute other centers of problem. Indeed, it is of importance to determine the risk factors before treatment, to follow up the weight, to re-organize nutritional habits and to schedule exercises. Another frequent problematic side effect of lithium treatment is renal dysfunction which clinically present as nephrogenic diabetes insipidus with the common symptoms of polyuria and polydipsia. Nephrogenic diabetes

  2. Side-to-side sutureless vascular anastomosis with magnets.

    Science.gov (United States)

    Erdmann, Detlev; Sweis, Ranya; Heitmann, Christoph; Yasui, Koji; Olbrich, Kevin C; Levin, L Scott; Sharkawy, A Adam; Klitzman, Bruce

    2004-09-01

    Abbe and Payr introduced vascular techniques and devices to facilitate vessel anastomosis over a century ago. Obora published the idea of a sutureless vascular anastomosis with use of magnetic rings in 1978. The purpose of this study was to assess the performance of a new magnetic device to perform a side-to-side arteriovenous anastomosis in a dog model. Male fox hounds (25 kg) were treated preoperatively and daily postoperatively with clopidogrel bisulfate (Plavix) and aspirin. The femoral artery and vein were exposed unilaterally in 3 dogs and bilaterally in 4 dogs (n = 11 anastomoses). A 4-mm arteriotomy was performed, and 1 oval magnet 0.5 mm thick was inserted into the lumen of the artery and a second magnet was applied external to the artery, compressing and stabilizing the arterial wall to create a magnetic port. An identical venous magnetic port was created with another pair of oval magnets. When the 2 ports were allowed to approach each other, they self-aligned and magnetically coupled to complete the arteriovenous anastomosis. Patency was assessed for the first hour with direct observation, again after 9 weeks with duplex ultrasound scanning, and at 10 weeks under direct open observation. The anastomoses were explanted after 10 weeks. Hydrodynamic resistance was measured ex vivo on the final 8 anastomoses by measuring the pressure drop across an anastomosis with a known flow rate. After implantation, very high flow created visible turbulence and palpable vibration. All 11 anastomoses were patent under direct observation and palpation. Ten of 11 anastomoses were clearly patent on duplex scans, and patency of 1 anastomosis was questionable. Hydrodynamic resistance averaged 0.73 +/- 0.33 mm Hg min/mL (mean +/- SEM). Vascular anastomoses performed with magnets demonstrated feasibility; exhibited 100% patency after 10 weeks in a dog arteriovenous shunt model; lacked apparent aneurysm or other potentially catastrophic failure; demonstrated remodeling of the

  3. Photosensitive and all-optically fast-controllable photonic bandgap device and laser in a dye-doped blue phase with a low-concentration azobenzene liquid crystal.

    Science.gov (United States)

    Lin, Jia-De; Lin, Yu-Meng; Mo, Ting-Shan; Lee, Chia-Rong

    2014-04-21

    This work demonstrates the feasibility of a novel photosensitive and all-optically fast-controllable photonic bandgap (PBG) device based on a dye-doped blue phase (DDBP), embedded with a low-concentration azobenzene liquid crystal (azo-LC). PBG of the DDBP can be reversibly fast-tuned off and on with the successive illumination of a weak UV and green beams. UV irradiation can transform the trans azo-LCs into bend cis isomers, which can easily disturb LCs at the boundary between the double twisting cylinders (DTCs) and the disclinations, and, then, quickly destabilize BPI to become a BPIII-like texture with randomly-oriented DTCs. Doing so may quickly destroy the BP PBG structure. However, with the successive illumination of a green beam, the BPI PBG device can be fast-turned on, owing to the fast disappearance of the disturbance of the azo-LCs on the boundary LCs via the green-beam-induced cis → trans back isomerization. The response time and irradiated energy density for turning off (on) the BP PBG device under the UV (green) beam irradiation are only 120 ms (120 ms) and 0.764 mJ/cm(2) (2.12 mJ/cm(2)), respectively, which are a thousand-fold reduction in photoswitching a traditional cholesteric LC (CLC) PBG device based on similar experimental conditions (i.e., materials used, azo-LC concentration (1 wt%), spectral position of PBG peak, sample thickness, and temperature difference for a working temperature lower than the clearing one). The BP PBG device can significantly contribute to efforts to develop a photosensitive and all-optically fast-controlling LC laser.

  4. The design of the modular Side-By-Side HTGR

    International Nuclear Information System (INIS)

    Murata, R.E.; Gotschall, H.L.; Dilling, D.A.; Mehta, D.D.; Ducat, G.A.; Weisbrodt, I.A.

    1985-01-01

    The modular Side-By-Side (SBS) High Temperature Gas-Cooled Reactor is an innovative advanced nuclear concept developed by Interatom/KWU. The design relies on inherent, and passive safety features to prevent the release of radioactive fission products and minimizes the dependence of engineered safety systems. Key design parameters have been selected such that the SBS module can accommodate reactivity excursions and the full spectrum of loss of core heat removal events without exceeding fuel temperatures that result in the release of radioactive fission products. This eliminates the need for a high-pressure containment and filtering of the exhaust from the low leakage reactor confinement. For emergency situations each SBS module is designed to dissipate its decay heat passively to the reactor cavity cooling system which is a passive air-cooled system. Without the need for engineered safety systems to provide large capacity for emergency power, rapid reactivity shutdown, auxiliary decay heat removal, or reactor containment and with the possibility to embed the SBS module to attenuate the effects of potentially damaging earthquakes the modular SBS-HTGR is a promising system for providing safe, economical nuclear power

  5. The side-to-side fashion for individual distal coronary anastomosis using venous conduit.

    Science.gov (United States)

    Kato, Takayoshi; Tsunekawa, Tomohiro; Motoji, Yusuke; Hirakawa, Akihiro; Okawa, Yasuhide; Tomita, Shinji

    2017-04-01

    Regarding to coronary artery bypass grafting (CABG), the end-to-side anastomosis (ESA) has been performed as a gold standard. Recently, the effectiveness of the distal side-to-side anastomosis (SSA) in CABG using internal mammary artery has been reported. The benefit of SSA comparing to ESA also has been disclosed by computing simulation. However, use of SSA by venous conduit for individual CABG has not been reported. In this study, we investigated feasibility of SSA. From January 2013 to October 2014, we conducted 114 CABGs. There were 92 venous distal anastomoses without sequential anastomotic site (61 SSA and 31 ESA). The anastomosis was evaluated before discharge and at 1 year after the procedure by angiography or multi-detector row computed tomographic coronary angiography. The median values for time to anastomosis were 13 min in the two group (p = 0.89). There was no revision of anastomosis in both groups. Additional stitches for hemostasis were required significantly less in SSA than ESA (18.0 vs 45.2 %, respectively, p fashion is easy to perform and maybe beneficial in blood flow pattern.

  6. A Diffusion Model for Two-sided Service Systems

    Science.gov (United States)

    Homma, Koichi; Yano, Koujin; Funabashi, Motohisa

    A diffusion model is proposed for two-sided service systems. ‘Two-sided’ refers to the existence of an economic network effect between two different and interrelated groups, e.g., card holders and merchants in an electronic money service. The service benefit for a member of one side depends on the number and quality of the members on the other side. A mathematical model by J. H. Rohlfs explains the network (or bandwagon) effect of communications services. In Rohlfs' model, only the users' group exists and the model is one-sided. This paper extends Rohlfs' model to a two-sided model. We propose, first, a micro model that explains individual behavior in regard to service subscription of both sides and a computational method that drives the proposed model. Second, we develop macro models with two diffusion-rate variables by simplifying the micro model. As a case study, we apply the models to an electronic money service and discuss the simulation results and actual statistics.

  7. Prevalence of left-sided melanomas in an Irish population.

    LENUS (Irish Health Repository)

    de Blacam, C

    2011-04-17

    BACKGROUND: A predominance of melanomas on the left side of the body has recently been described. No associations between tumour laterality and gender, age or anatomical site have been identified. AIM: The aim of this study was to investigate the prevalence of left-sided melanomas in an Irish population and to examine potential associations with various patient and tumour characteristics. METHODS: A retrospective chart review of patients with cutaneous melanoma who were treated over a 10-year period was carried out. Lateral distribution of melanoma on either side of the body was compared using χ(2) analysis and evaluated by gender, age group, anatomic location, histologic subtype and Breslow depth. RESULTS: More melanomas occurred on the left side (57%, P = 0.015), and this finding was particularly significant in females. For both genders combined, there were no statistically significant differences in laterality by age group, anatomic location, type of melanoma and Breslow depth. There were significantly more superficial spreading melanomas on the left side in both men and women. CONCLUSIONS: This study demonstrates a predominance of left-sided melanomas in Irish patients. While a number of demographic and molecular associations have been proposed, further research is required to fully explain this phenomenon.

  8. Prevalence of left-sided melanomas in an Irish population.

    LENUS (Irish Health Repository)

    de Blacam, C

    2012-02-01

    BACKGROUND: A predominance of melanomas on the left side of the body has recently been described. No associations between tumour laterality and gender, age or anatomical site have been identified. AIM: The aim of this study was to investigate the prevalence of left-sided melanomas in an Irish population and to examine potential associations with various patient and tumour characteristics. METHODS: A retrospective chart review of patients with cutaneous melanoma who were treated over a 10-year period was carried out. Lateral distribution of melanoma on either side of the body was compared using chi(2) analysis and evaluated by gender, age group, anatomic location, histologic subtype and Breslow depth. RESULTS: More melanomas occurred on the left side (57%, P = 0.015), and this finding was particularly significant in females. For both genders combined, there were no statistically significant differences in laterality by age group, anatomic location, type of melanoma and Breslow depth. There were significantly more superficial spreading melanomas on the left side in both men and women. CONCLUSIONS: This study demonstrates a predominance of left-sided melanomas in Irish patients. While a number of demographic and molecular associations have been proposed, further research is required to fully explain this phenomenon.

  9. Side-by side intercomparison between two TCCON instruments

    Science.gov (United States)

    Feist, Dietrich G.; Griffith, David W. T.; Velazco, Voltaire A.; Deutscher, Nicholas M.

    2017-04-01

    The Total Carbon Colummn Observing Network (TCCON) observes column-averaged dry-air mole fractions of CO2, CH4, CO, N2O, and other trace gases at more than 20 stations worldwide. These measurements are the calibration basis for all current and many future satellite greenhouse-gas-observing missions. TCCON's goal is to provide the most precise and accurate data with uncertainties better than 0.25%. Especially inter-station biases in the network are critical and should be reduced to a minimum. TCCON uses Fourier Transform Spectrometers (FTS) which are comparatively large and expensive instruments that are not easily moved around. In the network, the typical distance between TCCON stations is hundreds to thousands of kilometers. Therefore, opportunities to directly compare the performance of TCCON instruments are very rare. In 2010, the TCCON instrument from the Max Planck Institute for Biogeochemistry (MPI-BGC) in Jena, Germany, was set up close to a TCCON instrument at the University of Wollongong, Wollongong, Australia, for six months. This was part of a test campaign before the final deployment of the MPI-BGC instrument to Ascension Island. Due to problems with the acquisition and processing of TCCON data at the time, the results of the intercomparison were inconclusive at first. Spectroscopic artifacts known as ghosts affected TCCON data until 2011. The ghosts created relatively large biases between individual instruments that were in the range of TCCON's precision and accuracy goals. The ghost problem was fixed by a hardware upgrade for all TCCON instruments in 2011 but still remained in older data. Only with the latest TCCON processing software GGG2014, the ghosts could finally be removed from the pre-2011 TCCON data. Therefore, a detailed side-by-side intercomparison between the two TCCON instruments at Wollongong in 2010 has now become possible.

  10. Comparison of Breastfeeding Outcomes Between Using the Laid-Back and Side-Lying Breastfeeding Positions in Mothers Delivering by Cesarean Section: A Randomized Controlled Trial.

    Science.gov (United States)

    Puapornpong, Pawin; Raungrongmorakot, Kasem; Laosooksathit, Wipada; Hanprasertpong, Tharangrut; Ketsuwan, Sukwadee

    2017-05-01

    The breastfeeding position routinely used following a cesarean section is the side-lying position. However, there have been few studies about the effect of breastfeeding positions, including laid-back position on breastfeeding outcomes. To compare the breastfeeding outcomes between using laid-back and side-lying breastfeeding positions in mothers delivering by cesarean section. A randomized controlled trial was conducted. The postpartum mothers delivering by cesarean section who delivered term newborns were randomly assigned to learn the use of a laid-back or side-lying breastfeeding position. The breastfeeding outcomes were assessed by LATCH scores at the second day postpartum and exclusive breastfeeding rates during the 6-week postpartum period. The mother's satisfaction of each breastfeeding position was collected before discharge from the hospital. The data from 152 postpartum mothers delivering by cesarean section were available for analysis, 76 from the laid-back position group and 76 from side-lying position group. The baseline characteristics of both groups were similar. There were no statistically significant differences of the breastfeeding outcomes, LATCH scores at the second day postpartum and the exclusive breastfeeding rates during the 6-week postpartum period. But the mothers had expressed more satisfaction from the side-lying than the laid-back position. Among the mothers who delivered by cesarean section, the use of the laid-back breastfeeding position had not shown different breastfeeding outcomes from the side-lying breastfeeding position. It might be an alternative breastfeeding position, which can be taught for mothers delivering by cesarean section along with the side-lying position.

  11. Simultaneous in vivo truncation of pectic side chains

    DEFF Research Database (Denmark)

    Øbro, Jens; Borkhardt, Bernhard; Harholt, Jesper

    2009-01-01

    . These modifications often prevent gelation, which has been a major functional requirement of commercial pectins until recently. We have previously shown that modification of pectin is possible through heterologous expression of pectin degrading enzymes in planta. To test the effect of simultaneous modification......Despite the wide occurrence of pectin in nature only a few source materials have been used to produce commercial pectins. One of the reasons for this is that many plant species contain pectins with high levels of neutral sugar side chains or that are highly substituted with acetyl or other groups...... of the two main neutral pectic side chains in pectic rhamnogalacturonan I (RGI), we constitutively expressed two different enzymes in Arabidopsis thaliana that would either modify the galactan or the arabinan side chains, or both side chains simultaneously. Our analysis showed that the simultaneous...

  12. Side effects after diagnostic lumbar puncture and lumbar iohexol myelography

    International Nuclear Information System (INIS)

    Sand, T.; Stovner, L.J.; Salvesen, R.; Dale, L.

    1987-01-01

    A prospective, controlled study was performed to compare side effect incidences after lumbar iohexol myelography (n=97) and diagnostic lumbar puncture (n=85). No significant side effect incidence differences (iohexol vs. controls) were found regarding number of patients with any side effect (63 vs. 73%), headache (44 vs. 54%), nausea, dizziness, visual, auditory, or psychic symptoms. Early-onset headache occurred significantly more often in the iohexol group (16 vs 5%), while postural headache occurred most frequently after lumbar puncture (25 vs. 41%). These results suggest that apart from the slight early-onset headache, most side effets after lumbar iohexol myelography are related to the puncture per se, not to the contrast agent. (orig.)

  13. What side effects are problematic for patients prescribed antipsychotic medication? The Maudsley Side Effects (MSE) measure for antipsychotic medication.

    Science.gov (United States)

    Wykes, T; Evans, J; Paton, C; Barnes, T R E; Taylor, D; Bentall, R; Dalton, B; Ruffell, T; Rose, D; Vitoratou, S

    2017-10-01

    Capturing service users' perspectives can highlight additional and different concerns to those of clinicians, but there are no up to date, self-report psychometrically sound measures of side effects of antipsychotic medications. Aim To develop a psychometrically sound measure to identify antipsychotic side effects important to service users, the Maudsley Side Effects (MSE) measure. An initial item bank was subjected to a Delphi exercise (n = 9) with psychiatrists and pharmacists, followed by service user focus groups and expert panels (n = 15) to determine item relevance and language. Feasibility and comprehensive psychometric properties were established in two samples (N43 and N50). We investigated whether we could predict the three most important side effects for individuals from their frequency, severity and life impact. MSE is a 53-item measure with good reliability and validity. Poorer mental and physical health, but not psychotic symptoms, was related to side-effect burden. Seventy-nine percent of items were chosen as one of the three most important effects. Severity, impact and distress only predicted 'putting on weight' which was more distressing, more severe and had more life impact in those for whom it was most important. MSE is a self-report questionnaire that identifies reliably the side-effect burden as experienced by patients. Identifying key side effects important to patients can act as a starting point for joint decision making on the type and the dose of medication.

  14. THE TWO SIDES OF MONEY LAUNDERING

    Directory of Open Access Journals (Sweden)

    Corina – Maria ENE

    2014-12-01

    Full Text Available The mainly goal of money laundering is to carry out more and more illegal economic transactions or activities to produce individual or groups gains and then to legitimate them. Money laundering converts illicit source of money generated by criminal activities in order to hide the connection between money and their original illegal activities. This is one of money laundering side. The second side implies corruption. While money laundering is a passing channel for illicit funds due to its criminal origin source, such funds may derive from corruption offences. All corruption’s forms represent the most important illicit funds branches for money laundering process. Corrupt people methods used to exploit the national and international financial system reflect the relationship between those two criminal activities. Criminals achieve their personal interests by hiding their corruption proceeds and transfer these gains to official economies. Corruption spread in any society entails money laundering spread, and the converse, too. There is a quite “indecent” relationship between money laundering and corruption. This paper tries to identify the multiple connections between the two phenomenons showing the negative impacts these criminal behaviours are having on the national and international economy. We conclude by highlighting the necessity of a multidisciplinary approach in order to fight against money laundering and corruption by integrating these problem frameworks at national level. International community must focus their resources on money laundering and corruption risks areas and maximize their response impact.

  15. The dark side of technology

    CERN Document Server

    Townsend, Peter

    2016-01-01

    Technological progress comes with a dark side where good ideas and intentions produce undesirable results (extreme downsides include atomic and biological weapons). The many and various unexpected outcomes of technology span humorous to bizarre, to situations that threaten human survival. Development can be positive for some, but negative and isolating for others (e.g. older or poorer people). Progress is often transient, as faster electronics and computers dramatically shorten retention time of data, knowledge, and information loss (e.g. even photos may be unreadable within a generation). Progress and globalization are also destroying past languages and cultures. Advances cut across all areas of science and life, and the scope is vast from biology, medicine, agriculture, transport, electronics, computers, long-range communications, to a global economy. Reliance on technology causes unexpected technology-driven vulnerability to natural events (e.g. intense sunspot activity) that could annihilate advanced soci...

  16. Insidious Side Effects of Design

    DEFF Research Database (Denmark)

    Vissonova, Karina

    2015-01-01

    The purpose of this paper is to propose a way of using the concept of sustainability in design of technical artefacts. Given the recent efforts in designing a more sustainable environment of the artificial, there is a need for an explication of the concept of sustainability as characteristic...... to the design of technical artefacts. I argue that technical artefacts are designed as sustainable based on the extent side effects are addressed with the design. I present necessary and sufficient conditions in the presence of which the design of technical artefacts falls under the concept of sustainability...... in design, and argue for the usefulness of the resulting conception of sustainability. The proposed paper is a philosophical approach to a conceptual analysis and as such is aimed at contributing to the epistemology of design....

  17. Three entropic classes of side chain in a globular protein

    Energy Technology Data Exchange (ETDEWEB)

    Glass, Dennis C. [Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Krishnan, Marimuthu [International Institute of Information Technology, Hyderbad (India); Smith, Jeremy C. [Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Baudry, Jerome Y. [Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2013-02-19

    The relationship between the NMR methyl group axial order parameter and the side chain conformational entropy is investigated in inhibitor-bound and apo human HIV protease using molecular dynamics simulation. Three distinct entropic classes of methyl-bearing side chains, determined by the topological distance of the methyl group from the protein backbone (i.e., the number of -bonds between the C and the carbon of the CH3 group), are revealed by atomistic trajectory analyses performed in the local frame of reference of individual methyl probes. The results demonstrate that topologically equivalent methyl groups experience similar nonbonded microenvironments regardless of the type of residues to which they are attached. Similarly, methyl groups that belong to the same side chain but that are not topologically equivalent exhibit different thermodynamic and dynamic properties. As a result, the two-parameter classification (based upon entropy and methyl axial order parameter) of side chains described here permits improved estimates of the conformational entropies of proteins from NMR motional parameters.

  18. Client-Side Monitoring for Web Mining.

    Science.gov (United States)

    Fenstermacher, Kurt D.; Ginsburg, Mark

    2003-01-01

    Discusses mining Web data to draw conclusions about Web users and proposes a client-side monitoring system that supports flexible data collection and encompasses client-side applications beyond the Web browser to incorporate standard office productivity tools. Highlights include goals for client-side monitoring; framework for user monitoring,…

  19. Cutaneous side effects of chemotherapy in pediatric oncology patients.

    Science.gov (United States)

    Ceylan, Can; Kantar, Mehmet; Tuna, Arzu; Ertam, Ilgen; Aksoylar, Serap; Günaydın, Aslı; Çetingül, Nazan

    2015-01-01

    Pediatric oncology patients can present with various skin lesions related to both primary disease and immunosuppressive treatments. This study aimed to evaluate the cutaneous side effects of chemotherapy in pediatric oncology patients. Sixty-five pediatric oncology patients who were scheduled to undergo chemotherapy from May 2011 to May 2013 were included in the study. Three patients were excluded from the results, as 2 patients died during treatment and 1 patient withdrew from the study; therefore, a total of 62 patients were evaluated for mucocutaneous findings. Patients were grouped according to their oncological diagnoses and a statistical analysis was performed. There was no statistical significance in the incidence of cutaneous side effects of chemotherapy among the different diagnostic groups. Awareness among dermatologists of the possible cutaneous side effects of chemotherapy in pediatric patients and their causes can promote early diagnosis and treatment in this patient population.

  20. SIDE EFFECTS OF TUBERCULOSIS TREATMENT WITH FIXED-DOSE COMBINATIONS.

    Science.gov (United States)

    Zhang, H Q; Xi, X E; Wang, Y L; Han, W; Zhang, C X; Jiao, J H

    2015-01-01

    This paper aimed to explore the therapeutic effect and safety of Fixed-dose Combinations (FDCs) on tuberculosis. A computer search was carried out to review the literature related to clinical randomized controlled trials (RCTs) and clinical controlled trails (CCTs) on the curative effect and safety of treating pulmonary tuberculosis with FDCs. The results demonstrated that, in the 22 studies examined, comparison of sputum negative conservation rate of treating smear-positive pulmonary tuberculosis with FDCs and single drug, the relative risk (RR) value and 95% confidence interval (CI) were 1.02 (1.01, 1.03) and 1.01 (1.00, 1.02), respectively, at the end of the 2nd month and 6th month (P0.05). No statistically significant differences were found between the two groups in total occurrence of the rates of side effects pertaining to skin reaction, gastrointestinal tract side reaction, occurrence rate of liver and gall side reaction or occurrence rate of drug withdrawal because of side effects (P>0.05). After sensitivity analysis, it was found that occurrence rate of gastrointestinal tract side effects and occurrence rate of liver and gall side effects were unstable. All the findings suggest that the curative effect of treating tuberculosis with FDCs is better than that of a single drug. More reliable evidence is required since the safety evaluation results are not stable.

  1. Long-term side effects of glucocorticoids.

    Science.gov (United States)

    Oray, Merih; Abu Samra, Khawla; Ebrahimiadib, Nazanin; Meese, Halea; Foster, C Stephen

    2016-01-01

    Glucocorticoids represent the standard therapy for reducing inflammation and immune activation in various diseases. However, as with any potent medication, they are not without side effects. Glucocorticoid-associated side effects may involve most major organ systems. Musculoskeletal, gastrointestinal, cardiovascular, endocrine, neuropsychiatric, dermatologic, ocular, and immunologic side effects are all possible. This article analyzes English-language literature and provides an update on the most recent literature regarding side effects of systemic glucocorticoid treatment. The risk/benefit ratio of glucocorticoid therapy can be improved by proper use. Careful monitoring and using appropriate preventive strategies can potentially minimize side effects.

  2. A Typology of Multi-sided Platforms

    DEFF Research Database (Denmark)

    Staykova, Kalina Stefanova; Damsgaard, Jan

    2015-01-01

    In this paper we address how the composition of a platform impacts the platform’s business model. By platform’s business model we mean platform features, platform architecture and platform governance. To this end, we construct the Platform Business Model Framework. We apply the framework to three...... which evolved several steps into being multi-sided (Facebook). Our analysis shows a structural difference between one-sided, two-sided and multi-sided platforms and that platforms consist of a core and potentially also a periphery. The sides of a platform and the ties which connect them can be arranged...

  3. 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.

  4. The Other Side of Rapport: Data Collection Mode and Interviewer ...

    African Journals Online (AJOL)

    AJRH Managing Editor

    SHORT REPORT. The Other Side of Rapport: Data Collection Mode and Interviewer. Gender Effects on Sexual Health Reporting in Ghana. Justina Agula. 1. , Jennifer B. Barrett*. 2 and Hilde Tobi. 3. Project Fives Alive, National Catholic Health Service1; Independent research consultant; Research Methodology Group,.

  5. Chair side simple caries activity test: Ora test.

    Science.gov (United States)

    Bhasin, S; Sudha, P; Anegundi, R T

    2006-06-01

    Oratest, a caries activity test was performed on 48 school going children of Mangalore city to estimate efficacy of the test. High statistical significance was found when the means of control and test group were compared [gamma = 0.913]. The Oratest is found to be a simple chair side, less time consuming and inexpensive caries activity test.

  6. Distributed video coding with multiple side information

    DEFF Research Database (Denmark)

    Huang, Xin; Brites, C.; Ascenso, J.

    2009-01-01

    Distributed Video Coding (DVC) is a new video coding paradigm which mainly exploits the source statistics at the decoder based on the availability of some decoder side information. The quality of the side information has a major impact on the DVC rate-distortion (RD) performance in the same way...... the quality of the predictions had a major impact in predictive video coding. In this paper, a DVC solution exploiting multiple side information is proposed; the multiple side information is generated by frame interpolation and frame extrapolation targeting to improve the side information of a single...... estimation mode. Compared with the best available single side information solutions, the proposed DVC solution with multiple side information robustly improves the RD performance for the set of test sequences....

  7. Synthesis and Characterization of Novel Dendrons Bearing Amino-Nitro-Substituted Azobenzene Units and Oligo(ethylene glycol Spacers: Thermal, Optical Properties, Langmuir Blodgett Films and Liquid-Crystalline Behaviour

    Directory of Open Access Journals (Sweden)

    Ernesto Rivera

    2013-01-01

    Full Text Available In this work, we report the synthesis and characterization of a novel series of first and second generation Fréchet type dendrons bearing amino-nitro substituted azobenzene units and tetra(ethylene glycol spacers. These compounds were fully characterized by FTIR, 1H and 13C-NMR spectroscopies, and their molecular weights were determined by MALDI-TOF-MS. The thermal properties of the obtained dendrons were studied by TGA and DSC and their optical properties by absorption spectroscopy in solution and cast film. Molecular calculations were performed in order to determine the optimized geometries of these molecules in different environments. Besides, Langmuir and Langmuir Blodgett films were prepared with the first generation dendrons that were shown to be amphiphilic. Finally, some of the dendrons showed a liquid crystalline behaviour, which was studied by light polarized microscopy as a function of the temperature in order to determine the transition temperatures and the structure of the mesophase.

  8. Solvent Exchange Rates of Side-chain Amide Protons in Proteins

    International Nuclear Information System (INIS)

    Rajagopal, Ponni; Jones, Bryan E.; Klevit, Rachel E.

    1998-01-01

    Solvent exchange rates and temperature coefficients for Asn/Gln side-chain amide protons have been measured in Escherichia coli HPr. The protons of the eight side-chain amide groups (two Asn and six Gln) exhibit varying exchange rates which are slower than some of the fast exchanging backbone amide protons. Differences in exchange rates of the E and Z protons of the same side-chain amide group are obtained by measuring exchange rates at pH values > 8. An NOE between a side-chain amide proton and a bound water molecule was also observed

  9. Controlled amino-functionalization by electrochemical reduction of bromo and nitro azobenzene layers bound to Si(111) surfaces.

    Science.gov (United States)

    Ullien, Daniela; Thüne, Peter C; Jager, Wolter F; Sudhölter, Ernst J R; de Smet, Louis C P M

    2014-09-28

    4-Nitrobenzenediazonium (4-NBD) and 4-bromobenzenediazonium (4-BBD) salts were grafted electrochemically onto H-terminated, p-doped silicon (Si) surfaces. Atomic force microscopy (AFM) and ellipsometry experiments clearly showed layer thicknesses of 2-7 nm, which indicate multilayer formation. Decreasing the diazonium salt concentration and the reaction time resulted in a smaller layer thickness, but did not prevent the formation of multilayers. It was demonstrated, mainly by X-ray photoelectron spectroscopy (XPS), that the diazonium salts not only react with the H-terminated Si surface, but also with electrografted phenyl groups via azo-bond formation. These azo bonds can be electrochemically reduced at Ered = -1.5 V, leading to the corresponding amino groups. This reduction resulted in a modest decrease in layer thickness, and did not yield monolayers. This indicates that other coupling reactions, notably a biphenyl coupling, induced by electrochemically produced phenyl radicals, take place as well. In addition to the azo functionalities, the nitro functionalities in electrografted layers of 4-NBD were independently reduced to amino functionalities at a lower potential (Ered = -2.1 V). The presence of amino functionalities on fully reduced layers, both from 4-NBD- and 4-BBD-modified Si, was shown by the presence of fluorine after reaction with trifluoroacetic anhydride (TFAA). This study shows that the electrochemical reduction of azo bonds generates amino functionalities on layers produced by electrografting of aryldiazonium derivatives. In this way multifunctional layers can be formed by employing functional aryldiazonium salts, which is believed to be very practical in the fabrication of sensor platforms, including those made of multi-array silicon nanowires.

  10. Oseltamivir efficacy, side effects, and safety in children with influenza

    Directory of Open Access Journals (Sweden)

    Eun Sun Seo

    2010-01-01

    Full Text Available Purpose : Although oseltamivir is widely used for treatment of influenza, few clinical studies of its efficacy and resistance have been performed in Korea. We evaluated the safety, side effects, and efficacy of oseltamivir treatment in Korean pediatric patients. Methods : We analyzed 321 children diagnosed with influenza at Busan St. Mary's Medical Center, Korea, between January 2008 and June 2008 (first study period and November 2008 and January 2009 (second study period. Patients were divided into two groups: those receiving oseltamivir treatment for 5 days and those receiving only symptomatic treatment. We investigated clinical symptoms, side effects, and resistance to oseltamivir. We also identified influenza strains and evaluated resistance to oseltamivir using an influenza virus culture. Results : One hundred eighty-six patients were assigned to the treatment group, and 135 were assigned to the control group. The treatment group showed shorter admission duration (4.4 days compared with controls (5.0 days (P=0.000 and had fewer lower respiratory tract complications compared with controls (P&lt;0.05. No significant statistical difference in the virus antigenic type was observed between the groups. In the first study period, virus culture showed influenza B (41.7% vs. 49.6%, A/H3N2 (7.9% vs. 8.4%, and A/H1N1 (9.4% vs. 6.5%. In the second study period, only A/H1N1 (55.3% vs. 50.0% was isolated, except for one case of A (H3N2 in the treatment group. No differences in short- and long-term side effects, including neuropsychologic side effects, were noted between groups. There was no resistance to oseltamivir before or after treatment in the first study period. Conclusion : Based on our results, we suggest that osetalmivir therapy in pediatric patients is effective.

  11. Synthesis and characterization of novel liquid-crystalline azo-dyes bearing two amino-nitro substituted azobenzene units and a well-defined, oligo(ethylene glycol) spacer

    Energy Technology Data Exchange (ETDEWEB)

    Caicedo, Carolina [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria, C.P. 04510 Mexico D.F. (Mexico); Rivera, Ernesto, E-mail: riverage@iim.unam.mx [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria, C.P. 04510 Mexico D.F. (Mexico); Valdez-Hernandez, Yazmin; Carreon-Castro, Maria del Pilar [Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria, C.P. 04510 Mexico D.F. (Mexico)

    2011-10-17

    Highlights: {yields} Novel dyes containing azobenzene and oligo(ethylene glycol) were synthesized. {yields} Absorption spectra of RED-PEG dyes in CHCl{sub 3} showed {lambda}{sub max} = 440-480 nm. {yields} Absorption spectra of RED-PEG dyes in film revealed the formation of H-aggregates. {yields} Their liquid-crystalline behaviour was confirmed by light polarized microscopy. {yields} These liquid-crystalline dyes can form Langmuir films on the air-water interface. - Abstract: Four novel liquid-crystalline azo-dyes bearing two amino-nitro substituted azobenzene units linked by a well-defined oligo(ethylene glycol) spacer (DIRED-PEG series): (E)-N,N'-(2,2'-oxybis(ethane-2,1-diyl))bis(N-methyl-4-((E)-(4-nitrophenyl) diazenyl) benzenamine) (DIRED-PEG-2), (E)-N,N'-(2,2'-(ethane-1,2-diylbis(oxy)) bis(ethane-2,1-diyl)) bis(N-methyl-4-((E)-(4-nitrophenyl) diazenyl) benzenamine) (DIRED-PEG-3), (E)-N,N'-(2,2'-(2,2'-oxybis (ethane-2,1-diyl) bis(oxy)) bis(ethane-2,1-diyl)) bis(N-methyl-4-((E)-(4-nitrophenyl) diazenyl) benzenamine) (DIRED-PEG-4) and N1,N17-dimethyl-N1,N17-bis (4-((E)-(4-nitrophenyl) diazenyl) phenyl)-3,6,9,12,15-pentaoxaheptadecane-1,17-diamine (DIRED-PEG-6) have been synthesized. These dyes were fully characterized by FTIR, {sup 1}H and {sup 13}C NMR spectroscopies, and their thermal and optical properties were studied. Besides, the liquid-crystalline behaviour of these compounds was monitored in function of the temperature by light polarized microscopy. Finally, Langmuir films were prepared with these dyes.

  12. Sexual side effects induced by psychotropic drugs

    DEFF Research Database (Denmark)

    Kristensen, Ellids

    2002-01-01

    The majority of psychotropic drugs entail sexual side effects. The sexual side effects may reduce quality of life and may give rise to non-compliance. For example, 30-60 per cent of patients treated with antidepressants are known to develop a sexual dysfunction. However, some psychotropic drugs...... with no or very few sexual side effects have begun to emerge. The treatment of sexual side effects induced by psychotropic drugs may consist of: modified sexual habits, reduction in dosage, switching to another medication, possibly in combination with different psychotropic agents, other varieties...

  13. Anticipating drug side effects by comparative pharmacology.

    Science.gov (United States)

    Garcia-Serna, Ricard; Mestres, Jordi

    2010-10-01

    Anticipating the likely side effect profile of drugs is an aspect of key importance in current drug discovery, development and marketing. It was recently shown that drug pairs having similar side effect profiles had also affinity for a common target. Acknowledging that most drugs have a rich polypharmacology, we provide proof that drugs related by side effect similarity have in fact affinities for multiple common targets beyond their primary targets and set the basis for the use of comparative pharmacology to anticipate drug side effects. Nomenclature issues to be able to identify and properly store drugs, targets and side effects from multiple public sources; the construction of drug networks from side effect similarity and the inference of common targets among them; polypharmacology and data completeness; methods for in silico target profiling; and comparative pharmacology and inference of common side effects. The reader is provided with a detailed step-by-step analysis of the entire process from predicting the target profile of a compound to anticipating its side effect profile, and a discussion on the particular needs and limitations found at each stage of the process through illustrative examples. Comparing preclinical pharmacology data obtained in vitro but also predicted in silico using modern virtual screening methods represents an attractive strategy to anticipate clinical drug side effects.

  14. Demand Side Management Performance Evaluation for Commercial Enterprises

    Directory of Open Access Journals (Sweden)

    Jun Dong

    2016-10-01

    Full Text Available Demand Side Management in power systems plays an important role in ensuring a reliable power supply and protecting the environment. Demand Side Management in the commercial sector is vital for sustainable development during China’s industrial restructuring. A hybrid multi-criteria decision making framework for evaluating Demand Side Management performance of commercial enterprises is proposed from a sustainability perspective. A fuzzy Analytic Hierarchy Process is employed to determine the weights of the criteria and a fuzzy technique for order preference by similarity to an ideal solution is applied to rank Demand Side Management performance. An evaluation index system is built, containing economic, social, environmental and technical criteria associated with 15 sub-criteria. Four groups of expert panels from government departments, research institutions, electricity utilities and commercial enterprises gave judgments on criteria weights and criteria performances for alternatives. The effectiveness of the proposed hybrid framework was demonstrated through a case study in Beijing, in which Demand Side Management performances of four alternatives were ranked. Sensitivity analysis results indicate that the hybrid framework is robust.

  15. Estimation of K(OA) values of 209 polychlorinated trans-azobenzenes by PM6 and DFT methods.

    Science.gov (United States)

    Wilczyńska-Piliszek, Agata J; Piliszek, Sławomir; Falandysz, Jerzy

    2012-01-01

    The octanol-air partition coefficients (K(OA)) of all 209 PCt-ABs were determined computationally to fill gaps on their environmentally relevant physical and chemical properties. These properties have been determined using two computational approaches: the semi-empirical quantum chemistry method for property parameterization (PM6) of the molecular orbital package (MOPAC) and density functional theory (DFT) method using B3LYP functional and 6-311++G** basis set in Gaussian 03 software and artificial neural network (ANN) predicting abilities. Both computational methods enabled estimation of log K(OA) partition coefficients of PCt-ABs with a similar accuracy and precision. The PM6 method compared to DFT was highly superior because it requires much less time, manpower and cost of hardware. The determined log K(OA) values of the investigated PCt-ABs for standard condition (25 °C) varied between 8.30 and 8.75 for Mono-; 8.71 and 9.92 for Di-; 9.58 and 10.72 for Tri-; 10.11 and 11.34 for Tetra-, 10.83 and 11.85 for Penta-; 11.24 and 12.36 for Hexa-; 11.87 and 12.66 for Hepta-; 12.31 and 12.97 for Octa-; 12.89 and 13.21 for Nona-Ct-ABs; and 13.17- and 13.49 for Deca-Ct-AB. PCt-ABs, in view of these log K(OA) values, can be classified as compounds of relatively low (Mono-, Di- and some of Tri- Ct-ABs with values of log K(OA) around 8 to 10) environmental mobility (most of Tri- to Nona-Ct-ABs and Deca-Ct-AB homologues with values of log K(OA) >10), and with a potential to be adsorbed by soil particles. Copyright © Taylor & Francis Group, LLC

  16. Video-assisted thoracoscopic thymectomy for non-thymomatous myasthenia gravis: a right-sided or left-sided approach?

    Science.gov (United States)

    Elsayed, Hany Hasan; Gamal, Mahmoud; Raslan, Saleh; Abdel Hamid, Hossam

    2017-10-01

    A best evidence topic in thoracic surgery was written according to a structured protocol. The question addressed was in [patients undergoing video-assisted thoracoscopic thymectomy for myasthenia gravis (MG)] is a [left-sided approach] superior to a [right-sided approach] in terms of [clinical outcome]? Two hundred and fifty-nine papers were found using the reported search. In looking at both procedures, we selected studies with a sizeable number of patients performing or studying both procedures and comparing their outcome. Hence, only 4 studies represented the best evidence to answer the clinical question. The authors, journal, date, country, study type, patient group, relevant outcomes and results of these papers are tabulated. Two studies compared their clinical experience with a right-sided versus a left-sided video assisted thoracoscopic surgery thymectomy approach, while 1 study compared using a bilateral versus a unilateral right-sided approach in patients with non-thymomatous MG. The number of patients studied included 31, 107 and 103 patients, respectively. All 3 studies demonstrated no difference regarding surgical time, intraoperative blood loss, postoperative hospital stay, postoperative complications and therapeutic effects (the last study compared the 5-year complete stable remission rate). All 3 studies concluded that both approaches are feasible, effective and comparable in operative and long-term results for the treatment of non-thymomatous MG. One anatomical study compared both approaches in 10 cadavers, 5 in each group. They studied the size of the specimen resected and visualization of different anatomic sites via each approach. Visualization was superior using the left-sided approach, while a right-sided approach resulted in slightly higher chances of an incomplete resection. The study concluded that a left-sided approach achieves a better chance of radical thoracoscopic thymectomy due to anatomic considerations. In conclusion, despite 1

  17. Comparing outcomes between side-to-side anastomosis and other anastomotic configurations after intestinal resection for patients with Crohn's disease: a meta-analysis.

    Science.gov (United States)

    Guo, Zhen; Li, Yi; Zhu, Weiming; Gong, Jianfeng; Li, Ning; Li, Jieshou

    2013-04-01

    Anastomotic configurations may be a predictor of postoperative recurrence for Crohn's disease. One previous meta-analysis showed side-to-side anastomosis was associated with fewer anastomotic leaks but did not reduce postoperative recurrence rates. After 2007, more articles that found distinct results were published. We aimed to update the meta-analysis comparing outcomes between side-to-side anastomosis and other anastomotic configurations after intestinal resection for patients with Crohn's disease. A literature search that included PubMed, EMBASE, the Science Citation Index, and the Cochrane Library was conducted to identify studies up to May 2012. Trials comparing side-to-side anastomosis with other anastomotic configurations for Crohn's disease were analyzed. Sensitivity analysis and heterogeneity assessment were also performed. Eleven trials compared side-to-side with other anastomotic configurations were included. Overall, results showed a significant reduction in the overall postoperative complications [n = 777; odds ratio (OR) = 0.60; P = 0.01], but side-to-side anastomosis did not reduce the anastomotic leak rate (n = 879; OR = 0.48; P = 0.07), complications other than anastomotic leak (n = 777; OR = 0.72; P = 0.13), endoscopic recurrence rates [hazard ratio (HR) = 0.73; P = 0.07], symptomatic recurrence rates (HR = 0.74; P = 0.20), and reoperation rates for recurrence (HR = 0.37; P = 0.06). Sensitivity analysis including two randomized controlled trials found no significant differences in short-term complications between the two groups. Sensitivity analysis including nine trials comparing only stapled side-to-side anastomosis with other anastomotic configurations showed stapled side-to-side anastomosis could reduce reoperation rates (HR = 0.38; P = 0.01). Side-to-side anastomosis did not reduce short-term complications and postoperative recurrence for Crohn's disease. Stapled side-to-side anastomosis may lead to fewer reoperations needed for recurrence

  18. Lift on side by side intruders of various geometries within a granular flow

    Directory of Open Access Journals (Sweden)

    Acevedo-Escalante M. F.

    2017-01-01

    Full Text Available Obstacles within fluids have been widely used in engineering and in physics to study hydrodynamic interactions. In granular matter, objects within a granular flow have helped to understand fundamental features of drag and lift forces. In our group, we have studied numerically the flow mediated interaction between two static disks within a vertical granular flow in a two-dimensional container where the flow velocity and the distance between obstacles were varied. Attractive and repulsive forces were found depending on flow velocity and separation between intruders. The simulations evidenced a relationship between the average flow velocity in a specific section ahead of the obstacles and the attractive-repulsive lift. On the other hand, it was showed that the lift force on an object dragged within a granular medium depends on the shape of the intruder. Here we present experimental results of the interaction between two side-by-side intruders of different shapes within a vertical granular flow. We built a quasi-two-dimensional container in which we placed the intruders and using load cells we measured lift and drag forces during the discharge process for different flow velocities.

  19. European side markers effect on traffic safety

    NARCIS (Netherlands)

    Roelfsema, A.; Theeuwes, J.; Alferdinck, J.W.A.M

    1999-01-01

    In 1993 new European legislation regarding side-markers for passenger cars became effective. Volvo requested the TNO-Human Factors Research Institute (HFRI) to investigate the possible safety benefit of this European side-markers configuration. A test panel at TNO- HFRI was used to determine the

  20. Single side Emitting Transparent OLED lamp

    NARCIS (Netherlands)

    Lifka, H.; Verschuren, C.A.; Bruls, D.M.; Tanase, C.

    2011-01-01

    Transparent OLEDs offer great potential for novel applications. Preferably, the light should be emitted from one side only. This can bedone to some extent by modifying electrode thicknesses, but at the cost of reduced transparency. Here, we demonstrate a new approach tomake single side emissive

  1. Side-emitting fiber optic position sensor

    Science.gov (United States)

    Weiss, Jonathan D [Albuquerque, NM

    2008-02-12

    A side-emitting fiber optic position sensor and method of determining an unknown position of an object by using the sensor. In one embodiment, a concentrated beam of light source illuminates the side of a side-emitting fiber optic at an unknown axial position along the fiber's length. Some of this side-illuminated light is in-scattered into the fiber and captured. As the captured light is guided down the fiber, its intensity decreases due to loss from side-emission away from the fiber and from bulk absorption within the fiber. By measuring the intensity of light emitted from one (or both) ends of the fiber with a photodetector(s), the axial position of the light source is determined by comparing the photodetector's signal to a calibrated response curve, look-up table, or by using a mathematical model. Alternatively, the side-emitting fiber is illuminated at one end, while a photodetector measures the intensity of light emitted from the side of the fiber, at an unknown position. As the photodetector moves further away from the illuminated end, the detector's signal strength decreases due to loss from side-emission and/or bulk absorption. As before, the detector's signal is correlated to a unique position along the fiber.

  2. A Study of Clinicopathological Differences Between Right-sided and Left-sided Colon Cancers

    OpenAIRE

    芳賀, 駿介; 遠藤, 俊吾; 加藤, 博之; 高橋, 直樹; 吉松, 和彦; 橋本, 雅彦; 石橋, 敬一郎; 梅原, 有弘; 横溝, 肇; 梶原, 哲郎; Shunsuke, HAGA; Shungo, ENDO; Hiroyuki, KATO; Naoki, TAKAHASHI; Kazuhiko, YOSHIMATSU

    1996-01-01

    The present study was aimed to determine the clinicopathological features of cancers of the right-sided colon (cecum, ascending colon, transverse colon) and left-sided colon (descending colon, sigmoid colon) in order to help improve the efficacy of their treatment. Excluding multiple cancer cases, 364 patients with primary colon cancer underwent surgey at our department between 1974 and 1994; they comprised 171 individuals with right-sided colon cancer and 193 with left-sided colon cancer. A ...

  3. Side Effects of Chemotherapy and Radiation (For Parents)

    Science.gov (United States)

    ... Safe Videos for Educators Search English Español Side Effects of Chemotherapy and Radiation KidsHealth / For Parents / Side ... contact your doctor right away. Duration of Side Effects Most side effects go away gradually once cancer ...

  4. Footballers' movement behaviour during 2-, 3-, 4- and 5-a-side small-sided games

    NARCIS (Netherlands)

    Aguiar, Marco; Goncalves, Bruno; Botelho, Goreti; Lemmink, Koen; Sampaio, Jaime

    2015-01-01

    The aim of this study was to compare footballers' movement behaviour during 2-, 3-, 4- and 5-a-side small-sided games. Ten young professional players (age=18.0 +/- 0.67years) participated in 3 bouts of each small-sided games for 6min with 1min of active rest between bouts. Positional data were

  5. Air Quality Side Event Proposal November 2016 GEO XIII Plenary in St. Petersburg, Russia

    Science.gov (United States)

    The Group on Earth Observations (GEO), which EPA has participated in since 2003, has put out a call for Side Events for its thirteenth annual international Plenary Meeting which is in St. Petersburg, Russia this year during November, 2016. EPA has put on Side Events on Air Quali...

  6. The far-side solar magnetic index

    International Nuclear Information System (INIS)

    Hernandez, Irene Gonzalez; Jain, Kiran; Hill, Frank; Tobiska, W Kent

    2011-01-01

    Several magnetic indices are used to model the solar irradiance and ultimately to forecast it. However, the observation of such indices are generally limited to the Earth-facing hemisphere of the Sun. Seismic maps of the far side of the Sun have proven their capability to locate and track medium-large active regions at the non-visible hemisphere. We present here the possibility of using the average signal from these seismic far-side maps as a proxy to the non-visible solar activity which can complement the current front-side solar activity indices.

  7. The DarkSide Program at LNGS

    OpenAIRE

    Wright, Alex; Collaboration, for the DarkSide

    2011-01-01

    DarkSide is a direct detection dark matter program based on two phase time projection chambers with depleted argon targets. The DarkSide detectors are designed, using novel low background techniques and active shielding, to be capable of demonstrating in situ a very low level of residual background. This means that each detector in the DarkSide program should have the ability to make a convincing claim of dark matter detection based on the observation of a few nuclear recoil events. The colla...

  8. Highly conductive side chain block copolymer anion exchange membranes.

    Science.gov (United States)

    Wang, Lizhu; Hickner, Michael A

    2016-06-28

    Block copolymers based on poly(styrene) having pendent trimethyl styrenylbutyl ammonium (with four carbon ring-ionic group alkyl linkers) or benzyltrimethyl ammonium groups with a methylene bridge between the ring and ionic group were synthesized by reversible addition-fragmentation radical (RAFT) polymerization as anion exchange membranes (AEMs). The C4 side chain polymer showed a 17% increase in Cl(-) conductivity of 33.7 mS cm(-1) compared to the benzyltrimethyl ammonium sample (28.9 mS cm(-1)) under the same conditions (IEC = 3.20 meq. g(-1), hydration number, λ = ∼7.0, cast from DMF/1-propanol (v/v = 3 : 1), relative humidity = 95%). As confirmed by small angle X-ray scattering (SAXS), the side chain block copolymers with tethered ammonium cations showed well-defined lamellar morphologies and a significant reduction in interdomain spacing compared to benzyltrimethyl ammonium containing block copolymers. The chemical stabilities of the block copolymers were evaluated under severe, accelerated conditions, and degradation was observed by (1)H NMR. The block copolymer with C4 side chain trimethyl styrenylbutyl ammonium motifs displayed slightly improved stability compared to that of a benzyltrimethyl ammonium-based AEM at 80 °C in 1 M NaOD aqueous solution for 30 days.

  9. Conducting the Softer Side of Counterinsurgency

    National Research Council Canada - National Science Library

    Ransone, Bart D

    2008-01-01

    .... These changes in doctrine have forced the US military s conventional force to reconsider its use of the kinetic force and begin to understand the use of more non-kinetic means, or the softer side...

  10. Managing Chemotherapy Side Effects: Hair Loss (Alopecia)

    Science.gov (United States)

    ... C ancer I nstitute Managing Chemotherapy Side Effects Hair Loss (Alopecia) “Losing my hair was hard at first. Then ... and anywhere on your body may fall out. Hair loss is called alopecia. When will my hair start ...

  11. Neglected Side Effects After Radical Prostatectomy

    DEFF Research Database (Denmark)

    Frey, Anders Ullmann; Sønksen, Jens; Fode, Mikkel

    2014-01-01

    been shown to double the risk of OAP. PS occurs in 15-68% of RP patients. Nerve sparing and preservation of erectile function may help preserve penile length. With regard to all side effects, studies indicate that they are reduced over time. CONCLUSIONS: The sexually related side effects summarized......INTRODUCTION: A series of previously neglected sexually related side effects to radical prostatectomy (RP) has been identified over the recent years. These include orgasm-associated incontinence (OAI), urinary incontinence in relation to sexual stimulation (UISS), altered perception of orgasm......, orgasm-associated pain (OAP), penile shortening (PS), and penile deformity. AIM: The aim of this article is to conduct a systematic review of the literature regarding the above-mentioned side effects. METHODS: A predefined search strategy was applied in a thorough search of Medline, Web of science...

  12. Side Effects - Memory or Concentration Problems

    Science.gov (United States)

    Cancer treatments, such as chemo, may cause difficulty thinking, concentrating, or other cognitive problems. Learn about steps people with cancer can take to manage these side effects. See a list of helpful questions for families to ask the doctor.

  13. Side Effects: Mouth and Throat Problems

    Science.gov (United States)

    Cancer treatments may cause dental, mouth, and throat side effects such as changes in taste (dysgeusia), dry mouth (xerostomia), infections, mouth sores, pain or swelling in your mouth (oral mucositis), sensitivity to foods, and swallowing problems.

  14. Possible Side-Effects from Vaccines

    Science.gov (United States)

    ... Fever Varicella (Chickenpox) Yellow Fever Live Zoster (Shingles) Vaccine, ZVL Recombinant Zoster (Shingles) Vaccine, RZV Any vaccine can cause ... RZV side-effects What are the risks from recombinant shingles vaccine? With any medicine, including vaccines, there is a ...

  15. Side Effects of Yttrium-90 Radioembolization

    Directory of Open Access Journals (Sweden)

    Ahsun eRiaz

    2014-07-01

    Full Text Available Limited therapeutic options are available for hepatic malignancies. Image guided targeted therapies have established their role in management of primary and secondary hepatic malignancies. Radioembolization with yttrium-90 (90Y microspheres is safe and efficacious for treatment of hepatic malignancies. The tumoricidal effect of radioembolization is predominantly due to radioactivity and not ischemia. This article will present a comprehensive review of the side effects that have been associated with radioembolization using 90Y microspheres. Some of the described side effects are associated with all transarterial procedures. Side effects specific to radioembolization will also be discussed in detail. Methods to decrease the incidence of these potential side effects will also be discussed.

  16. Sexual side effects induced by psychotropic drugs

    DEFF Research Database (Denmark)

    Kristensen, Ellids

    2002-01-01

    The majority of psychotropic drugs entail sexual side effects. The sexual side effects may reduce quality of life and may give rise to non-compliance. For example, 30-60 per cent of patients treated with antidepressants are known to develop a sexual dysfunction. However, some psychotropic drugs...... of pharmacologically active substances or specific products for the treatment of sexual dysfunction such as sildenafil. Above all, it should be acknowledged that relatively few data are available in this field and in particular that there is a lack of controlled studies....... with no or very few sexual side effects have begun to emerge. The treatment of sexual side effects induced by psychotropic drugs may consist of: modified sexual habits, reduction in dosage, switching to another medication, possibly in combination with different psychotropic agents, other varieties...

  17. Side- ja turvanguamet / Indrek Süld

    Index Scriptorium Estoniae

    Süld, Indrek

    2004-01-01

    Ilmunud ka: 2003 : annual report : [Eesti Raudtee]. - Tallinn, 2004, lk. 34-35; 2003 : godovoi ottshjot : [Eesti Raudtee]. - Tallinn, 2004, lk. 34-35. Ülevaade AS-i Eesti Raudtee side- ja turvanguameti tegevusest 2003. aastal. Skeem

  18. Clooten Siding & Window, Inc. Information Sheet

    Science.gov (United States)

    Clooten Siding & Window, Inc. (the Company) is located in Bismarck, North Dakota. The settlement involves renovation activities conducted at a property constructed prior to 1978, located in Bismarck, North Dakota.

  19. The Simulation of DFIG Grid Side Converter

    Directory of Open Access Journals (Sweden)

    LU Yan-Ling

    2017-02-01

    Full Text Available Firstly,DFIG basic structure of grid side converter was analyzed according to basic principles of voltage converter, and a mathematical model of grid side converter was established in the three-phase stationary coordinate system and the two-phase rotating coordinate system respectively. Then use the grid voltage oriented vector control strategy based On dq coordinate model of the grid side converter and its essential principles and realization scheme were introduced. Finally,SVPWM,Park,control systems and other power electronics model were built in matlab/simulink,converter was simulated based On vector control strategy under rectifier state and inverter state respectively. The simulation results show that the control strategy has a good dynamic response,and by choosing the appropriate inductance,capacitance,the network side current will reach stable state quickly with smooth waveform and small harmonic,while the DC voltage will reach stable value quickly with small overshoot.

  20. Managing Chemotherapy Side Effects: Memory Changes

    Science.gov (United States)

    N ational C ancer I nstitute Managing Chemotherapy Side Effects Memory Changes What is causing these changes? Your doctor will work to find out what is causing these problems. They may be caused by ...

  1. SIDES - Segment Interconnect Diagnostic Expert System

    International Nuclear Information System (INIS)

    Booth, A.W.; Forster, R.; Gustafsson, L.; Ho, N.

    1989-01-01

    It is well known that the FASTBUS Segment Interconnect (SI) provides a communication path between two otherwise independent, asynchronous bus segments. The SI is probably the most important module in any FASTBUS data acquisition network since it's failure to function can cause whole segments of the network to be inaccessible and sometimes inoperable. This paper describes SIDES, an intelligent program designed to diagnose SI's both in situ as they operate in a data acquisition network, and in the laboratory in an acceptance/repair environment. The paper discusses important issues such as knowledge acquisition; extracting knowledge from human experts and other knowledge sources. SIDES can benefit high energy physics experiments, where SI problems can be diagnosed and solved more quickly. Equipment pool technicians can also benefit from SIDES, first by decreasing the number of SI's erroneously turned in for repair, and secondly as SIDES acts as an intelligent assistant to the technician in the diagnosis and repair process

  2. Side Stream Filtration for Cooling Towers

    Energy Technology Data Exchange (ETDEWEB)

    None

    2012-10-20

    This technology evaluation assesses side stream filtration options for cooling towers, with an objective to assess key attributes that optimize energy and water savings along with providing information on specific technology and implementation options. This information can be used to assist Federal sites to determine which options may be most appropriate for their applications. This evaluation provides an overview of the characterization of side stream filtration technology, describes typical applications, and details specific types of filtration technology.

  3. Side effects of endoscopic variceal ligation by using Indonesian Endoscopic Ligator versus Endoscopic Variceal Sclerotherapy.

    Science.gov (United States)

    Simadibrata, Marcellus; Syam, Ari F; Fauzi, Achmad; Abdullah, Murdani; Rani, Abdul A

    2011-01-01

    to investigate the side effects and survival of endoscopic variceal ligation by using Indonesian Endoscopic Ligator versus Endoscopic Variceal Sclerotherapy. we studied the medical records and endoscopy reports of patients who underwent endoscopic variceal ligation (EVL) or endoscopic sclerotherapy (EST) from January 2003 until December 2006. EST was done using ethoxysclerol injection; and ligation was done using a home-made Indonesian endoscopic ligating device. Patient characteristics, side effects of EVL and EST, as well as survival and length of stay were collected. Data of side effects was analyzed by chi-square test. there were no statistically significant differences of patients characteristics among both groups. The side effects in EVL group (29.2%) were less frequent than the EST group (60.9%) (p = 0.009). The death side effect in the EVL group (1.0%) was less frequent than in the EST group (21.7%) (pEVL and EST were 91.7% and 16.7%, respectively (pEVL had fewer side effects than EST in the treatment of esophageal varices bleeding. Death in the EVL group was lower than in the EST group.

  4. Emergency surgery for obstructing colonic cancer: a comparison between right-sided and left-sided lesions.

    Science.gov (United States)

    Faucheron, J-L; Paquette, B; Trilling, B; Heyd, B; Koch, S; Mantion, G

    2018-02-01

    Few studies compare management and outcomes of obstructive colonic cancer, depending on the tumor site. We aim to evaluate the differences in patient characteristics, tumor characteristics, and outcomes of emergency surgery for obstructive right-sided versus left-sided colonic cancers. Between 2000 and 2009, 71 consecutive patients had an emergency colectomy following strict and clear definition of obstruction in a single institution. We retrospectively analyzed pre, per, and postoperative data that were prospectively collected. There were 31 and 40 patients in the right and left group, respectively. Patients aged over 80 were more frequent in the right group (p = 0.03). At operation, ileocecal valve was less often competent in the right group (p = 0.03). The one-stage strategy was more frequent in the right group (p = 0.008). Patients in the right group had a higher rate of nodes invasion (p = 0.04). One- and two-year mortality rate in the right group had a tendency to be higher. Patients presenting with a right obstructive colonic cancer are older, have a more advanced locoregional disease, and are more often treated in a one-stage strategy than patients with a left obstructive tumor.

  5. Use of quantitative-structure property relationship (QSPR) and artificial neural network (ANN) based approaches for estimating the octanol-water partition coefficients of the 209 chlorinated trans-azobenzene congeners.

    Science.gov (United States)

    Wilczyńska-Piliszek, Agata J; Piliszek, Sławomir; Falandysz, Jerzy

    2012-01-01

    Polychlorinated azobenzenes (PCABs) can be found as contaminant by products in 3,4-dichloroaniline and its derivatives and in the herbicides Diuron, Linuron, Methazole, Neburon, Propanil and SWEP. Trans congeners of PCABs are physically and chemically more stable and so are environmentally relevant, when compared to unstable cis congeners. In this study, to fulfill gaps on environmentally relevant partitioning properties of PCABs, the values of n-octanol/water partition coefficients (log K(OW)) have been determined for 209 congeners of chloro-trans-azobenzene (Ct-AB) by means of quantitative structure-property relationship (QSPR) approach and artificial neural networks (ANN) predictive ability. The QSPR methods used based on geometry optimalization and quantum-chemical structural descriptors, which were computed on the level of density functional theory (DFT) using B3LYP functional and 6-311++G basis set in Gaussian 03 and of the semi-empirical quantum chemistry method (PM6) of the molecular orbital package (MOPAC). Polychlorinated dibenzo-p-dioxins (PCDDs), -furans (PCDFs) and -biphenyls (PCBs), to which PCABs are related, were reference compounds in this study. An experimentally obtained data on physical and chemical properties of PCDD/Fs and PCBs were reference data for ANN predictions of log K(OW) values of Ct-ABs in this study. Both calculation methods gave similar results in term of absolute log K(OW) values, while the models generated by PM6 are considered highly efficient in time spent, when compared to these by DFT. The estimated log K(OW) values of 209 Ct-ABs varied between 5.22-5.57 and 5.45-5.60 for Mono-, 5.56-6.00 and 5.59-6.07 for Di-, 5.89-6.56 and 5.91-6.46 for Tri-, 6.10-7.05 and 6.13-6.80 for Tetra-, 6.43-7.39 and 6.48-7.14 for Penta-, 6.61-7.78 and 6.98-7.42 for Hexa-, 7.41-7.94 and 7.34-7.86 for Hepta-, 7.99-8.17 and 7.72-8.20 for Octa-, 8.35-8.42 and 8.10-8.62 for NonaCt-ABs, and 8.52-8.60 and 8.81-8.83 for DecaCt-AB. These log K(OW) values

  6. Temporomandibular disorders: the habitual chewing side syndrome.

    Directory of Open Access Journals (Sweden)

    Urbano Santana-Mora

    Full Text Available BACKGROUND: Temporomandibular disorders are the most common cause of chronic orofacial pain, but, except where they occur subsequent to trauma, their cause remains unknown. This cross-sectional study assessed chewing function (habitual chewing side and the differences of the chewing side and condylar path and lateral anterior guidance angles in participants with chronic unilateral temporomandibular disorder. This is the preliminary report of a randomized trial that aimed to test the effect of a new occlusal adjustment therapy. METHODS: The masticatory function of 21 randomly selected completely dentate participants with chronic temporomandibular disorders (all but one with unilateral symptoms was assessed by observing them eat almonds, inspecting the lateral horizontal movement of the jaw, with kinesiography, and by means of interview. The condylar path in the sagittal plane and the lateral anterior guidance angles with respect to the Frankfort horizontal plane in the frontal plane were measured on both sides in each individual. RESULTS: Sixteen of 20 participants with unilateral symptoms chewed on the affected side; the concordance (Fisher's exact test, P = .003 and the concordance-symmetry level (Kappa coefficient κ = 0.689; 95% confidence interval [CI], 0.38 to 0.99; P = .002 were significant. The mean condylar path angle was steeper (53.47(10.88 degrees versus 46.16(7.25 degrees; P = .001, and the mean lateral anterior guidance angle was flatter (41.63(13.35 degrees versus 48.32(9.53 degrees P = .036 on the symptomatic side. DISCUSSION: The results of this study support the use of a new term based on etiology, "habitual chewing side syndrome", instead of the nonspecific symptom-based "temporomandibular joint disorders"; this denomination is characterized in adults by a steeper condylar path, flatter lateral anterior guidance, and habitual chewing on the symptomatic side.

  7. Endomorphisms on half-sided modular inclusions

    International Nuclear Information System (INIS)

    Svegstrup, Rolf Dyre

    2006-01-01

    In algebraic quantum field theory we consider nets of von Neumann algebras indexed over regions of the space time. Wiesbrock [''Conformal quantum field theory and half-sided modular inclusions of von Neumann algebras,'' Commun. Math. Phys. 158, 537-543 (1993)] has shown that strongly additive nets of von Neumann algebras on the circle are in correspondence with standard half-sided modular inclusions. We show that a finite index endomorphism on a half-sided modular inclusion extends to a finite index endomorphism on the corresponding net of von Neumann algebras on the circle. Moreover, we present another approach to encoding endomorphisms on nets of von Neumann algebras on the circle into half-sided modular inclusions. There is a natural way to associate a weight to a Moebius covariant endomorphism. The properties of this weight have been studied by Bertozzini et al. [''Covariant sectors with infinite dimension and positivity of the energy,'' Commun. Math. Phys. 193, 471-492 (1998)]. In this paper we show the converse, namely, how to associate a Moebius covariant endomorphism to a given weight under certain assumptions, thus obtaining a correspondence between a class of weights on a half-sided modular inclusion and a subclass of the Moebius covariant endomorphisms on the associated net of von Neumann algebras. This allows us to treat Moebius covariant endomorphisms in terms of weights on half-sided modular inclusions. As our aim is to provide a framework for treating endomorphisms on nets of von Neumann algebras in terms of the apparently simpler objects of weights on half-sided modular inclusions, we lastly give some basic results for manipulations with such weights

  8. Experimental research on end-to-side anastomosis of peripheral nerves and effect of FK506 on end-to-side anastomosis.

    Science.gov (United States)

    Yang, L M; Wu, Y X; Zhang, X P; Li, X H

    2014-01-01

    To study the effects of end-to-side anastomosis of initially-denatured nerves at different times. 60 male Wistar albino rats were used to fabricate animal models for the experiment on end-to-side anastomosis of peripheral nerves and 50 female Wistar albino rats were used to fabricate animal models for the experiment on the effect of FK506 on end-to-side anastomosis. Bilateral common peroneal nerve, tibialis anterior muscle electrophysiological and histological examinations, tibialis anterior muscle wet muscle weight determination, and motor end plate examination were performed 3 months after operation. All recovery rates of action potential, single muscle contraction force and tetanic contraction force of the FK506 experimental group are significantly higher than those of the control group and the sectional area of muscle fiber is also higher than that of the control group of normal saline. The best time for end-to-side anastomosis of nerves should be controlled within 2 weeks and the effect of end-to-side anastomosis of nerves will gradually become unsatisfactory. FK506 plays a role in promoting functional rehabilitation following nerve end-to-side anastomosis (Tab. 7, Fig. 4, Ref. 31).

  9. Energy perspectives 2035 - Volume 4, side-notes

    International Nuclear Information System (INIS)

    2007-01-01

    This comprehensive report published by the Swiss Federal Office of Energy (SFOE) presents a number of side-notes pertaining to the first three volumes of the Energy Perspectives series of reports. Various topics are discussed by the authors of the first three volumes of the perspectives in the meetings held by the Energy Perspectives Working Group. The sixteen side-notes presented here cover the following topics: General conditions, fossil resources, the influence of climate warming, CO 2 emissions trading (Joint Implementation JI and Clean Development Mechanism CDM), definition of potentials, air traffic, imported renewable electricity, hydro power, electricity cost calculation, sensitivity analysis of centralised power production facilities, heat-pumps and their power consumption, cold spells and heat-waves, risk and its perception, the 2000-Watt society and international and national energy perspectives

  10. Group X

    Energy Technology Data Exchange (ETDEWEB)

    Fields, Susannah

    2007-08-16

    This project is currently under contract for research through the Department of Homeland Security until 2011. The group I was responsible for studying has to remain confidential so as not to affect the current project. All dates, reference links and authors, and other distinguishing characteristics of the original group have been removed from this report. All references to the name of this group or the individual splinter groups has been changed to 'Group X'. I have been collecting texts from a variety of sources intended for the use of recruiting and radicalizing members for Group X splinter groups for the purpose of researching the motivation and intent of leaders of those groups and their influence over the likelihood of group radicalization. This work included visiting many Group X websites to find information on splinter group leaders and finding their statements to new and old members. This proved difficult because the splinter groups of Group X are united in beliefs, but differ in public opinion. They are eager to tear each other down, prove their superiority, and yet remain anonymous. After a few weeks of intense searching, a list of eight recruiting texts and eight radicalizing texts from a variety of Group X leaders were compiled.

  11. Algebraic Side-Channel Attack on Twofish

    Directory of Open Access Journals (Sweden)

    Chujiao Ma

    2017-05-01

    Full Text Available While algebraic side-channel attack (ASCA has been successful in breaking simple cryptographic algorithms, it has never been done on larger or more complex algorithms such as Twofish. Compared to other algorithms that ASCA has been used on, Twofish is more difficult to attack due to the key-dependent S-boxes as well as the complex key scheduling. In this paper, we propose the first algebraic side-channel attack on Twofish, and examine the importance of side-channel information in getting past the key-dependent S-boxes and the complex key scheduling. The cryptographic algorithm and side-channel information are both expressed as boolean equations and a SAT solver is used to recover the key. While algebraic attack by itself is not sufficient to break the algorithm, with the help of side-channel information such as Hamming weights, we are able to correctly solve for 96 bits of the 128 bits key in under 2 hours with known plaintext/ciphertext.

  12. Stabilization of Gob-Side Entry with an Artificial Side for Sustaining Mining Work

    OpenAIRE

    Hong-sheng Wang; Dong-sheng Zhang; Lang Liu; Wei-bin Guo; Gang-wei Fan; KI-IL Song; Xu-feng Wang

    2016-01-01

    A concrete artificial side (AS) is introduced to stabilize a gob-side entry (GSE). To evaluate the stability of the AS, a uniaxial compression failure experiment was conducted with large and small-scale specimens. The distribution characteristics of the shear stress were obtained from a numerical simulation. Based on the failure characteristics and the variation of the shear stress, a failure criterion was determined and implemented in the strengthening method for the artificial side. In an e...

  13. Functionally Graded Ceramics Fabricated with Side-by-Side Tape Casting for Use in Magnetic Refrigeration

    DEFF Research Database (Denmark)

    Bulatova, Regina; Bahl, Christian; Andersen, Kjeld Bøhm

    2015-01-01

    Functionally graded ceramic tapes have been fabricated by a side-by-side tape casting technique. This study shows the possibility and describes the main principles of adjacent coflow of slurries resulting in formation of thin plates of graded ceramic material. Results showed that the small...... variations of solvent and binder system concentrations have a substantial effect on slurry viscosity. Varying these parameters showed that side-by-side tape casting with a well-defined interface area is possible for slurries with viscosities above 3500 mPa s at a casting shear rate of 3.3 s -1...

  14. Piriformis electromyography activity during prone and side-lying hip joint movement.

    Science.gov (United States)

    Morimoto, Yasuhiro; Oshikawa, Tomoki; Imai, Atsushi; Okubo, Yu; Kaneoka, Koji

    2018-01-01

    [Purpose] To measure electromyographic activity of the piriformis using fine-wire electrodes during 7 hip movements. [Subjects and Methods] Eleven healthy men, without severe low back pain or lower limb injury, participated in this study. Fine-wire electrodes were inserted into the piriformis and surface electrodes were attached to the muscles in the hip region and the trunk muscles on the dominant arm side. Electromyographic signal amplitude was measured during 7 hip movements: side-lying external rotation in hip neutral position, side-lying abduction in hip neutral position, side-lying abduction in hip external rotation, side-lying abduction in hip internal rotation, prone extension in hip neutral position, prone extension in hip external rotation, and prone extension in hip internal rotation. Repeated-measures one-way analysis of variance was used to examine electromyographic activity in each of the 7 hip movements. [Results] Piriformis electromyographic activity was highest during prone hip extension in external rotation. Both the superior and inferior portions of the gluteus maximus were also highly activated during prone hip extension in external rotation. [Conclusion] Prone hip extension in external rotation induced high electromyographic activity in the piriformis and superior and inferior gluteus maximus muscles.

  15. Group Flow and Group Genius

    Science.gov (United States)

    Sawyer, Keith

    2015-01-01

    Keith Sawyer views the spontaneous collaboration of group creativity and improvisation actions as "group flow," which organizations can use to function at optimum levels. Sawyer establishes ideal conditions for group flow: group goals, close listening, complete concentration, being in control, blending egos, equal participation, knowing…

  16. [Morphological features of utilization intraperitoneal double-sided prostheses in inguinoplasty in dogs].

    Science.gov (United States)

    de Andrade, Luiz Carlos; Ceneviva, Reginaldo; Coutinho-Netto, Joaquim; Silva Júnior, Orlando de Castro e; dos Santos, José Sebastião; Sukeda, Daniel Hirochi

    2009-10-01

    To asses the morphological features of the behavior of a double-sided prostheses using inguinoplasty laparotomy in dogs with latex side turned to the visceras. Twenty dogs were divided into two groups of 10 and submitted into infraumbilical laparotomy with double-sided prostheses fixed in an inguinal area and in the other side area a control prostheses of polipropilene (PPL). Macroscopics itens were studied on the 14th and 28th day post-operatory, and they were related to obstruction and intestinal fistulas, encystation, fusion and especially sticker. The microscopic analysis covered the inflammatory process in its acute, chronic and restored phase Infectious process, obstruction or intestinal fistula did not happen. The prostheses presented good accommodation and incorporation. The stickers happened with more prevalent and intensity with the PPL (p0,05). The double-sided prostheses in its parietal side adds the advantages of the incorporation's potential to the noticed material with PPL to the biocompatibility from the latex in its visceral side. The little distance between the PPL disc and the edge of the double-sided prostheses (2 cm) allied to its sticking with just five staples is not enough to avoid gaps, through which the epíploon migrated towards to the inflammatory process provoked by PPL in the parietal side.

  17. Diode-side-pumped Alexandrite slab lasers.

    Science.gov (United States)

    Damzen, M J; Thomas, G M; Minassian, A

    2017-05-15

    We present the investigation of diode-side-pumping of Alexandrite slab lasers in a range of designs using linear cavity and grazing-incidence bounce cavity configurations. An Alexandrite slab laser cavity with double-pass side pumping produces 23.4 mJ free-running energy at 100 Hz rate with slope efficiency ~40% with respect to absorbed pump energy. In a slab laser with single-bounce geometry output power of 12.2 W is produced, and in a double-bounce configuration 6.5 W multimode and 4.5 W output in TEM 00 mode is produced. These first results of slab laser and amplifier designs in this paper highlight some of the potential strategies for power and energy scaling of Alexandrite using diode-side-pumped Alexandrite slab architectures with future availability of higher power red diode pumping.

  18. DarkSide search for dark matter

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, T.; Alton, D.; Arisaka, K.; Back, H. O.; Beltrame, P.; Benziger, J.; Bonfini, G.; Brigatti, A.; Brodsky, J.; Bussino, S.; Cadonati, L.; Calaprice, F.; Candela, A.; Cao, H.; Cavalcante, P.; Chepurnov, A.; Chidzik, S.; Cocco, A. G.; Condon, C.; D' Angelo, D.; Davini, S.; Vincenzi, M. De; Haas, E. De; Derbin, A.; Pietro, G. Di; Dratchnev, I.; Durben, D.; Empl, A.; Etenko, A.; Fan, A.; Fiorillo, G.; Franco, D.; Fomenko, K.; Forster, G.; Gabriele, F.; Galbiati, C.; Gazzana, S.; Ghiano, C.; Goretti, A.; Grandi, L.; Gromov, M.; Guan, M.; Guo, C.; Guray, G.; Hungerford, E. V.; Ianni, Al; Ianni, An; Joliet, C.; Kayunov, A.; Keeter, K.; Kendziora, C.; Kidner, S.; Klemmer, R.; Kobychev, V.; Koh, G.; Komor, M.; Korablev, D.; Korga, G.; Li, P.; Loer, B.; Lombardi, P.; Love, C.; Ludhova, L.; Luitz, S.; Lukyanchenko, L.; Lund, A.; Lung, K.; Ma, Y.; Machulin, I.; Mari, S.; Maricic, J.; Martoff, C. J.; Meregaglia, A.; Meroni, E.; Meyers, P.; Mohayai, T.; Montanari, D.; Montuschi, M.; Monzani, M. E.; Mosteiro, P.; Mount, B.; Muratova, V.; Nelson, A.; Nemtzow, A.; Nurakhov, N.; Orsini, M.; Ortica, F.; Pallavicini, M.; Pantic, E.; Parmeggiano, S.; Parsells, R.; Pelliccia, N.; Perasso, L.; Perasso, S.; Perfetto, F.; Pinsky, L.; Pocar, A.; Pordes, S.; Randle, K.; Ranucci, G.; Razeto, A.; Romani, A.; Rossi, B.; Rossi, N.; Rountree, S. D.; Saggese, P.; Saldanha, R.; Salvo, C.; Sands, W.; Seigar, M.; Semenov, D.; Shields, E.; Skorokhvatov, M.; Smirnov, O.; Sotnikov, A.; Sukhotin, S.; Suvarov, Y.; Tartaglia, R.; Tatarowicz, J.; Testera, G.; Thompson, J.; Tonazzo, A.; Unzhakov, E.; Vogelaar, R. B.; Wang, H.; Westerdale, S.; Wojcik, M.; Wright, A.; Xu, J.; Yang, C.; Zavatarelli, S.; Zehfus, M.; Zhong, W.; Zuzel, G.

    2013-11-22

    The DarkSide staged program utilizes a two-phase time projection chamber (TPC) with liquid argon as the target material for the scattering of dark matter particles. Efficient background reduction is achieved using low radioactivity underground argon as well as several experimental handles such as pulse shape, ratio of ionization over scintillation signal, 3D event reconstruction, and active neutron and muon vetos. The DarkSide-10 prototype detector has proven high scintillation light yield, which is a particularly important parameter as it sets the energy threshold for the pulse shape discrimination technique. The DarkSide-50 detector system, currently in commissioning phase at the Gran Sasso Underground Laboratory, will reach a sensitivity to dark matter spin-independent scattering cross section of 10-45 cm2 within 3 years of operation.

  19. Communication technologies for demand side management

    Energy Technology Data Exchange (ETDEWEB)

    Uuspaeae, P. [VTT Energy, Espoo (Finland)

    1998-08-01

    The scope of this research is data communications for electric utilities, specifically for the purposes of Demand Side Management (DSM). Demand Side Management has the objective to change the customer`s end use of energy in a manner that benefits both the customer and the utility. For example, peak demand may be reduced, and the peak demand may be relocated to off peak periods. Thus additional investments in generation and network may be avoided. A number of Demand Side Management functions can be implemented if a communication system is available between the Electric Utility and the Customer. The total communication capacity that is needed, will depend on several factors, such as the functions that are chosen for DSM, and on the number and type of customers. Some functions may be handled with one-way communications, while some other functions need to have two-way communication

  20. Areeda-turner in two-sided markets

    NARCIS (Netherlands)

    Behringer, S.; Filistrucchi, L.

    2015-01-01

    We extend the Areeda–Turner rule to two-sided markets. We show that a two-sided monopolist may find it short-run profit-maximizing to charge a price below marginal cost on one side of the market. Hence showing that the price is below marginal cost on one side of a two-sided market cannot be

  1. Isopermutation group

    Energy Technology Data Exchange (ETDEWEB)

    Muktibodh, A. S. [Department of Mathematics, Mohota College of Science, NAGPUR-440009 India E-mail: amukti2000@yahoo.com (India)

    2015-03-10

    The concept of ‘Isotopy’ as formulated by Ruggero Maria Santilli [1, 2, 3] plays a vital role in the development of Iso mathematics. Santilli defined iso-fields of characteristic zero. In this paper we extend this definition to define Iso-Galois fields [4] which are essentially of non-zero characteristic. Isotopically isomorphic realizations of a group define isopermutation group which gives a clear cut distinction between automorphic groups and isotopic groups.

  2. Side effects from intense pulsed light

    DEFF Research Database (Denmark)

    Thaysen-Petersen, Daniel; Erlendsson, Andres M; Nash, J F

    2017-01-01

    BACKGROUND AND OBJECTIVE: Intense pulsed light (IPL) is a mainstream treatment for hair removal. Side effects after IPL are known, but risk factors remain to be investigated. The objective of this study was to assess the contribution of skin pigmentation, fluence level, and ultraviolet radiation...... exposure of UVR did not exacerbate side effects (P ≥ 0.180). Clinical findings were confirmed objectively by reflectance spectrometry and qualitatively by histological changes in skin architecture, inflammatory infiltration, and pigmentation. Marker of cellular DNA damage, that is, p53, did not increase...

  3. A new series of two-ring-based side chain liquid crystalline polymers: synthesis and mesophase characterization

    CSIR Research Space (South Africa)

    Reddy, GSM

    2013-05-01

    Full Text Available A new series of side chain liquid crystalline polymers containing a core, a butamethylenoxy spacer, ester groups, and terminal alkoxy groups were synthesised and their structures were confirmed. The core was constructed with two phenyl rings...

  4. Permutation groups

    CERN Document Server

    Passman, Donald S

    2012-01-01

    This volume by a prominent authority on permutation groups consists of lecture notes that provide a self-contained account of distinct classification theorems. A ready source of frequently quoted but usually inaccessible theorems, it is ideally suited for professional group theorists as well as students with a solid background in modern algebra.The three-part treatment begins with an introductory chapter and advances to an economical development of the tools of basic group theory, including group extensions, transfer theorems, and group representations and characters. The final chapter feature

  5. Integrated planning in supply chains with buy-side and sell-side

    Indian Academy of Sciences (India)

    In this paper we develop a quadratic programming model for partner selection and planning in integrated supply chain networks embedded with both sell-side and buy-side electronic marketplaces. Such a scenario arises in several practical applications. In particular, we consider a contract manufacturer who procures ...

  6. SIDE-BY-SIDE TESTS OF DIFFERENTLY DESIGNED EVACUATED TUBULAR COLLECTORS

    DEFF Research Database (Denmark)

    Fan, Jianhua; Dragsted, Janne; Furbo, Simon

    2007-01-01

    . and one all-glass ETC with heat pipe from Exoheat AB. The collectors have been investigated side-by-side in an outdoor test facility for a long period. During the measurements, the operating conditions – such as weather conditions, inlet and mean solar collector fluid temperatures have been the same. Thus...

  7. EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Ai ds (CEF); Scientific Opinion on Flavouring Group Evaluation 208 (FGE.208): Consideration of genotoxicity data on representatives for 10 alicyclic aldehydes with the α , β - unsaturation in ring / side - chain

    DEFF Research Database (Denmark)

    Beltoft, Vibe Meister; Binderup, Mona-Lise; Lund, Pia

    The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to evaluate the genotoxic potential of one flavouring substance from subgroup 2.2 of FGE.19 in the Flavouring Group Evaluation 208. The Flavour Industry has provided a...

  8. 18FDG-PET in 733 consecutive patients with or without side-by-side CT evaluation. Analysis of 921 lesions

    International Nuclear Information System (INIS)

    Buell, U.; Wieres, F.J.; Schneider, W.; Reinartz, P.

    2004-01-01

    Side-by-side analysis of CT and conventional 18 FDG-PET in oncological imaging is well established. Aim of this study was to find out which patients or diagnostic groups may benefit the most from the newly introduced integrated PET/CT scanners. Patients, methods: 407 consecutively admitted oncological patients with accompanying CT (groups A-D) and 326 patients without CT (groups E-G) were examined by conventional ring PET. Two nuclear medicine physicians and two radiologists assessed each patient's PET and CT scans for pathological lesions with regard to localisation and infiltration of adjacent anatomical structures. Patients without pathological PET findings were assigned to groups A (with CT) or E (without CT). If the localisation and/or extent of a pathological PET focus could only be assessed by taking into account the CT scan, the patient was assigned to group C (with CT) or G (without CT). If PET alone was sufficient for both questions the patient was assigned to groups B (with CT) or F (without CT). If neither method allowed for a precise lesion characterisation, the patient was assigned to group D. Results: 38.6% (A, E) of all patients were PET-negative. PET alone sufficed in 20.6% (B, F). Side-by-side reading of PET and CT was needed for 43.5% (C) of patients referred to PET with a current CT. Side-by-side reading of CT and PET did not suffice for 7.3% (D) of patients in that cohort. A total of 28.2% (G) of the cases without CT would have profited from it. The most frequent oncological diagnoses in group D (PET and conventional CT not sufficient) were bronchial carcinoma with abdominal lesions, while in group G (without CT but CT required) head/neck cancer with thoracic lesions was predominant. Conclusions: Side-by-side reading of PET and already existing conventional CT failed to yield conclusive data with regard to lesion characterisation in only 7.4% of patients so that PET/CT might have been helpful in these cases. 28.2% of the patients without

  9. Side Effects of HIV Medicines: HIV and Rash

    Science.gov (United States)

    ... Drugs Clinical Trials Apps skip to content Side Effects of HIV Medicines Home Understanding HIV/AIDS Fact ... and Immunizations What is a Drug Interaction? Side Effects of HIV Medicines HIV Medicines and Side Effects ...

  10. Exploring the Other Side of the Brain.

    Science.gov (United States)

    O'Connor, Therese

    1984-01-01

    At a school for the deaf, weekly hobby classes encourage use of the right side of the brain. Mini courses have included oil painting, sewing, ceramics, gymnastics, and photography with a stress on such right-brain learning techniques as imaging, sequencing, and manipulating patterns. (CL)

  11. The Dark side of World of Warcraft

    DEFF Research Database (Denmark)

    Larsen, Lasse Juel

    understand, perceive or conceptualise fellow players in-side the game world. The analysis of ‘the other’ in WoW rests upon Jean-Paul Sartre’s phenomenological description of ‘the other’ through ‘the look’ in Being and Nothingness (1992). According to Sartre do living beings become aware of themselves through...

  12. Factors effecting paint performance on wood siding

    Science.gov (United States)

    Christopher G. Hunt; R. Sam Williams; Mark Knaebe; Peter Sotos; Steven Lacher

    2009-01-01

    Several different studies are compared to assess the effectiveness of commercial water repellent preservatives (WRP’s) in the late 1990’s on vertical and horizontal siding. Besides WRP, variables included wood species, exposure location (Wisconsin or Mississippi), and solid color stain vs. primer + paint. Data on substrate checking and paint flaking are presented....

  13. Demand side management using profile steering

    NARCIS (Netherlands)

    Gerards, Marco Egbertus Theodorus; Toersche, Hermen; Hoogsteen, Gerwin; van der Klauw, Thijs; Hurink, Johann L.; Smit, Gerardus Johannes Maria

    2015-01-01

    Many Demand Side Management (DSM) approaches use energy prices as steering signals. This paper shows that such steering signals may result in power quality problems and high losses. As an alternative, this paper proposes to use desired (e.g., flat) power profiles as steering signals and presents an

  14. Solar cell with back side contacts

    Science.gov (United States)

    Nielson, Gregory N; Okandan, Murat; Cruz-Campa, Jose Luis; Resnick, Paul J; Wanlass, Mark Woodbury; Clews, Peggy J

    2013-12-24

    A III-V solar cell is described herein that includes all back side contacts. Additionally, the positive and negative electrical contacts contact compoud semiconductor layers of the solar cell other than the absorbing layer of the solar cell. That is, the positive and negative electrical contacts contact passivating layers of the solar cell.

  15. Demand Side Management for Multiple Devices

    NARCIS (Netherlands)

    Molderink, Albert; Bakker, Vincent; Smit, Gerardus Johannes Maria

    Steering a heterogeneous set of devices in a Smart Grid using cost functions: Demand Side Management (DSM) is an important element in smart grids. DSM is already in operation for large consumers, but thorough research is required into DSM on a building level within the distribution grid.

  16. Side-Specific Reward Memories in Honeybees

    Science.gov (United States)

    Gil, Mariana; Menzel, Randolf; De Marco, Rodrigo J.

    2009-01-01

    We report a hitherto unknown form of side-specific learning in honeybees. We trained bees individually by coupling gustatory and mechanical stimulation of each antenna with either increasing or decreasing volumes of sucrose solution offered to the animal's proboscis along successive learning trials. Next, we examined their proboscis extension…

  17. Price discrimination in two-sided markets

    Directory of Open Access Journals (Sweden)

    Kai Zhang

    2016-03-01

    Full Text Available The use of a price discrimination strategy is an important tool in competition. It can hurt firms and benefit consumers in a one-sided market. However, in two-sided markets, its primary goal is to attract more agents or increase profits. Here, the performance of a second-degree price discrimination strategy in the context of duopoly two-sided platforms is analysed. Two exogenous variables, which include the discount rate and the price discrimination threshold, are used in order to examine whether the price discrimination strategy could help two-sided platforms achieve their objective, which is to maximise their market value. Three cases are considered, and we demonstrate that the price discrimination strategy cannot attract more agents and at the same time increase the profits; a lower price discrimination threshold cannot ensure larger markets shares; a higher discount rate is detrimental to the profit of a platform. However, this is good for its market shares. Moreover, discriminative pricing increases the competition.

  18. Side Chain Cyclized Aromatic Amino Acids

    DEFF Research Database (Denmark)

    Van der Poorten, Olivier; Knuhtsen, Astrid; Sejer Pedersen, Daniel

    2016-01-01

    Constraining the conformation of flexible peptides is a proven strategy to increase potency, selectivity, and metabolic stability. The focus has mostly been on constraining the backbone dihedral angles; however, the correct orientation of the amino acid side chains (χ-space) that constitute the p...

  19. A reverse side of the team medal

    NARCIS (Netherlands)

    Vermeulen, P.A.M.; Benders, J.G.J.M.

    2003-01-01

    Publications in the managerial press tend to stress the positive sides of teamworking. Teamworking is heralded at the neglect of possible downsides such as the propensity to withhold effort. This is, however, studied in at least two strands of academic work: social psychology and economic

  20. Struck by a lance through his side

    DEFF Research Database (Denmark)

    Leth, Peter Mygind; Boldsen, Jesper Lier

    2010-01-01

    The Danish King Canute the Saint was killed in St Alban church in Odense July 1086. According to a legend the king was kneeling in prayers when a lance thrust to his side killed him. Our re-examination of the skeleton presumed to belong to Canute showed a slimly build man with an approximate...