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Sample records for azobenzene nanoparticle-embedded polyacrylic

  1. Azobenzene

    Integrated Risk Information System (IRIS)

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

  2. Palladium Nanoparticles Embedded in a Layer-by-Layer Nanoreactor Built with Poly(Acrylic Acid) Using "Electro-Click Chemistry".

    PubMed

    Villalba, Matias; Bossi, Mariano; Pozo, Maria Del; Calvo, Ernesto J

    2016-07-12

    Palladium nanoparticles (Pd NPs) were formed by electrochemical reduction of Pd(NH3)4(3+) ions entrapped by ion exchange in poly(acrylic acid) (PAA) multilayer films grown by the Sharpless "click reaction." The alkyne (PAAalk) and azide (PAAaz) groups were covalently bound to the PAA, and the catalyzed buildup of the multilayer film was performed by electrochemical reduction of Cu(2+) to Cu(+). The size of the Pd NPs formed in Au/(PAAalk)3(PAAaz)2 multilayer films by the click reaction, that is, 50 nm, is larger than that of similar Pd NPs formed in electrostatically bound Au/(PAA)3(PAH)2 nanoreactors, that is, 6-9 nm, under similar conditions. A combination of electrochemical methods and electrochemical quartz crystal microbalance, polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), ellipsometry, and scanning electron microscopy has been used to follow these processes. Cyclic voltammetry of the resulting Pd NPs in a 0.1 M H2SO4 solution at 0.1 V·s(-1) shows the PdO reduction peak at the same potential as that on the clean Pd surface unlike the NPs formed in electrostatically self-assembled Au/(PAA)3(PAH)2 nanoreactors with a 0.2 V shift in the cathodic direction most probably because of the strong adsorption of amino groups on the Pd NP surfaces. PMID:27308840

  3. Nanoparticle embedded enzymes for improved lateral flow sensors.

    PubMed

    Özalp, Veli C; Zeydanlı, Uğur S; Lunding, Anita; Kavruk, Murat; Öz, M Tufan; Eyidoğan, Füsun; Olsen, Lars F; Öktem, Hüseyin A

    2013-08-01

    In this study, combining the nanoparticle embedded sensors with lateral flow assays, a novel strategy for ensuring the quality of signalling in lateral flow assays (LFAs) was developed. A LFA for reactive oxygen species (ROS) is reported that is based on horse radish peroxidase (HRP) which is co-entrapped with Texas Red dextran inside porous polyacrylamide nanoparticles. In this system, enzymes are protected in the porous matrix of polyacrylamide which freely allows the diffusion of the analyte. The sensor is rapid and sensitive for quantification of hydrogen peroxide concentrations. A test solution of hydrogen peroxides was quantified with this novel LFA-ROS sensor to obtain a linear range between 1 and 25 μM. Nanoparticle embedding of enzymes is proposed here as a general strategy for developing enzyme-based lateral flow assays, eliminating adverse effects associated with biological samples. PMID:23730687

  4. The azobenzene derivatives

    NASA Astrophysics Data System (ADS)

    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.

  5. Bimetallic ruthenium-copper nanoparticles embedded in mesoporous carbon as an effective hydrogenation catalyst.

    PubMed

    Liu, Jiajia; Zhang, Li Li; Zhang, Jiatao; Liu, Tao; Zhao, X S

    2013-11-21

    Bimetallic ruthenium-copper nanoparticles embedded in the pore walls of mesoporous carbon were prepared via a template route and evaluated in terms of catalytic properties in D-glucose hydrogenation. The existence of bimetallic entities was supported by Ru L3-edge and Cu K-edge X-ray absorption results. The hydrogen spillover effect of the bimetallic catalyst on the hydrogenation reaction was evidenced by the results of both hydrogen and carbon monoxide chemisorptions. The bimetallic catalyst displayed a higher catalytic activity than the single-metal catalysts prepared using the same approach, namely ruthenium or copper nanoparticles embedded in the pore walls of mesoporous carbon. This improvement was due to the changes in the geometric and electronic structures of the bimetallic catalyst because of the presence of the second metal. PMID:24072134

  6. Co3O4 nanoparticle embedded carbonaceous fibres: a nanoconfinement effect on enhanced lithium-ion storage.

    PubMed

    Sun, Jin; Li, Daohao; Xia, Yanzhi; Zhu, Xiaoyi; Zong, Lu; Ji, Quan; Jia, Yi Alec; Yang, Dongjiang

    2015-11-21

    Co3O4 nanoparticle embedded carbonaceous fibres were prepared from Co(2+) coordinated regenerated cellulose fibres, which showed high reversible capacity and excellent cycling stability as anode materials for Li-ion batteries. PMID:26399496

  7. Microwave absorber based on silver nanoparticle-embedded polymer thin film.

    PubMed

    Ramesh, G V; Sudheendran, K; Raju, K C James; Sreedhar, B; Radhakrishnan, T P

    2009-01-01

    Silver nanoparticle-embedded poly(vinyl alcohol) films are fabricated through a simple in situ process. The nanocomposite films are a few hundred nanometers thick with silver concentrations below 10% and the nanoparticles 5-10 nm in diameter. These films are shown to exhibit appreciable microwave absorption in the 8-12 GHz range; the return and insertion losses are found to be sensitive to the nanoparticle content. PMID:19441305

  8. Bimetallic ruthenium-copper nanoparticles embedded in mesoporous carbon as an effective hydrogenation catalyst

    NASA Astrophysics Data System (ADS)

    Liu, Jiajia; Zhang, Li Li; Zhang, Jiatao; Liu, Tao; Zhao, X. S.

    2013-10-01

    Bimetallic ruthenium-copper nanoparticles embedded in the pore walls of mesoporous carbon were prepared via a template route and evaluated in terms of catalytic properties in d-glucose hydrogenation. The existence of bimetallic entities was supported by Ru L3-edge and Cu K-edge X-ray absorption results. The hydrogen spillover effect of the bimetallic catalyst on the hydrogenation reaction was evidenced by the results of both hydrogen and carbon monoxide chemisorptions. The bimetallic catalyst displayed a higher catalytic activity than the single-metal catalysts prepared using the same approach, namely ruthenium or copper nanoparticles embedded in the pore walls of mesoporous carbon. This improvement was due to the changes in the geometric and electronic structures of the bimetallic catalyst because of the presence of the second metal.Bimetallic ruthenium-copper nanoparticles embedded in the pore walls of mesoporous carbon were prepared via a template route and evaluated in terms of catalytic properties in d-glucose hydrogenation. The existence of bimetallic entities was supported by Ru L3-edge and Cu K-edge X-ray absorption results. The hydrogen spillover effect of the bimetallic catalyst on the hydrogenation reaction was evidenced by the results of both hydrogen and carbon monoxide chemisorptions. The bimetallic catalyst displayed a higher catalytic activity than the single-metal catalysts prepared using the same approach, namely ruthenium or copper nanoparticles embedded in the pore walls of mesoporous carbon. This improvement was due to the changes in the geometric and electronic structures of the bimetallic catalyst because of the presence of the second metal. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr03813k

  9. Enhanced antioxidant activity of gold nanoparticle embedded 3,6-dihydroxyflavone: a combinational study

    NASA Astrophysics Data System (ADS)

    Medhe, Sharad; Bansal, Prachi; Srivastava, Man Mohan

    2012-12-01

    The antioxidative effect of selected dietary compounds (3,6-dihydroxyflavone, lutein and selenium methyl selenocysteine) was determined in single and combination using DPPH (2,2-diphenyl-l-picrylhydrazyl), OH (hydroxyl), H2O2 (hydrogen peroxide) and NO (nitric oxide) radical scavenging assays. Radical scavenging effect of the dietary phytochemicals individually are found to be in the order: ascorbic acid (standard) > lutein > 3,6-dihydroxyflavone > selenium methyl selenocysteine, at concentration 100 μg/ml, confirmed by all the four bioassays (p < 0.05). Among the various combinations studied, the triplet combination of 3,6-dihydroxyflavone, lutein and selenium methyl selenocysteine (1:1:1), exhibited enhancement in the target activity at same concentration level. Synthesized gold nanoparticle embedded 3,6-dihydroxyflavone further enhanced the target antioxidant activity. The combinational study including gold nanoparticle embedded 3,6-dihydroxyflavone with other native dietary nutrients showed remarkable increase in antioxidant activity at the same concentration level. The present in vitro study on combinational and nanotech enforcement of dietary phytochemicals shows the utility in the architecture of nanoparticle embedded phytoproducts having a wide range of applications in medical science.

  10. Nickel nanoparticles embedded in carbon foam for improving electromagnetic shielding effectiveness

    NASA Astrophysics Data System (ADS)

    Kumar, Rajeev; Kumari, Saroj; Dhakate, Sanjay R.

    2014-08-01

    To improve electromagnetic shielding effectiveness of light weight carbon foam (CF), magnetic nanoparticles were embedded in it during processing. The CF was developed from the coal tar pitch and mixture of coal tar pitch-Nickel (Ni) nanoparticles by sacrificial template technique and heat treated to up 1,000 °C. To ascertain the effect of Ni nanoparticles embedded in CF, it was characterized by scanning electron microscopy, X-ray diffraction, Raman spectroscopy, vector network analyzer and vibration sample magnetometer. It is observed that Ni nanoparticles embedded in the carbon material play an important role for improving the structure and electrical conductivity of CF-Ni by catalytic carbonization. The structural investigation suggests that the Ni nanoparticles embedded in the carbon material in bulk as well on the surface of CF. The CF demonstrates excellent shielding response in the frequency range 8.2-12.4 GHz in which total shielding effectiveness (SE) dominated by absorption losses. The total SE is -25 and -61 dB of CF and CF-Ni, it is governed by absorption losses -48.5 dB in CF-Ni. This increase is due to the increase in dielectric and magnetic losses of ferromagnetic Ni nanoparticles with high surface area. Thus, light weight CF embedded with small amount of magnetic nanoparticles can be useful material for stealth technology.

  11. Nickel nanoparticles embedded in carbon foam for improving electromagnetic shielding effectiveness

    NASA Astrophysics Data System (ADS)

    Kumar, Rajeev; Kumari, Saroj; Dhakate, Sanjay R.

    2015-06-01

    To improve electromagnetic shielding effectiveness of light weight carbon foam (CF), magnetic nanoparticles were embedded in it during processing. The CF was developed from the coal tar pitch and mixture of coal tar pitch-Nickel (Ni) nanoparticles by sacrificial template technique and heat treated to up 1,000 °C. To ascertain the effect of Ni nanoparticles embedded in CF, it was characterized by scanning electron microscopy, X-ray diffraction, Raman spectroscopy, vector network analyzer and vibration sample magnetometer. It is observed that Ni nanoparticles embedded in the carbon material play an important role for improving the structure and electrical conductivity of CF-Ni by catalytic carbonization. The structural investigation suggests that the Ni nanoparticles embedded in the carbon material in bulk as well on the surface of CF. The CF demonstrates excellent shielding response in the frequency range 8.2-12.4 GHz in which total shielding effectiveness (SE) dominated by absorption losses. The total SE is -25 and -61 dB of CF and CF-Ni, it is governed by absorption losses -48.5 dB in CF-Ni. This increase is due to the increase in dielectric and magnetic losses of ferromagnetic Ni nanoparticles with high surface area. Thus, light weight CF embedded with small amount of magnetic nanoparticles can be useful material for stealth technology.

  12. Surface Wave Velocity of Crosslinked Polyacrylate Gels

    NASA Astrophysics Data System (ADS)

    Matsuoka, Tatsuro; Kinouchi, Wataru; ShinobuKoda, ShinobuKoda; Nomura, Hiroyasu

    1999-05-01

    Surface wave velocities of crosslinked polyacrylate hydrogelswere measured as a function of water content with differentcompositions of sodium polyacrylate (NaPA) and polyacrylic acid (PAA).The water content and composition dependencies of the surface wavevelocity were discussed.

  13. Magnetoacoustic imaging of magnetic iron oxide nanoparticles embedded in biological tissues with microsecond magnetic stimulation

    NASA Astrophysics Data System (ADS)

    Hu, Gang; He, Bin

    2012-01-01

    We present an experimental study on magnetoacoustic imaging of superparamagnetic iron oxide (SPIO) nanoparticles embedded in biological tissues. In experiments, a large-current-carrying coil is used to deliver microsecond pulsed magnetic stimulation to samples. The ultrasound signals induced by magnetic forces on SPIO nanoparticles are measured by a rotating transducer. The distribution of nanoparticles is reconstructed by a back-projection imaging algorithm. The results demonstrated the feasibility to obtain cross-sectional image of magnetic nanoparticle targets with faithful dimensional and positional information, which suggests a promising tool for tomographic reconstruction of magnetic nanoparticle-labeled diseased tissues (e.g., cancerous tumor) in molecular or clinic imaging.

  14. Tunneling Anisotropic Magnetoresistance in Fe Nanoparticles Embedded in MgO Matrix

    NASA Astrophysics Data System (ADS)

    Pham, T. V.; Miwa, S.; Suzuki, Y.

    2016-05-01

    The tunnel magnetoresistance (TMR) effect is related to the relative orientation of the magnetizations of the two ferromagnetic electrodes in magnetic tunnel junctions (MTJs). The tunnel anisotropic magnetoresistance (TAMR) effect is related to the orientation of the magnetization with respect to the current direction or the crystallographic axes. Beyond the TMR, the TAMR is not only present in MTJs in which both electrodes are ferromagnetic but may also appear in tunnel structures with a single magnetic electrode. We investigated the magnetotransport properties in an Au/MgO/Fe nanoparticles/MgO/Cu tunnel junction. We found that both the TMR and TAMR can appear in tunnel junctions with Fe nanoparticles embedded in an MgO matrix. The TMR is attributed to spin-dependent tunneling between Fe nanoparticles, so the device resistance depends on the magnetization directions of adjacent Fe nanoparticles. The TAMR is attributed to the interfacial spin-orbit interaction, so the device resistance depends on each magnetization direction of an Fe nanoparticle. This is the first observation of the TAMR in Fe nanoparticles embedded in an MgO matrix.

  15. Silver nanoparticle-embedded polymersome nanocarriers for the treatment of antibiotic-resistant infections

    NASA Astrophysics Data System (ADS)

    Geilich, Benjamin M.; van de Ven, Anne L.; Singleton, Gloria L.; Sepúlveda, Liuda J.; Sridhar, Srinivas; Webster, Thomas J.

    2015-02-01

    The rapidly diminishing number of effective antibiotics that can be used to treat infectious diseases and associated complications in a physician's arsenal is having a drastic impact on human health today. This study explored the development and optimization of a polymersome nanocarrier formed from a biodegradable diblock copolymer to overcome bacterial antibiotic resistance. Here, polymersomes were synthesized containing silver nanoparticles embedded in the hydrophobic compartment, and ampicillin in the hydrophilic compartment. Results showed for the first time that these silver nanoparticle-embedded polymersomes (AgPs) inhibited the growth of Escherichia coli transformed with a gene for ampicillin resistance (bla) in a dose-dependent fashion. Free ampicillin, AgPs without ampicillin, and ampicillin polymersomes without silver nanoparticles had no effect on bacterial growth. The relationship between the silver nanoparticles and ampicillin was determined to be synergistic and produced complete growth inhibition at a silver-to-ampicillin ratio of 1 : 0.64. In this manner, this study introduces a novel nanomaterial that can effectively treat problematic, antibiotic-resistant infections in an improved capacity which should be further examined for a wide range of medical applications.

  16. Preparation and characterization of Ag nanoparticle-embedded blank and ligand-anchored silica gels.

    PubMed

    Im, Hee-Jung; Lee, Byung Cheol; Yeon, Jei-Won

    2013-11-01

    Ag nanoparticles, used for halogen (especially iodine) adsorption and an evaluation of halogen behavior, were embedded in synthesized inorganic-organic hybrid gels. In particular, an irradiation method using an electron beam plays a part in introducing Ag nanoparticles to the organofunctionalized silica gels from AgNO3 solutions in a simple way at atmospheric pressure and room temperature. For preparation of the Ag nanoparticle-embedded inorganic-organic hybrid gels, ligands of ethylenediamine (NH2CH2CH2NH-, TMSen) and mercapto (HS-) functionalized three-dimensional porous SiO2 sol-gels were first synthesized through hydrolysis and condensation reactions, and Ag nanoparticles were then embedded into the ethylenediamine- and mercapto-anchored silica gels each, through electron-beam irradiation. The addition of ligands yielded larger average pore sizes than the absence of any ligand. Moreover, the ethylenediamine ligand led to looser structures and better access of the Ag nanoparticles to the ethylenediamine-anchored gel. As a result, more Ag nanoparticles were introduced into the ethylenediamine-anchored gel. The preparation and characterization of Ag nanoparticle-embedded blank and ligand-anchored silica gels are discussed in detail. PMID:24245307

  17. Silver nanoparticle-embedded polymersome nanocarriers for the treatment of antibiotic-resistant infections.

    PubMed

    Geilich, Benjamin M; van de Ven, Anne L; Singleton, Gloria L; Sepúlveda, Liuda J; Sridhar, Srinivas; Webster, Thomas J

    2015-02-28

    The rapidly diminishing number of effective antibiotics that can be used to treat infectious diseases and associated complications in a physician's arsenal is having a drastic impact on human health today. This study explored the development and optimization of a polymersome nanocarrier formed from a biodegradable diblock copolymer to overcome bacterial antibiotic resistance. Here, polymersomes were synthesized containing silver nanoparticles embedded in the hydrophobic compartment, and ampicillin in the hydrophilic compartment. Results showed for the first time that these silver nanoparticle-embedded polymersomes (AgPs) inhibited the growth of Escherichia coli transformed with a gene for ampicillin resistance (bla) in a dose-dependent fashion. Free ampicillin, AgPs without ampicillin, and ampicillin polymersomes without silver nanoparticles had no effect on bacterial growth. The relationship between the silver nanoparticles and ampicillin was determined to be synergistic and produced complete growth inhibition at a silver-to-ampicillin ratio of 1 : 0.64. In this manner, this study introduces a novel nanomaterial that can effectively treat problematic, antibiotic-resistant infections in an improved capacity which should be further examined for a wide range of medical applications. PMID:25628231

  18. 21 CFR 173.73 - Sodium polyacrylate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium polyacrylate. 173.73 Section 173.73 Food and... Substances and Polymer Adjuvants for Food Treatment § 173.73 Sodium polyacrylate. Sodium polyacrylate (CAS... polyacrylic acid with an aqueous sodium hydroxide solution. As determined by a method entitled...

  19. Gold nanoparticles embedded in organic/inorganic hybrid matrix: electrical and electrochemical behavior (withdrawal notice)

    NASA Astrophysics Data System (ADS)

    Moreira, Sandra D. F. C.; Silva, J. P. B.; Silva, Carlos J. R.; Capan, I.; Gomes, M. J. M.; Costa, Manuel F. M.

    2013-05-01

    Gold nanoparticles (AuNPs) with different diameters, from 3 to 32 nm, were immobilized in amine-alcohol-silicate matrix by mixing a preformed nanoparticle colloid with the precursors of amine-alcohol-silicate (AAs) prior to the solgel transition. These nanocomposites show high optical quality and optical features dictated by the size of the nanoparticle dopants but also present a high degree of flexibility which can largely enhance the range of practical applications. The current-voltage, impedance and capacitance-voltage characteristics of these materials have been measured. The electrochemical and impedimetric results reveal that AuNPs with different sizes give different signals, thus providing useful information that allows the employment of AuNPs in electrochemical biosensors. Capacitance- voltage measurements showed that these composites embedded AuNPs exhibited a large hysteresis window of 2.4V which indicates the possibility of charge storage in the Au nanoparticles embedded AAs hybrids.

  20. Noble metal nanoparticles embedding into polymeric materials: From fundamentals to applications.

    PubMed

    Prakash, Jai; Pivin, J C; Swart, H C

    2015-12-01

    This review covers some key concepts related to embedding of the noble metal nanoparticles in polymer surfaces. The metal nanoparticles embedded into the polymer matrix can provide high-performance novel materials that find applications in modern nanotechnology. In particular, the origin of various processes that drive the embedding phenomenon, growth of the nanostructure at the surface, factors affecting the embedding including role of surface, interface energies and thermodynamic driving forces with emphasis on the fundamental and technological applications, under different conditions (annealing and ion beams) have been discussed. In addition to the conventional thermal process for embedding which includes the measure of fundamental polymer surface properties with relevant probing techniques, this review discusses the recent advances carried out in the understanding of embedding phenomenon starting from thin metal films to growth of the nanoparticles and embedded nanostructures using novel ion beam techniques. PMID:26584861

  1. The calculations of electromagnetic fields around nanoparticles embedded in biological media

    NASA Astrophysics Data System (ADS)

    Prytkova, Vera D.; Tuchin, Valery V.

    2010-08-01

    The goal of our project is to use computational methods, such as discrete dipole approximation (DDA) to study nanoparticles in biomedical photonics problems. Nanoparticle absorption and scattering are strongly affected by their shape, size, composition and dielectric environment. We focus on light scattering from nanoparticles embedded in biological or biocompatible media, such as water, glycerin and hemoglobin at erythrocyte hemoglobin concentration at concentration characteristic to intrinsic erythrocyte concentration. This method lets us consider complex refractive index of the nanoparticle and the surrounding medium as a function on the wavelength of light. We are interested in strong absorption and scattering around 800 nm that makes such nanoparticles potentially useful in biomedical applications, such as detection and curing cancer. Considering nanoparticles in living cells containing nanoparticles lets us understand light scattering from normal and pathological structures within biological tissue.

  2. Pt nanoparticles embedded on reduced graphite oxide with excellent electrocatalytic properties

    NASA Astrophysics Data System (ADS)

    Saravanan, Gengan; Mohan, Subramanian

    2016-11-01

    Economically viable electrochemical approach has been developed for the synthesis of Pt nanoparticles through electrodeposition technique on the surface of Reduced Graphite Oxide (RGO). Pt nanoparticles embedded Reduced Graphite Oxide on Glassy Carbon Electrode are employed (Pt-rGO/GCE) for electrooxidation of formic acid. Scanning Electron Microscopy (SEM) image and Transmission Electron Microscopy (TEM) image shows that reduced graphite oxide act as an excellent support to anchor the Pt nanoparticles. Cyclic voltammetry results confirmed that Pt-rGO/GCE enhanced current density as many folds than that of bare platinum electrode for electrooxidation of formic acid. X-ray diffraction (XRD) patterns for Pt-graphene composites illustrate that peaks at 69.15 and 23° for Pt (220) and graphene carbon (002) respectively. 13C NMR spectrum of the electrochemically reduced graphite oxide resonance contains only one peak at 133 ppm which retains graphitic sp2 carbon and does not contain any oxygenated carbon and the carbonyl carbons.

  3. Preparation and nonlinear characterization of zinc selenide nanoparticles embedded in polymer matrix

    NASA Astrophysics Data System (ADS)

    Sharma, Mamta; Tripathi, S. K.

    2012-09-01

    Nanocomposites of ZnSe nanoparticles embedded in polyvinyl alcohol (PVA) matrix have been prepared by in-situ synthesis. ZnSe/PVA nanocomposites are characterized by X-ray diffraction (XRD), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and UV/Vis spectra. The nanocomposite structure is confirmed by the blue-shift of the absorption edge. The nonlinear refractive index and two-photon absorption (TPA) coefficient are measured by the Z-scan technique using low power CW He-Ne laser light. The results show that the ZnSe nanocomposite films show large optical nonlinearity and the magnitude of the third-order nonlinear susceptibility χ(3) is calculated to be 2.62×13-11 m2/V2.

  4. 21 CFR 173.73 - Sodium polyacrylate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Sodium polyacrylate. 173.73 Section 173.73 Food... Polymer Substances and Polymer Adjuvants for Food Treatment § 173.73 Sodium polyacrylate. Sodium... the polyacrylic acid with an aqueous sodium hydroxide solution. As determined by a method...

  5. 21 CFR 173.73 - Sodium polyacrylate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Sodium polyacrylate. 173.73 Section 173.73 Food... Polymer Substances and Polymer Adjuvants for Food Treatment § 173.73 Sodium polyacrylate. Sodium... the polyacrylic acid with an aqueous sodium hydroxide solution. As determined by a method...

  6. 21 CFR 173.73 - Sodium polyacrylate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Sodium polyacrylate. 173.73 Section 173.73 Food... for Food Treatment § 173.73 Sodium polyacrylate. Sodium polyacrylate (CAS Reg. No. 9003-04-7) may be... aqueous sodium hydroxide solution. As determined by a method entitled “Determination of Weight Average...

  7. 21 CFR 173.73 - Sodium polyacrylate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Sodium polyacrylate. 173.73 Section 173.73 Food... Polymer Substances and Polymer Adjuvants for Food Treatment § 173.73 Sodium polyacrylate. Sodium... the polyacrylic acid with an aqueous sodium hydroxide solution. As determined by a method...

  8. Nature of chromogens of protonated azobenzene

    NASA Astrophysics Data System (ADS)

    Mikheev, Yu. A.; Guseva, L. N.; Ershov, Yu. A.

    2015-02-01

    Changes in the absorption spectra of azobenzene in UV-Vis light are studied with respect to its protonation in sulfuric acid solutions and interaction with gaseous HCl in cellulose triacetate films. In both processes, the emergence of an intense orange color is shown to represent the electronic structure of forming monocations where the positive charge of NH+ groups shifts electrons from the o- and p-positions of Nphfragment phenyls. It was found that the charge distribution and color was the same as observed for the cations of the benzyl and phenylaminyl types. The mechanism of azobenzene monocation photocyclization in sulfuric acid is presented, and the origin of the red color of azobenzene dications formed in oleum is explained.

  9. Transport properties of β-Ga2O3 nanoparticles embedded in Nb thin films

    NASA Astrophysics Data System (ADS)

    Vaidhyanathan, L. S.; Srinivasan, M. P.; Chandra Mohan, P.; Baisnab, D. K.; Mythili, R.; Janawadkar, M. P.

    2015-01-01

    The origin of ferromagnetism in nanoparticles of nonmagnetic oxides is an interesting area of research. In the present work, transport properties of niobium thin films, with β-Ga2O3 nanoparticles embedded within them, are presented. Nanoparticles of β-Ga2O3 embedded in a Nb matrix were prepared at room temperature by radio frequency co-sputtering technique on Si (100) and glass substrates held at room temperature. The thin films deposited on Si substrates were subjected to Ar annealing at a temperature range of 600-650 C for 1 hour. Films were characterized by X-ray diffraction (XRD), Micro-Raman and elemental identification was performed with an Energy Dispersive X-ray Spectroscopy (EDS). Transport measurements were performed down to liquid helium temperatures by four-probe contact technique, showed characteristics analogous to those observed in the context of a Kondo system. A comparison of the experimental data with the theoretical formalism of Kondo and Hamann is presented. It is suggested that this behavior arises from the existence of magnetic moments associated with the oxygen vacancy defects in the nanoparticles of the nonmagnetic oxide Ga2O3.

  10. Polymeric nanoparticles-embedded organogel for roxithromycin delivery to hair follicles.

    PubMed

    Główka, Eliza; Wosicka-Frąckowiak, Hanna; Hyla, Kinga; Stefanowska, Justyna; Jastrzębska, Katarzyna; Klapiszewski, Łukasz; Jesionowski, Teofil; Cal, Krzysztof

    2014-09-01

    Drug delivery into hair follicles with the use of nanoparticles (NPs) is gaining more importance as drug-loaded NPs may accumulate in hair follicle openings. The aim was to develop and evaluate a pluronic lecithin organogel (PLO) with roxithromycin (ROX)-loaded NPs for follicular targeting. Polymeric NPs were evaluated in terms of particle shape, size, zeta potential, suspension stability, encapsulation efficiency and in vitro drug release. Lyophilized NPs were incorporated into the PLO and rheological measurements of the nanoparticles-embedded organogels were done. The fate of the NPs in the skin was traced by incorporation of a fluorescent dye into the NPs. As a result, ROX was efficiently incorporated into polymeric NPs characterized by the appropriate size (approximately 300 nm) allowing drug delivery to hair follicles. In ex vivo human skin penetration studies, horizontal skin sections revealed fluorescence deep in the hair follicles. Although the organogel has higher affinity to the lipidic follicular area than an aqueous suspension of NPs, it did not seem to improve penetration of the NPs along the hair shaft. The results proved that it was possible to achieve preferential targeting to the pilosebaceous unit using polymeric NPs formulated either into the aqueous suspension or semisolid topical formulation. PMID:25014763

  11. Ion-irradiation-induced amorphization of Cu nanoparticles embedded in SiO2

    NASA Astrophysics Data System (ADS)

    Johannessen, B.; Kluth, P.; Llewellyn, D. J.; Foran, G. J.; Cookson, D. J.; Ridgway, M. C.

    2007-11-01

    Elemental Cu nanoparticles embedded in SiO2 were irradiated with 5MeVSn3+ . The nanoparticle structure was studied as a function of Sn3+ fluence by extended x-ray absorption fine structure spectroscopy, small-angle x-ray scattering, and transmission electron microscopy. Prior to irradiation, Cu nanoparticles exhibited the face-centered-cubic structure. Upon irradiation at intermediate fluences ( 1×1013 to 1×1014ions/cm2 ), the first nearest neighbor Cu-Cu coordination number decreased, while the Debye-Waller factor, bondlength, and third cumulant of the bondlength distribution increased. In particular, at a fluence of 1×1014ions/cm2 we argue for the presence of an amorphous Cu phase, for which we deduce the structural parameters. Low temperature annealing (insufficient for nanoparticle growth) of the amorphous Cu returned the nanoparticles to the initial preirradiation structure. At significantly higher irradiation fluences ( 1×1015 to 1×1016ions/cm2 ), the nanoparticles were dissolved in the matrix with a Cu coordination similar to that of Cu2O .

  12. Melting and Solidification Behaviour of Bi-Pb Multiphase Alloy Nanoparticles Embedded in Aluminum Matrix.

    PubMed

    Khan, Patan Yousaf; Biswas, Krishanu

    2015-01-01

    The present investigation reports the result of the investigation on the phase transformation of biphasic Bi-Pb alloy nanoparticles embedded in the aluminum matrix. The samples are prepared by rapid solidification route involving melt spinning of Al-6 wt% (Bi55.9Pb44.1) alloy on a rotating copper wheel in an argon-filled evacuated chamber. The detailed transmission electron microscope (TEM) investigation shows presence of near cuboctahedral shaped biphasic nano-inclusions consisting of the (Bi) solid solution and β, the intermediate phase. β constitutes bulk of the nanoparticle with (Bi) forming the cap. Both the phases bear distinct orientation relationship with the matrix. The compositional analysis indicates substantial increase in solid solubilities of Pb in the (Bi) and Bi in the β-phases as compared to the as-cast sample. Differential scanning calorimetric (DSC) studies indicate substantial superheating (16.4 K) of the embedded nanoparticles with appearance of sharp melting peak. The solidification is observed to be diffused, taking place over a large temperature range (344.5 K to 332 K). The in situ heating stage experiments carried out in TEM indicate formation of core shell morphology during heating with β forming the shell around (Bi). The melting starts from Al/β/(Bi) triple point and then the liquid spreads along matrix-particle interface. The solidification occurs in eutectic manner. PMID:26328350

  13. Magnetic properties of Ni nanoparticles embedded in silica matrix (KIT-6) synthesized via novel chemical route

    SciTech Connect

    Dalavi, Shankar B.; Panda, Rabi N.; Raja, M. Manivel

    2015-06-24

    Thermally stable Ni nanoparticles have been embedded in mesoporous silica matrix (KIT-6) via novel chemical reduction method by using superhydride as reducing agent. X-ray diffraction (XRD) study confirms that pure and embedded Ni nanoparticles crystallize in face centered cubic (fcc) structure. Crystallite sizes of pure Ni, 4 wt% and 8 wt% Ni in silica were estimated to be 6.0 nm, 10.4 nm and 10.5 nm, respectively. Morphology and dispersion of Ni in silica matrix were studied by scanning electron microscopy (SEM). Magnetic study shows enhancement of magnetic moments of Ni nanoparticles embedded in silica matrix compared with that of pure Ni. The result has been interpreted on the basis of size reduction and magnetic exchange effects. Saturation magnetization values for pure Ni, 4 wt% and 8 wt% Ni in silica were found to be 15.77 emu/g, 5.08 emu/g and 2.00 emu/g whereas coercivity values were 33.72 Oe, 92.47 Oe and 64.70 Oe, respectively. We anticipate that the observed magnetic properties may find application as soft magnetic materials.

  14. Photoluminescence study of PVP capped CdS nanoparticles embedded in PVA matrix

    SciTech Connect

    Pattabi, Manjunatha . E-mail: manjupattabi@yahoo.com; Saraswathi Amma, B.; Manzoor, K.

    2007-05-03

    Photoluminescence properties of polyvinyl pyrrolidone (PVP) capped cadmium sulphide (CdS) nanoparticles embedded in polyvinyl alcohol matrix (PVA) are reported. The PVP-CdS nanoparticles are prepared by non-aqueous method wherein cadmium nitrate is used as the cadmium source and hydrogen sulphide as the sulphur source. The synthesized nanoparticles are dispersed in polyvinyl alcohol (PVA) matrix and cast as self-standing flexible (PVP-CdS)-PVA films. The nanocomposites are characterized by optical absorption spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM) studies. XRD and TEM studies show the formation of cubic CdS particles with average size {approx}3-5 nm. Thermal studies, carried out to observe the changes in PVA matrix due to the incorporation of PVP-CdS nanoparticles show strong interaction between the polymer matrix and nanoparticles. The photoluminescence emission spectra of the nanocomposites show two peaks, at 502 and 636 nm, which are attributed to the band edge and surface defects respectively, of CdS nanoparticles. Effective surface capping with optimum concentration of polyvinyl pyrrolidone leads to the quenching of surface defect-related emission.

  15. Health and environmental effects profile for azobenzene

    SciTech Connect

    Not Available

    1985-03-01

    The Health and Environmental Effects Profile for azobenzene was prepared by the Office of Health and Environmental Assessment, Environmental Criteria and Assessment Office, Cincinnati, OH for the Office of Solid Waste and Emergency Response to support listings of hazardous constituents of a wide range of waste streams under Section 3001 of the Resource Conservation and Recovery Act (RCRA) and to provide health-related limits for emergency actions under Section 101 of the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA). Both published literature and information obtained from Agency program office files were evaluated as they pertained to potential human health, aquatic life, and environmental effects of hazardous-waste constituents. Quantitative estimates are presented, provided sufficient data are available. Azobenzene has been evaluated as a carcinogen. The human carcinogen potency factor (ql*) for azobenzene is .108 (mg/kg/day)-1 for oral exposure. The Reportable Quantity (RQ) value of 1, 10, 100, 1000, or 5000 pounds is used to determine the quantity of a hazardous substance for which notification is required in the event of a release as specified by CERCLA based on chronic toxicity. The RQ value for azobenzene is 100.

  16. Hydrothermal Synthesis and Processing of Barium Titanate Nanoparticles Embedded in Polymer Films.

    PubMed

    Toomey, Michael D; Gao, Kai; Mendis, Gamini P; Slamovich, Elliott B; Howarter, John A

    2015-12-30

    Barium titanate nanoparticles embedded in flexible polymer films were synthesized using hydrothermal processing methods. The resulting films were characterized with respect to material composition, size distribution of nanoparticles, and spatial location of particles within the polymer film. Synthesis conditions were varied based on the mechanical properties of the polymer films, ratio of polymer to barium titanate precursors, and length of aging time between initial formulations of the solution to final processing of nanoparticles. Block copolymers of poly(styrene-co-maleic anhydride) (SMAh) were used to spatially separate titanium precursors based on specific chemical interactions with the maleic anhydride moiety. However, the glassy nature of this copolymer restricted mobility of the titanium precursors during hydrothermal processing. The addition of rubbery butadiene moieties, through mixing of the SMAh with poly(styrene-butadiene-styrene) (SBS) copolymer, increased the nanoparticle dispersion as a result of greater diffusivity of the titanium precursor via higher mobility of the polymer matrix. Additionally, an aminosilane was used as a means to retard cross-linking in polymer-metalorganic solutions, as the titanium precursor molecules were shown to react and form networks prior to hydrothermal processing. By adding small amounts of competing aminosilane, excessive cross-linking was prevented without significantly impacting the quality and composition of the final barium titanate nanoparticles. X-ray diffraction and X-ray photoelectron spectroscopy were used to verify nanoparticle compositions. Particle sizes within the polymer films were measured to be 108 ± 5 nm, 100 ± 6 nm, and 60 ± 5 nm under different synthetic conditions using electron microscopy. Flexibility of the films was assessed through measurement of the glass transition temperature using dynamic mechanical analysis. Dielectric permittivity was measured using an impedance analyzer. PMID

  17. Subsurface Synthesis and Characterization of Ag Nanoparticles Embedded in MgO

    SciTech Connect

    Vilayur Ganapathy, Subramanian; Devaraj, Arun; Colby, Robert J.; Pandey, Archana; Varga, Tamas; Shutthanandan, V.; Manandhar, Sandeep; El-Khoury, Patrick Z.; Kayani, Asghar N.; Hess, Wayne P.; Thevuthasan, Suntharampillai

    2013-03-08

    Metal nanoparticles exhibit localized surface plasmon resonance (LSPR) which is very sensitive to the size and shape of the nanoparticle and the dielectric medium surrounding it. LSPR causes field enhancement near the surface of the nanoparticle making them interesting candidates for plasmonic applications. In particular, partially exposed metallic nanoparticles distributed in a dielectric matrix form hotspots which are prime locations for LSPR spectroscopy and sensing. This study involves synthesizing partially buried Ag nanoparticles in MgO and investigating the characteristics of this material system. Ag nanoparticles of different shapes and size distributions were synthesized below the surface of MgO by implanting 200 keV Ag+ ions followed by annealing at 10000C for 10 and 30 hours. A detailed optical and structural characterization was carried out to understand the evolution of Ag nanoparticle microstructure and size distribution inside the MgO matrix. Micro x-ray diffraction (MicroXRD) was employed to investigate the structural properties and estimate the crystallite size. The nanoparticles evolved from a spherical to faceted morphology with annealing time, assuming an octahedral shape truncated at the (001) planes as seen from aberration corrected transmission electron microscopy (TEM) images. The nanoparticles embedded in MgO were shown to be pure metallic Ag using atom probe tomography (APT). The nanoparticles were partially exposed to the surface employing plasma etch techniques to remove the overlaying MgO. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed to study the surface morphology and obtain a height distribution for the partially exposed nanoparticles.

  18. Subsurface synthesis and characterization of Ag nanoparticles embedded in MgO.

    PubMed

    Vilayurganapathy, S; Devaraj, A; Colby, R; Pandey, A; Varga, T; Shutthanandan, V; Manandhar, S; El-Khoury, P Z; Kayani, Asghar; Hess, W P; Thevuthasan, S

    2013-03-01

    Metal nanoparticles exhibit a localized surface plasmon resonance (LSPR) which is very sensitive to the size and shape of the nanoparticle and the surrounding dielectric medium. The coupling between the electromagnetic radiation and the localized surface plasmon in metallic nanoparticles results in a sizable enhancement of the incident fields, making them possible candidates for plasmonic applications. In particular, partially exposed metallic nanoparticles distributed in a dielectric matrix can provide prime locations for LSPR spectroscopy and sensing. We report the synthesis and characterization of a plasmonic substrate consisting of Ag nanoparticles partially buried in MgO. Ag nanoparticles of different shapes and size distributions were synthesized below the surface of MgO by implanting 200 keV Ag(+) ions followed by annealing at 1000 °C for 10 and 30 h. A detailed optical and structural characterization was carried out to understand the evolution of the Ag nanoparticle and size distribution inside the MgO matrix. Micro x-ray diffraction (Micro-XRD) was employed to investigate the structural properties and estimate the crystallite size. The nanoparticles evolved from a spherical to a faceted morphology with annealing time, assuming an octahedral shape truncated at the (001) planes, as visualized from aberration-corrected transmission electron microscopy (TEM) images. The nanoparticles embedded in MgO were shown to be pure metallic Ag using atom probe tomography (APT). The nanoparticles were partially exposed to the surface by employing plasma etch techniques to remove the overlaying MgO. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed to study the surface morphology and obtain a height distribution for the partially exposed nanoparticles. PMID:23403363

  19. Subsurface synthesis and characterization of Ag nanoparticles embedded in MgO

    NASA Astrophysics Data System (ADS)

    Vilayurganapathy, S.; Devaraj, A.; Colby, R.; Pandey, A.; Varga, T.; Shutthanandan, V.; Manandhar, S.; El-Khoury, P. Z.; Kayani, Asghar; Hess, W. P.; Thevuthasan, S.

    2013-03-01

    Metal nanoparticles exhibit a localized surface plasmon resonance (LSPR) which is very sensitive to the size and shape of the nanoparticle and the surrounding dielectric medium. The coupling between the electromagnetic radiation and the localized surface plasmon in metallic nanoparticles results in a sizable enhancement of the incident fields, making them possible candidates for plasmonic applications. In particular, partially exposed metallic nanoparticles distributed in a dielectric matrix can provide prime locations for LSPR spectroscopy and sensing. We report the synthesis and characterization of a plasmonic substrate consisting of Ag nanoparticles partially buried in MgO. Ag nanoparticles of different shapes and size distributions were synthesized below the surface of MgO by implanting 200 keV Ag+ ions followed by annealing at 1000 °C for 10 and 30 h. A detailed optical and structural characterization was carried out to understand the evolution of the Ag nanoparticle and size distribution inside the MgO matrix. Micro x-ray diffraction (Micro-XRD) was employed to investigate the structural properties and estimate the crystallite size. The nanoparticles evolved from a spherical to a faceted morphology with annealing time, assuming an octahedral shape truncated at the (001) planes, as visualized from aberration-corrected transmission electron microscopy (TEM) images. The nanoparticles embedded in MgO were shown to be pure metallic Ag using atom probe tomography (APT). The nanoparticles were partially exposed to the surface by employing plasma etch techniques to remove the overlaying MgO. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed to study the surface morphology and obtain a height distribution for the partially exposed nanoparticles.

  20. Deflocculation of clay suspensions using sodium polyacrylates

    NASA Technical Reports Server (NTRS)

    Jedlicka, P.

    1984-01-01

    Rheological properties of elutriated kaolin suspensions deflocculated by Na polyacrylate (DAC 3 and DAC 4) were studied and compared to those deflocculated by the conventional Na2CO3 water and glass and imported Dispex N40. The deflocculating effect of Na polyacrylate was comparable to that of Dispex N40. The optimum amounts of Na polyacrylate were determined for suspensions based on 5-type kaolin. The Na polyacrylate can be successfully used for decreasing the water content of ceramic slips for casting and spray drying.

  1. Phase decomposition of AuFe alloy nanoparticles embedded in silica matrix under swift heavy ion irradiation

    NASA Astrophysics Data System (ADS)

    Pannu, Compesh; Bala, Manju; Singh, U. B.; Srivastava, S. K.; Kabiraj, D.; Avasthi, D. K.

    2016-07-01

    AuFe alloy nanoparticles embedded in silica matrix are synthesized using atom beam sputtering technique and subsequently irradiated with 100 MeV Au ions at various fluences ranging from 1 × 1013 to 6 × 1013 ions/cm2. The X-ray diffraction, absorption spectroscopy, X-ray photo electron spectroscopy and transmission electron microscopy results show that swift heavy ion irradiation leads to decomposition of AuFe alloy nanoparticles from surface region and subsequent reprecipitation of Au and Fe nanoparticles occur. The process of phase decomposition and reprecipitation of individual element nanoparticles is explained on the basis of inelastic thermal spike model.

  2. DNA compaction by azobenzene-containing surfactant

    NASA Astrophysics Data System (ADS)

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

    2011-08-01

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

  3. Cooperative Switching in Nanofibers of Azobenzene Oligomers

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  4. Cooperative Switching in Nanofibers of Azobenzene Oligomers.

    PubMed

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

    2016-01-01

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

  5. Cooperative Switching in Nanofibers of Azobenzene Oligomers

    PubMed Central

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

    2016-01-01

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

  6. DNA compaction by azobenzene-containing surfactant

    SciTech Connect

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

    2011-08-15

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

  7. Binding of calcium and carbonate to polyacrylates.

    PubMed

    Tribello, Gareth A; Liew, CheeChin; Parrinello, Michele

    2009-05-21

    Polyacrylate molecules can be used to slow the growth of calcium carbonate. However, little is known about the mechanism by which the molecules impede the growth rate. A recent computational study (Bulo et al. Macromolecules 2007, 40, 3437) used metadynamics to investigate the binding of calcium to polyacrylate chains and has thrown some light on the coiling and precipitation of these polymers. We extend these simulations to examine the binding of calcium and carbonate to polyacrylate chains. We show that calcium complexed with both carbonate and polyacrylate is a very stable species. The free energies of calcium-carbonate-polyacrylate complexes, with different polymer configurations, are calculated, and differences in the free energy of the binding of carbonate are shown to be due to differences in the amount of steric hindrance about the calcium, which prevents the approach of the carbonate ion. PMID:19400592

  8. Electrical Bistabilities and Memory Mechanisms of Organic Bistable Devices Fabricated Utilizing CdSe/ZnS Nanoparticles Embedded in Polystyrene and Poly(4-vinylphenol) Hybrid Composites

    NASA Astrophysics Data System (ADS)

    Son, Dong Ick; Yoo, Chan Ho; Jung, Jae Hun; Kim, Tae Whan

    2010-01-01

    The electrical bistabilities of core/shell CdSe/ZnS nanoparticles embedded in polystyrene (PS) and poly(4-vinylphenol) (PVP) hybrid polymer composites were investigated. Transmission electron microscopy images showed that CdSe/ZnS nanoparticles were formed inside the hybrid polymer matrix. Current-voltage (I-V) measurement at 300 K of Al/(PS + PVP)/(CdSe/ZnS nanoparticles)/(PS + PVP)/indium-tin oxide/glass devices showed electrical bistability behavior. The memory mechanisms of the organic bistable devices fabricated utilizing CdSe/ZnS nanoparticles embedded in hybrid polymer composites are described on the basis of the I-V results.

  9. Direct electrochemical oxidation of polyacrylates.

    PubMed

    Bellagamba, Riccardo; Comninellis, Christos; Vatistas, Nicolaos

    2002-10-01

    A promising elimination treatment of non-biodegradable organic pollutants is the direct electro-oxidation. In this work has been proposed the electrochemical elimination of polyacrylates by using boron-doped diamond (BDD) as anodic material. The complete elimination of organic contaminants has been obtained and this is the first case of successful electrochemical treatment of polymeric and bio-refractory species. The tests of the electrochemical oxidation have been conducted at constant current conditions and a complete elimination of organic species has been reached. The decrease of the COD value with time follows the behaviour of an ideal anode as in the case of low molecular organic compounds. PMID:12489259

  10. Photoswitchable azobenzene-appended iridium(iii) complexes.

    PubMed

    Pérez-Miqueo, J; Altube, A; García-Lecina, E; Tron, A; McClenaghan, N D; Freixa, Z

    2016-09-21

    Iridium(iii) cyclometalated complexes have been used as models to study the effect that extended conjugation and substitution pattern has on the photochromic behavior of azobenzene-appended 2-phenylpyridyl (ppy) ligands. For this purpose four azobenzene-containing ppy ligands were synthesized. With these ligands, nine iridium(iii) complexes containing up to three appended azobenzenes were synthesized. Analysis of their photochromic behaviour by means of UV-vis and (1)H-NMR spectroscopy permitted us to conclude that the light-induced trans-to-cis isomerization of the azobenzene was strongly inhibited upon coordination to the Ir(iii) cation when the electronic conjugation was extended along the whole ligand. The use of an aliphatic spacer unit (either -CH2- or -OCH2-) between the azobenzene and the ppy fragment of the ligand sufficed to disrupt the electronic communication, and obtain photochromic organometallic complexes. PMID:27460186

  11. Photocontrolled micellar aggregation of amphiphilic DNA-azobenzene conjugates.

    PubMed

    Gu, Renpeng; Lamas, Joseph; Rastogi, Shiva K; Li, Xiaopeng; Brittain, William; Zauscher, Stefan

    2015-11-01

    We demonstrate the reversible micellar aggregation of a DNA-azobenzene conjugate in aqueous conditions, in which the photoisomerization of the initially apolar trans-azobenzene moiety to the polar cis isomer causes disassembly of the aggregates. The molecular basis for this phenomena is a change in the hydrophobic/hydrophilic balance of the conjugate as the more polar cis azobenzene isomer is formed upon exposure to 365 nm irradiation. The conjugates were prepared by copper-free Click chemistry between an azide-modified, 53-base ssDNA and a cyclooctyne derivative of azobenzene. The photocontrolled aggregation of the conjugate was studied by dynamic light scattering and atomic force microscopy. The reversible micellar aggregation for a DNA-azobenzene conjugate has not been previously reported and holds promise for photocontrolled drug delivery applications. PMID:26247877

  12. Frequency-Dependent Magnetic Susceptibility of Magnetite and Cobalt Ferrite Nanoparticles Embedded in PAA Hydrogel

    PubMed Central

    van Berkum, Susanne; Dee, Joris T.; Philipse, Albert P.; Erné, Ben H.

    2013-01-01

    Chemically responsive hydrogels with embedded magnetic nanoparticles are of interest for biosensors that magnetically detect chemical changes. A crucial point is the irreversible linkage of nanoparticles to the hydrogel network, preventing loss of nanoparticles upon repeated swelling and shrinking of the gel. Here, acrylic acid monomers are adsorbed onto ferrite nanoparticles, which subsequently participate in polymerization during synthesis of poly(acrylic acid)-based hydrogels (PAA). To demonstrate the fixation of the nanoparticles to the polymer, our original approach is to measure low-field AC magnetic susceptibility spectra in the 0.1 Hz to 1 MHz range. In the hydrogel, the magnetization dynamics of small iron oxide nanoparticles are comparable to those of the particles dispersed in a liquid, due to fast Néel relaxation inside the particles; this renders the ferrogel useful for chemical sensing at frequencies of several kHz. However, ferrogels holding thermally blocked iron oxide or cobalt ferrite nanoparticles show significant decrease of the magnetic susceptibility resulting from a frozen magnetic structure. This confirms that the nanoparticles are unable to rotate thermally inside the hydrogel, in agreement with their irreversible fixation to the polymer network. PMID:23673482

  13. Frequency-dependent magnetic susceptibility of magnetite and cobalt ferrite nanoparticles embedded in PAA hydrogel.

    PubMed

    van Berkum, Susanne; Dee, Joris T; Philipse, Albert P; Erné, Ben H

    2013-01-01

    Chemically responsive hydrogels with embedded magnetic nanoparticles are of interest for biosensors that magnetically detect chemical changes. A crucial point is the irreversible linkage of nanoparticles to the hydrogel network, preventing loss of nanoparticles upon repeated swelling and shrinking of the gel. Here, acrylic acid monomers are adsorbed onto ferrite nanoparticles, which subsequently participate in polymerization during synthesis of poly(acrylic acid)-based hydrogels (PAA). To demonstrate the fixation of the nanoparticles to the polymer, our original approach is to measure low-field AC magnetic susceptibility spectra in the 0.1 Hz to 1 MHz range. In the hydrogel, the magnetization dynamics of small iron oxide nanoparticles are comparable to those of the particles dispersed in a liquid, due to fast Néel relaxation inside the particles; this renders the ferrogel useful for chemical sensing at frequencies of several kHz. However, ferrogels holding thermally blocked iron oxide or cobalt ferrite nanoparticles show significant decrease of the magnetic susceptibility resulting from a frozen magnetic structure. This confirms that the nanoparticles are unable to rotate thermally inside the hydrogel, in agreement with their irreversible fixation to the polymer network. PMID:23673482

  14. Nanocomposite thin films of gold nanoparticles embedded in yttria-stabilized zirconia for plasmonic-based harsh environment gas detection

    NASA Astrophysics Data System (ADS)

    Rogers, Phillip H.

    Increased health concerns due to the emission of gases linked to the production of tropospheric ozone by petroleum based fuel burning engines has resulted in the codification of more stringent emissions regulations domestically. Emissions regulations on commercial jetliners are one of the areas to be met with stricter standards. Currently there is not a sensing technology that can detect the emissions gases in the exhaust stream of a jet turbine engine with lower detection limits that meet these standards. The localized surface plasmon resonance (LSPR) of noble metal nanoparticles embedded in dielectric matrices is an optical response that can be extremely sensitive to many environmental parameters. Nanocomposites of Au nanoparticles embedded in yttria-stabilized zirconia (Au-YSZ) are an ideal case study for these plasmonic materials. Using a metal oxide matrix with oxygen ion vacancies, such as YSZ, allows one to finely tune the local environmental charge of the embedded metal nanoparticles upon varying the oxygen and hydrogen content of the gas exposure mixture. After gas exposure data is collected in the form of optical absorption spectra, the LSPR spectra due to the Au nanoparticles embedded in the YSZ matrix undergo automated Lorentzian and Drude model fitting for calculating fundamental charge exchange and plasmonic dampening effects versus gas exposure concentration. These titration experiments have been performed for Au-YSZ nanocomposites exposed to O2, H2, NO 2, and CO in N2 backgrounds at 500°C and equilibrium data has been acquired for both the average charge per Au nanoparticle and the scattering frequency of the plasmons over a variety of exposure conditions. One paramount result made possible by this plasmonic based gas detection by Au-YSZ nanocomposite thin films was a repeatable 5 ppm lower detection limit towards NO2 in air at 500°C. In comparing the charge exchange observed using both the fitted exposure data and an electrochemical model

  15. Anomalous thermal hysteresis in the high-field magnetic moments of magnetic nanoparticles embedded in multi-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Zhao, Guo-Meng; Wang, Jun; Ren, Yang; Beeli, Pieder

    2012-02-01

    We report high-temperature (300-1120 K) magnetic properties of Fe and Fe3O4 nanoparticles embedded in multi-walled carbon nanotubes. We unambiguously show that the magnetic moments of Fe and Fe3O4 nanoparticles are seemingly enhanced by a factor of about 3 compared with what they would be expected to have for free (unembedded) magnetic nanoparticles. What is more intriguing is that the enhanced moments were completely lost when the sample was heated up to 1120 K and the lost moments at 1120 K were completely recovered through several thermal cycles below 1020 K. The anomalous thermal hysteresis of the high-field magnetic moments is unlikely to be explained by existing physical models except for the high-field paramagnetic Meissner effect due to the existence of ultrahigh temperature superconductivity in the multi-walled carbon nanotubes.

  16. Ag nanoparticles-embedded surface plasmonic InGaN-based solar cells via scattering and localized field enhancement.

    PubMed

    Shim, Jae-Phil; Choi, Sang-Bae; Kong, Duk-Jo; Seo, Dong-Ju; Kim, Hyung-Jun; Lee, Dong-Seon

    2016-07-11

    Ag nanoparticles are embedded in intentionally etched micro-circle p-GaN holes by means of a thermal agglomeration process to enhance the light absorption efficiency in InGaN/GaN multi-quantum-well (MQW) solar cells. The Ag nanoparticles are theoretically and experimentally verified to generate the plasmon light scattering and the localized field enhancement near the MQW absorption layer. The external quantum efficiency enhancement at a target wavelength region is demonstrated by matching the plasmon resonance of Ag nanoparticles, resulting in a Jsc improvement of 9.1%. Furthermore, the Ag-nanoparticle-embedded InGaN solar cell is effectively fabricated considering the carrier extraction that more than 70% of F.F. and 2.2 V of high Voc are simultaneously attained. PMID:27410903

  17. Base effects on fabrication of silver nanoparticles embedded silica nanocomposite for surface-enhanced Raman scattering (SERS).

    PubMed

    Kang, Homan; Kang, Taegyu; Kim, Seongyong; Kim, Jong-Ho; Jun, Bong-Hyun; Chae, Jinjoo; Park, Juyoung; Jeong, Dae-Hong; Lee, Yoon-Sik

    2011-01-01

    In this paper, we studied on the effect of organic bases in the case of ethylene glycol based fabrication of silver nanoparticles embedded silica nanocomposite (Ag SNC) without heating. Considering their chemical structures, butylamine (BA), ethanolamine (EA), triethanolamine (TEA), tributylamine (TBA), octylamine (OA) and Jeffamine 500 (JA) were used as an organic base. In addition, the effect of the concentrations of AgNO3 and organic bases on the formation of Ag SNC was also examined. In conformity with the characteristics of Ag SNC, SERS signal intensity of benzenethiol on Ag SNC was measured. As a result, the SERS signal intensity of Ag SNCs was strongly dependent on the reaction conditions. Furthermore, when reacted under the best reaction condition with concentrations of AgNO3 and OA, 3 mM and 5 mM, respectively, a large-scale production of Ag SNC was possible under the mild conditions. PMID:21446501

  18. Plasmonic properties of Ag nanoparticles embedded in GeO2-SiO2 matrix by atom beam sputtering.

    PubMed

    Mohapatra, Satyabrata

    2016-02-01

    Nanocomposite thin films containing Ag nanoparticles embedded in the GeO2-SiO2 matrix were synthesized by the atom beam co-sputtering technique. The structural, optical and plasmonic properties and the chemical composition of the nanocomposite thin films were studied by transmission electron microscopy (TEM) with energy dispersive X-ray spectroscopy (EDX), UV-visible absorption spectroscopy and X-ray photoelectron spectroscopy (XPS). UV-visible absorption studies on Ag-SiO2 nanocomposites revealed the presence of a strong localized surface plasmon resonance (LSPR) peak characteristic of Ag nanoparticles at 413 nm, which showed a blue shift of 26 nm (413 to 387 nm) along with a significant broadening and drastic decrease in intensity with the incorporation of 16 at% of Ge into the SiO2 matrix. TEM studies on Ag-GeO2-SiO2 nanocomposite thin films confirmed the presence of Ag nanoparticles with an average size of 3.8 nm in addition to their aggregates with an average size of 16.2 nm. Thermal annealing in air resulted in strong enhancement in the intensity of the LSPR peak, which showed a regular red shift of 51 nm (from 387 to 438 nm) with the increase in annealing temperature up to 500 °C. XPS studies showed that annealing in air resulted in oxidation of excess Ge atoms in the nanocomposite into GeO2. Our work demonstrates the possibility of controllably tuning the LSPR of Ag nanoparticles embedded in the GeO2-SiO2 matrix by single-step thermal annealing, which is interesting for optical applications. PMID:26766559

  19. Photoswitching of azobenzene multilayers on a layered semiconductor

    NASA Astrophysics Data System (ADS)

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

    2010-08-01

    In situ photoelectron spectroscopy is used to study the adsorption and photoisomerization of azobenzene multilayers on the layered semiconductor HfS2 at liquid nitrogen temperatures. The measured valence band spectra indicate weak molecule-substrate coupling and provide evidence for reversible switching of azobenzene multilayers by light with different wavelengths. The photoswitching manifests itself in spectral shifts due to changes in the electrical surface conductance and in modifications of the electronic structure consistent with the results of outer valence Green's function calculations. The photoemission results appear to establish azobenzene as an optoelectrical molecular switch.

  20. Synthesis and Photochromic Properties of Configurationally Varied Azobenzene Glycosides

    PubMed Central

    Chandrasekaran, Vijayanand; Johannes, Eugen; Kobarg, Hauke; Sönnichsen, Frank D; Lindhorst, Thisbe K

    2014-01-01

    Spatial orientation of carbohydrates is a meaningful parameter in carbohydrate recognition processes. To vary orientation of sugars with temporal and spatial resolution, photosensitive glycoconjugates with favorable photochromic properties appear to be opportune. Here, a series of azobenzene glycosides were synthesized, employing glycoside synthesis and Mills reaction, to allow “switching” of carbohydrate orientation by reversible E/Z isomerization of the azobenzene N=N double bond. Their photochromic properties were tested and effects of azobenzene substitution as well as the effect of anomeric configuration and the orientation of the sugars 2-hydroxy group were evaluated. PMID:25050228

  1. Photochemical properties of multi-azobenzene compounds.

    PubMed

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

    2013-03-01

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

  2. Light scattering measurement of sodium polyacrylate products

    NASA Astrophysics Data System (ADS)

    Lama, Nisha; Norwood, David; Boone, Steven; Massie-Boyer, Valerie

    2015-03-01

    In the presentation, we will describe the use of a multi-detector HPLC incorporating the DAWN EOS multi-angle laser light scattering (MALLS) detector to measure the properties such as molecular weight, RMS radius, contour and persistence length and polydispersity of sodium polyacrylate products. The samples of sodium polyacrylate are used in various industries as thickening agents, coating dispersants, artificial snow, laundry detergent and disposable diapers. Data and results obtained from the experiment will be presented.

  3. Azobenzene Photoisomerization-Induced Destabilization of B-DNA

    PubMed Central

    Biswas, Mithun; Burghardt, Irene

    2014-01-01

    Molecular photoswitches provide a promising way for selective regulation of nanoscaled biological systems. It has been shown that conformational changes of azobenzene, one of the widely used photoswitches, can be used to reversibly control DNA duplex formation. Here, we investigate the conformational response of DNA upon azobenzene binding and isomerization, using a threoninol linker that has been experimentally investigated recently. To this end, nonequilibrium molecular dynamics simulations are carried out using a switching potential describing the photoinduced isomerization. Attachment of azobenzene leads to a distortion of the DNA helical conformation that is similar for the trans and cis forms. However, the trans form is stabilized by favorable stacking interactions whereas the cis form is found to remain flipped out of the basepair-stacked position. Multiple azobenzene attachment augments the distortion in DNA helical conformation. The distorted DNA retains nativelike pairing of bases at ambient temperatures, but shows weaker basepairing compared to native DNA at an elevated temperature. PMID:25140428

  4. Azobenzene-based Polymers for Solar Thermal Batteries

    NASA Astrophysics Data System (ADS)

    Venkataraman, Dhandapani

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

  5. Photoinduced Bending of Self-Assembled Azobenzene-Siloxane Hybrid.

    PubMed

    Guo, Sufang; Matsukawa, Kimihiro; Miyata, Takashi; Okubo, Tatsuya; Kuroda, Kazuyuki; Shimojima, Atsushi

    2015-12-16

    A novel azobenzene-siloxane hybrid material displaying photoinduced macroscopic motions has been prepared by one-step organosilane self-assembly. Two types of alkoxysilane precursors with either pendant or bridging azobenzene groups were synthesized via thiol-ene click reactions. Hybrid films with well-ordered lamellar structures were obtained by hydrolysis and polycondensation of these precursors. The film with solely pendant azobenzene groups showed reversible and rapid d-spacing variation upon UV-vis irradiation, which was induced by the trans-cis isomerization of azobenzene moieties. The flexible, free-standing film obtained by co-condensation of two types of precursors showed reversible bending-unbending motions upon UV-vis irradiation. The partial cross-linking between the siloxane layers by bridging azobenzene groups was crucial for photoinduced distortion of the film. This film possesses high elastic modulus, good thermal stability, and shows large amplitude of photoinduced bending-unbending over a wide temperature range. This is the first report on photoinduced macroscopic motions of azobenzene-containing siloxane-based materials. These materials possess great potential for applications in smart devices and energy conversion systems. PMID:26575345

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

    PubMed

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

    2014-02-12

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

  7. Photoisomerization of azobenzenes isolated in cryogenic matrices.

    PubMed

    Duarte, Luís; Khriachtchev, Leonid; Fausto, Rui; Reva, Igor

    2016-06-22

    2,2'-Dihydroxyazobenzene (DAB), 2,2'-azotoluene (AT) and azobenzene (AB) were isolated in argon and xenon matrices and their molecular structures and photochemical transformations were characterized by infrared spectroscopy and theoretical calculations. All these compounds can adopt the E and Z isomeric forms around the central CNNC moiety, which can be enriched by several conformational and tautomeric modifications for DAB and AT. A number of DAB and AT isomeric forms were identified for the first time. For DAB, the E azo-enol isomer with two intramolecular six-membered quasi-rings formed via OHN hydrogen bonds was found after deposition. Irradiation with UV light generated a different E azo-enol form with two intramolecular H-bonded five-membered quasi-rings. Phototransformation was shown to be reversible and the forms could be interconverted by irradiation at different wavelengths. The isomerization between these two forms constitutes a direct experimental observation of an E → E isomerization in azobenzene-type molecules. Further irradiation generated a form(s) bearing both OH and NH groups. For AT, two E isomers with the CH3 groups forming five-membered and five/six-membered quasi-rings with the azo group were observed in the as-deposited matrices. Irradiation of AT with UV light generated a Z form that can be converted back to the E form at different irradiation wavelengths. E-AB was deposited in a xenon matrix and both E → Z and Z → E phototransformations were observed (contrary to what was previously reported in an argon matrix where only the Z → E conversion occurred). AB photoisomerization becomes more pronounced at elevated temperatures, thus indicating that the matrix effects responsible for hindering the AB photoisomerization are essentially due to steric restrictions. The different photoisomerization channels observed for these compounds are discussed in terms of a small-amplitude pedal motion. PMID:27279432

  8. Cobalt nanoparticles embedded in N-doped carbon as an efficient bifunctional electrocatalyst for oxygen reduction and evolution reactions

    NASA Astrophysics Data System (ADS)

    Su, Yunhe; Zhu, Yihua; Jiang, Hongliang; Shen, Jianhua; Yang, Xiaoling; Zou, Wenjian; Chen, Jianding; Li, Chunzhong

    2014-11-01

    Cobalt based catalysts are promising bifunctional electrocatalysts for both oxygen reduction and oxygen evolution reactions (ORR and OER) in unitized regenerative fuel cells (URFCs) operating with alkaline electrolytes. Here we report a hybrid composite of cobalt nanoparticles embedded in nitrogen-doped carbon (Co/N-C) via a solvothermal carbonization strategy. With the synergistic effect arising from the N-doped carbon and cobalt nanoparticles in the composite, the Co/N-C hybrid catalyst exhibits highly efficient bifunctional catalytic activity and excellent stability toward both ORR and OER. The ΔE (oxygen electrode activity parameter for judging the overall electrocatalytic activity of a bifunctional electrocatalyst) value for Co/N-C is 0.859 V, which is smaller than those of Pt/C and most of the non-precious metal catalysts in previous studies. Furthermore, the Co/N-C composite also shows better bifunctional catalytic activity than its oxidative counterparts, which could be attributed to the high specific surface area and the efficient charge transfer ability of the composite, as well as the good synergistic effect between N-doped carbon and the Co nanoparticles in the Co/N-C composite.Cobalt based catalysts are promising bifunctional electrocatalysts for both oxygen reduction and oxygen evolution reactions (ORR and OER) in unitized regenerative fuel cells (URFCs) operating with alkaline electrolytes. Here we report a hybrid composite of cobalt nanoparticles embedded in nitrogen-doped carbon (Co/N-C) via a solvothermal carbonization strategy. With the synergistic effect arising from the N-doped carbon and cobalt nanoparticles in the composite, the Co/N-C hybrid catalyst exhibits highly efficient bifunctional catalytic activity and excellent stability toward both ORR and OER. The ΔE (oxygen electrode activity parameter for judging the overall electrocatalytic activity of a bifunctional electrocatalyst) value for Co/N-C is 0.859 V, which is smaller than those

  9. Cobalt nanoparticle-embedded carbon nanotube/porous carbon hybrid derived from MOF-encapsulated Co3O4 for oxygen electrocatalysis.

    PubMed

    Dou, Shuo; Li, Xingyue; Tao, Li; Huo, Jia; Wang, Shuangyin

    2016-08-11

    We successfully obtained a novel bi-functional electrocatalyst towards the ORR and OER: Co nanoparticle-embedded N-doped carbon nanotube (CNT)/porous carbon (PC) by pyrolyzing metal organic framework (MOF) encapsulated Co3O4. The as-obtained hybrid exhibited highly efficient electrocatalytic activity for the ORR and OER. Furthermore, the assembled Zn-air batteries also revealed promising performance and long-term stability. PMID:27411845

  10. Optical absorption and TEM studies of silver nanoparticle embedded BaO-CaF2-P2O5 glasses

    NASA Astrophysics Data System (ADS)

    Narayanan, Manoj Kumar; Shashikala, H. D.

    2016-05-01

    Silver nanoparticle embedded 30BaO-20CaF2-50P2O5-4Ag2O-4SnO glasses were prepared by melt-quenching and subsequent heat treatment process. Silver-doped glasses were heat treated at temperatures 500 °C, 525°C and 550 °C for a fixed duration of 10 hours to incorporate metal nanoparticles into the glass matrix. Appearance and shift in peak positions of the surface plasmon resonance (SPR) bands in the optical absorption spectra of heat treated glass samples indicated that both formation and growth of nanoparticle depended on heat treatment temperature. Glass sample heat treated at 525 °C showed a SPR peak around 3 eV, which indicated that spherical nanoparticles smaller than 20 nm were formed inside the glass matrix. Whereas sample heat treated at 550 °C showed a size dependent red shift in SPR peak due to the presence of silver nanoparticles of size larger than 20 nm. Size of the nanoparticles calculated using full-width at half-maximum (FWHM) of absorption band showed a good agreement with the particle size obtained from transmission electron microscopy (TEM) analysis.

  11. Two-Solvent Method Synthesis of NiO/ZnO Nanoparticles Embedded in Mesoporous SBA-15: Photocatalytic Properties Study.

    PubMed

    Dai, Peng; Yan, Tao-Tao; Yu, Xin-Xin; Bai, Zhi-Man; Wu, Ming-Zai

    2016-12-01

    Different loadings of NiO/ZnO nanoparticles embedded in mesoporous silica (SBA-15) were prepared via a two-solvent method with the ordered hexagonal mesoporous structure of SBA-15 kept. X-ray diffraction, transmission electron microscope, X-ray photoelectron spectroscopy, diffusive reflective UV-vis spectroscopy, and N2 adsorption porosimetry were employed to characterize the nanocomposites. The results indicate that the ordered hexagonal mesoporous structure of SBA-15 is kept and the absorption band edges of the nanocomposites shift into the ultraviolet light regime. The photocatalytic activity of our samples for degradation of methylene orange was investigated under UV light irradiation, and the results show that the nanocomposites have higher photodegradation ability toward methylene orange than commercial pure P-25. The photocatalytic activity of the nanocomposites was found to be dependent on both the adsorption ability of the SBA-15 and the photocatalytic activity of NiO-ZnO nanoparticles encapsulated in SBA-15. In addition, there is an optimal loading of NiO-ZnO nanoparticles. Too high or low loading will lower the photodegradation ability of the nanocomposites. PMID:27119154

  12. PdCo alloy nanoparticle-embedded carbon nanofiber for ultrasensitive nonenzymatic detection of hydrogen peroxide and nitrite.

    PubMed

    Liu, Dong; Guo, Qiaohui; Zhang, Xueping; Hou, Haoqing; You, Tianyan

    2015-07-15

    PdCo alloy nanoparticle-embedded carbon nanofiber (PdCo/CNF) prepared by electrospinning and thermal treatment was employed as a high-performance platform for the determination of hydrogen peroxide and nitrite. The as-obtained PdCo/CNF were characterized by transmission electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction. Electrochemical impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry were employed to investigate the electrochemical behaviors of the resultant biosensor. The proposed PdCo/CNF-based biosensor showed excellent analytical performances toward hydrogen peroxide (detection limit: 0.1 μM; linear range: 0.2 μM-23.5 mM) and nitrite (detection limit: 0.2 μM; linear range: 0.4-30 μM and 30-400 μM). The superior analytical properties could be attributed to the synergic effect and firmly embedment of well-dispersed PdCo alloy nanoparticles. These attractive electrochemical properties make this robust electrode material promising for the development of effective electrochemical sensors. PMID:25818356

  13. MOF-Derived Hollow Co9 S8 Nanoparticles Embedded in Graphitic Carbon Nanocages with Superior Li-Ion Storage.

    PubMed

    Liu, Jun; Wu, Chao; Xiao, Dongdong; Kopold, Peter; Gu, Lin; van Aken, Peter A; Maier, Joachim; Yu, Yan

    2016-05-01

    Novel electrode materials consisting of hollow cobalt sulfide nanoparticles embedded in graphitic carbon nanocages (HCSP⊂GCC) are facilely synthesized by a top-down route applying room-temperature synthesized Co-based zeolitic imidazolate framework (ZIF-67) as the template. Owing to the good mechanical flexibility and pronounced structure stability of carbon nanocages-encapsulated Co9 S8 , the as-obtained HCSP⊂GCC exhibit superior Li-ion storage. Working in the voltage of 1.0-3.0 V, they display a very high energy density (707 Wh kg(-1) ), superior rate capability (reversible capabilities of 536, 489, 438, 393, 345, and 278 mA h g(-1) at 0.2, 0.5, 1, 2, 5, and 10C, respectively), and stable cycling performance (≈26% capacity loss after long 150 cycles at 1C with a capacity retention of 365 mA h g(-1) ). When the work voltage is extended into 0.01-3.0 V, a higher stable capacity of 1600 mA h g(-1) at a current density of 100 mA g(-1) is still achieved. PMID:26938777

  14. Reduction of charge and discharge polarization by cobalt nanoparticles-embedded carbon nanofibers for Li-O2 batteries.

    PubMed

    Kim, Yun-Jung; Lee, Hongkyung; Lee, Dong Jin; Park, Jung-Ki; Kim, Hee-Tak

    2015-08-10

    The problem of high charge polarization is one of the most significant challenges in current nonaqueous Li-O2 batteries. The development of an electrode for the oxygen evolution reaction (OER) at reduced overpotential is thus essential. Here, we suggest a binder-free electrode based on Co nanoparticles embedded in carbon nanofibers (Co-CNFs), which simultaneously reduces the charge and discharge polarization and extends cycling stability. Co-CNF gives rise to a lower discharge polarization because of an enhanced oxygen reduction reaction activity compared to Co-free CNF. Although the embedment of Co does not enhance the OER activity, it significantly reduces charge overvoltage by forming easily decomposable amorphous Li2 O2 . A mechanism for the formation of amorphous Li2 O2 is suggested in terms of charge localization induced by the Co NPs. The findings suggest a new electrode design strategy of combining inexpensive metals and carbon materials for modulating the phase of the discharge product. PMID:26178625

  15. Two-Solvent Method Synthesis of NiO/ZnO Nanoparticles Embedded in Mesoporous SBA-15: Photocatalytic Properties Study

    NASA Astrophysics Data System (ADS)

    Dai, Peng; Yan, Tao-tao; Yu, Xin-xin; Bai, Zhi-man; Wu, Ming-zai

    2016-04-01

    Different loadings of NiO/ZnO nanoparticles embedded in mesoporous silica (SBA-15) were prepared via a two-solvent method with the ordered hexagonal mesoporous structure of SBA-15 kept. X-ray diffraction, transmission electron microscope, X-ray photoelectron spectroscopy, diffusive reflective UV-vis spectroscopy, and N2 adsorption porosimetry were employed to characterize the nanocomposites. The results indicate that the ordered hexagonal mesoporous structure of SBA-15 is kept and the absorption band edges of the nanocomposites shift into the ultraviolet light regime. The photocatalytic activity of our samples for degradation of methylene orange was investigated under UV light irradiation, and the results show that the nanocomposites have higher photodegradation ability toward methylene orange than commercial pure P-25. The photocatalytic activity of the nanocomposites was found to be dependent on both the adsorption ability of the SBA-15 and the photocatalytic activity of NiO-ZnO nanoparticles encapsulated in SBA-15. In addition, there is an optimal loading of NiO-ZnO nanoparticles. Too high or low loading will lower the photodegradation ability of the nanocomposites.

  16. Enhancement in field emission current density of Ni nanoparticles embedded in thin silica matrix by swift heavy ion irradiation

    SciTech Connect

    Sarker, Debalaya; Patra, Rajkumar; Srivastava, P.; Ghosh, S.; Kumar, H.; Kabiraj, D.; Avasthi, D. K.; Vayalil, Sarathlal K.; Roth, S. V.

    2014-05-07

    The field emission (FE) properties of nickel nanoparticles embedded in thin silica matrix irradiated with 100 MeV Au{sup +7} ions at various fluences are studied here. A large increase in FE current density is observed in the irradiated films as compared to their as deposited counterpart. The dependence of FE properties on irradiation fluence is correlated with surface roughness, density of states of valence band and size distribution of nanoparticles as examined with atomic force microscope, X-ray photoelectron spectroscopy, and grazing incidence small angle x-ray scattering. A current density as high as 0.48 mA/cm{sup 2} at an applied field 15 V/μm has been found for the first time for planar field emitters in the film irradiated with fluence of 5.0 × 10{sup 13} ions/cm{sup 2}. This significant enhancement in the current density is attributed to an optimized size distribution along with highest surface roughness of the same. This new member of field emission family meets most of the requirements of cold cathodes for vacuum micro/nanoelectronic devices.

  17. Transport properties of β-Ga{sub 2}O{sub 3} nanoparticles embedded in Nb thin films

    SciTech Connect

    Vaidhyanathan, L.S. Baisnab, D.K.; Janawadkar, M.P.; Srinivasan, M.P.; Chandra Mohan, P.; Mythili, R.

    2015-01-15

    The origin of ferromagnetism in nanoparticles of nonmagnetic oxides is an interesting area of research. In the present work, transport properties of niobium thin films, with β-Ga{sub 2}O{sub 3} nanoparticles embedded within them, are presented. Nanoparticles of β-Ga{sub 2}O{sub 3} embedded in a Nb matrix were prepared at room temperature by radio frequency co-sputtering technique on Si (100) and glass substrates held at room temperature. The thin films deposited on Si substrates were subjected to Ar annealing at a temperature range of 600-650 C for 1 hour. Films were characterized by X-ray diffraction (XRD), Micro-Raman and elemental identification was performed with an Energy Dispersive X-ray Spectroscopy (EDS). Transport measurements were performed down to liquid helium temperatures by four-probe contact technique, showed characteristics analogous to those observed in the context of a Kondo system. A comparison of the experimental data with the theoretical formalism of Kondo and Hamann is presented. It is suggested that this behavior arises from the existence of magnetic moments associated with the oxygen vacancy defects in the nanoparticles of the nonmagnetic oxide Ga{sub 2}O{sub 3}.

  18. Simulation of Photo-isomerization of Functionalized Azobenzene Derivatives

    NASA Astrophysics Data System (ADS)

    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.

  19. Approximate photochemical dynamics of azobenzene with reactive force fields

    SciTech Connect

    Li, Yan; Hartke, Bernd

    2013-12-14

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

  20. Azobenzene compound-based photomechanical actuator devices

    NASA Astrophysics Data System (ADS)

    Ye, Xianjun; Kuzyk, Mark G.

    2012-10-01

    It has been shown that the chromophore disperse red 1 azobenzene (DR1) when doped into poly(methyl methacrylate) (PMMA) optical fiber can be used to make an optical cantilever in which an asymmetrically propagating beam at 633nm causes the fiber to bend. The fast response process is purported to be due to elongation of the material as molecules change between cis and trans isomers. In our work, UV light of 350nm will be used to investigate trans to cis somerization, which should induce contraction. Short fiber segments in a three-contactpoint geometry will be used to control the position and tilt of silver- or aluminum-coated coverslips that together with microscope glass slides as the substrate make optically-actuated beam-controlling mounts and Fabry-Perot interferometers. A Michelson interferometer is used to measure the length change of the fiber actuator. Azodye doped liquid crystal (LC) elastomers have been demonstrated to have a photomechanical effect that is at least ten times bigger than thermoplastic-based polymer fiber. However, the optical quality of thermoplastics are much better, enabling the cascading of devices in series. We will report on visible and UV laser-actuation of LC elastomer and polymer device structures using a quadrant photodetector to record the beam deflection caused by the shape change of the material, which will allow for dynamical measurements of the mechanisms. All measurements will be calibrated against a piezoelectric crystal actuator. Photomechanical devices provide an inexpensive but versatile, small-form factor, vibration free and high precision solution to optomechanics, sensing, positioning and other space applications.

  1. Azobenzene-Bridged Porphyrin Nanorings: Syntheses, Structures, and Photophysical Properties.

    PubMed

    Huang, Weiming; Lee, Seung-Kyu; Sung, Young Mo; Peng, Fulei; Yin, Bangshao; Ma, Ming; Chen, Bo; Liu, Shubin; Kirk, Steven Robert; Kim, Dongho; Song, Jianxin

    2015-10-19

    Azobenzene-bridged β-to-β and meso-to-meso porphyrin nanorings were successfully synthesized by a palladium-catalyzed Suzuki-Miyaura coupling reaction in a logical synthesis. The dimeric structure was confirmed by XRD analysis. The azo linkages in di- and tetramers are in the all-trans conformation, whereas in the trimers one azo linkage can be interconverted between cis and trans under external stimulation. When trimeric isomers are heated to 333 K or higher, the azo linkages will be in the all-trans configurations: the pure all-trans trimer can be kept in the dark for several months. Fluorescence anisotropy and pump-power-dependent decay results revealed excitation energy transfer for azobenzene-bridged zinc-porphyrin nanorings. The distances between porphyrin units of these azobenzene-bridged porphyrin arrays are almost the same, but the exciton energy hopping (EEH) times for each wheel are markedly different. The dimer and meso-to-meso tetramer possess relatively short excitation energy transfer (EET) times (1.28 and 2.48 ps, respectively) due to their good planarity and rigidity. In contrast, the EET time for the trimeric zinc(II)-porphyrin array (6.9 ps) is relatively long due to its nonradiative decay pathway (i.e., cis/trans isomerization of azobenzene). Both di- and tetramers exhibit relatively high fluorescence quantum yields, whereas the trimers show weak emission because of structural differences. PMID:26338286

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Photoswitchable ring-opening polymerization of lactide catalyzed by azobenzene-based thiourea.

    PubMed

    Dai, Zhongran; Cui, Yaqin; Chen, Changjuan; Wu, Jincai

    2016-07-01

    The reactivity of a catalytic polymerization system using photoresponsive azobenzene-based thiourea/PMDETA as a catalyst could be switched between slow and fast states by alternating exposure to UV and ambient light, because the active site of azobenzene thiourea is blocked via intramolecular hydrogen bonding when the azobenzene thiourea transfers from the E isomer to the Z isomer under UV irradiation. PMID:27345287

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

  5. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... weight of aqueous sodium chloride solution at 20 °C for 24 hours. The low molecular weight extractives... applied mass). The solvent used shall be at least 60 milliliters aqueous sodium chloride solution per gram... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified...

  6. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... weight of aqueous sodium chloride solution at 20 °C for 24 hours. The low molecular weight extractives... applied mass). The solvent used shall be at least 60 milliliters aqueous sodium chloride solution per gram... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified...

  7. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... weight of aqueous sodium chloride solution at 20 °C for 24 hours. The low molecular weight extractives... applied mass). The solvent used shall be at least 60 milliliters aqueous sodium chloride solution per gram... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified...

  8. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... weight of aqueous sodium chloride solution at 20 °C for 24 hours. The low molecular weight extractives... applied mass). The solvent used shall be at least 60 milliliters aqueous sodium chloride solution per gram... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified...

  9. Industrial solution contaminated by polyacrylates: their elimination by electrochemical combustion.

    PubMed

    Masci, M; Chiti, L; De Lorenzo, A; Mantione, D; De Battisti, A; Vatistas, N

    2001-01-01

    The electrochemical combustion of polyacrylates was studied through both direct and indirect oxidation. The obtained results indicate the non elimination of the polyacrylates with the direct oxidation, while the indirect oxidation with NaCl completely eliminates these organic compounds. In the last case the effects of different initial concentrations of NaCl, anode materials and current densities was studied. PMID:11381543

  10. Azobenzene Modified Polymer Electrolyte Membrane for Ion Gating

    NASA Astrophysics Data System (ADS)

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

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

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

    NASA Astrophysics Data System (ADS)

    Rezaee, Mohammadreza; Compton, Robert

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

  12. Switching of an Azobenzene-Tripod Molecule on Ag(111).

    PubMed

    Scheil, Katharina; Gopakumar, Thiruvancheril G; Bahrenburg, Julia; Temps, Friedrich; Maurer, Reinhard Johann; Reuter, Karsten; Berndt, Richard

    2016-06-01

    The trans-cis isomerization makes azobenzene (AB) a robust molecular switch. Once adsorbed to a metal, however, the switching is inefficient or absent due to rapid excited-state quenching or loss of the trans-cis bistability. We find that tris-[4-(phenylazo)-phenyl]-amine is a rather efficient switch on Ag(111). Using scanning tunneling and atomic force microscopy at submolecular resolution along with density functional theory calculations, we show that the switching process is no trans-cis isomerization but rather a reorientation of the N-N bond of an AB unit. It proceeds through a twisting motion of the azo-bridge that leads to a lateral shift of a phenyl ring. Thus, the role of the Ag substrate is ambivalent. While it suppresses the original bistability of the azobenzene units, it creates a new one by inducing a barrier for the rotation of the N-N bond. PMID:27193044

  13. Mesogenic linear azobenzene polymer-stabilized nematic liquid crystals

    SciTech Connect

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

    2011-03-15

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

  14. Charge Transport in Azobenzene-Based Single-Molecule Junctions

    NASA Astrophysics Data System (ADS)

    Garcia-Lekue, Aran; Kim, Youngsang; Sysoiev, Dmytro; Frederiksen, Thomas; Groth, Ulrich; Scheer, Elke

    2013-03-01

    The azobenzene class of molecules has become an archetype of molecular photoswitch research, due to their simple structure and the significant difference of the electronic system between their cis and trans isomers. However, a detailed understanding of the charge transport for the two isomers, when embedded in a junction with electrodes is still lacking. In order to clarify this issue, we investigate charge transport properties through single Azobenzene-ThioMethyl (AzoTM) molecules in a mechanically controlled break junction (MCBJ) system at 4.2 K. Single-molecule conductance, I-V characteristics, and IETS spectra of molecular junctions are measured and compared with first-principles transport calculations. Our studies elucidate the origin of a slightly higher conductance of junctions with cis isomer and demonstrate that IETS spectra of cis and trans forms show distinct vibrational fingerprints that can be used for identifying the isomer.

  15. Ordering of azobenzenes by two-photon isomerization.

    PubMed

    Ishitobi, Hidekazu; Sekkat, Zouheir; Kawata, Satoshi

    2006-10-28

    We report on light induced orientation by two-photon isomerization of azobenzenes in films of polymer. The dynamics of isomerization and orientation by one-photon absorption and two-photon absorption (TPA) are similar, and TPA creates a degree of molecular orientation which is comparable to that achieved by single-photon isomerization, in agreement with the theoretical predictions of two-photon isomeric orientation. PMID:17092131

  16. Ordering of azobenzenes by two-photon isomerization

    SciTech Connect

    Ishitobi, Hidekazu; Sekkat, Zouheir; Kawata, Satoshi

    2006-10-28

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

  17. Azobenzene - functionalized polyelectrolyte nanolayers as ultrafast optoacoustic transducers.

    PubMed

    Pavlenko, E S; Sander, M; Mitzscherling, S; Pudell, J; Zamponi, F; Rössle, M; Bojahr, A; Bargheer, M

    2016-07-21

    We introduce azobenzene-functionalized polyelectrolyte multilayers as efficient, inexpensive optoacoustic transducers for hyper-sound strain waves in the GHz range. By picosecond transient reflectivity measurements we study the creation of nanoscale strain waves, their reflection from interfaces, damping by scattering from nanoparticles and propagation in soft and hard adjacent materials like polymer layers, quartz and mica. The amplitude of the generated strain ε∼ 5 × 10(-4) is calibrated by ultrafast X-ray diffraction. PMID:27341685

  18. Azobenzene - functionalized polyelectrolyte nanolayers as ultrafast optoacoustic transducers

    NASA Astrophysics Data System (ADS)

    Pavlenko, E. S.; Sander, M.; Mitzscherling, S.; Pudell, J.; Zamponi, F.; Rössle, M.; Bojahr, A.; Bargheer, M.

    2016-07-01

    We introduce azobenzene-functionalized polyelectrolyte multilayers as efficient, inexpensive optoacoustic transducers for hyper-sound strain waves in the GHz range. By picosecond transient reflectivity measurements we study the creation of nanoscale strain waves, their reflection from interfaces, damping by scattering from nanoparticles and propagation in soft and hard adjacent materials like polymer layers, quartz and mica. The amplitude of the generated strain ε ~ 5 × 10-4 is calibrated by ultrafast X-ray diffraction.

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

    PubMed

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

    2013-11-01

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

  20. Room temperature observation of size dependent single electron tunneling in a sub-2 nm size tunable Pt nanoparticle embedded metal-oxide-semiconductor structure.

    PubMed

    Yun, Minseong; Ramalingam, Balavinayagam; Gangopadhyay, Shubhra

    2011-11-18

    In this paper we report size dependent single electron tunneling behavior at room temperature in a metal-oxide-semiconductor structure with uniformly sized Pt nanoparticles embedded in an Al(2)O(3) dielectric. The sub-2 nm size Pt nanoparticles sandwiched between the Al(2)O(3) layers are deposited by a unique tilted target sputter deposition technique which produces metal nanoparticles as small as 0.5 nm with narrow size distributions at room temperature. The charging behavior of these nanoparticles shows clear single electron tunneling peaks due to the Coulomb blockade effect. Moreover, the average single electron addition energy and height of the single electron tunneling current strongly depend on the size of the Pt nanoparticle. These controllable single electron tunneling behaviors suggest a new route for fabrication of single electron devices. PMID:22024690

  1. Plasmonic modification of electron-longitudinal-optical phonon coupling in Ag-nanoparticle embedded InGaN/GaN quantum wells

    NASA Astrophysics Data System (ADS)

    Llopis, Antonio; Pereira, Sérgio M. S.; Watson, Ian M.; Neogi, Arup

    2014-09-01

    Surface plasmon enhanced GaN and InGaN quantum wells (QWs) show promise for use as room-temperature light emitters. The effectiveness of the plasmon enhancement, however, is limited by the strong electron/hole and longitudinal optical phonon coupling found in the III-V nitrides. The electron-phonon coupling within semiconductor QWs has been modified using silver nanoparticles embedded within the QWs. Direct evidence is provided for this change via confocal Raman spectroscopy of the samples. This evidence is augmented by Angle-dependent photoluminescence experiments which show the alteration of the electron-phonon coupling strength through measurement of the emitted phonon replicas. Together these demonstrate a direct modification of carrier-phonon interactions within the system, opening up the possibility of controlling the coupling strength to produce high-efficiency room-temperature light emitters.

  2. A tristable [2]rotaxane that is doubly gated by foldamer and azobenzene kinetic barriers.

    PubMed

    Wang, Wei-Kun; Xu, Zi-Yue; Zhang, Yun-Chang; Wang, Hui; Zhang, Dan-Wei; Liu, Yi; Li, Zhan-Ting

    2016-06-14

    A hydrogen bonded foldamer unit and an azobenzene unit have been incorporated into the linear component of a tristable [2]rotaxane to give rise to a doubly gated switching system tuned by the folding-defolding of the foldamer unit and the photo-initiated trans-cis isomerization of the azobenzene unit. PMID:27203526

  3. Polyanionic and polyzwitterionic azobenzene ionic liquid-functionalized silica materials and their chromatographic applications.

    PubMed

    Qiu, Hongdeng; Jiang, Shengxiang; Takafuji, Makoto; Ihara, Hirotaka

    2013-03-25

    New polyanionic and polyzwitterionic azobenzene ionic liquid-functionalized silica materials were designed based on the preparation of a new polymerizable azobenzene anionic monomer and either its cation-exchange with alkylimidazolium after grafting or the formation of an ionic liquid monomer pair before grafting onto silica. PMID:23417018

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

    PubMed

    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. PMID:26340405

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

    NASA Astrophysics Data System (ADS)

    Vaia, R. A.

    2013-03-01

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

  6. Picosecond dynamics in water-soluble azobenzene-peptides

    NASA Astrophysics Data System (ADS)

    Satzger, H.; Root, C.; Renner, C.; Behrendt, R.; Moroder, L.; Wachtveitl, J.; Zinth, W.

    2004-09-01

    Ultrafast absorption changes are recorded for water-soluble cyclic azobenzene peptides containing the photoswitch (4-aminomethyl)-phenyl-azobenzoic acid (AMPB) and a bioactive peptide motif. They can be separated into the fast reactions in the AMPB chromophore and the slower response of the peptide moiety. While the fastest reactions display similar time constants as observed for AMPB peptides dissolved in DMSO the slower reaction dynamics assigned to vibrational cooling and motions of the peptide moiety are faster in water by a factor of up to two. The changes in the reaction times are explained by solvent heat capacity and viscosity.

  7. Structure-Correlation NMR Spectroscopy for Macromolecules Using Repeated Bidirectional Photoisomerization of Azobenzene.

    PubMed

    Nagashima, Toshio; Ueda, Keisuke; Nishimura, Chiaki; Yamazaki, Toshio

    2015-11-17

    Control over macromolecular structure offers bright potentials for manipulation of macromolecular functions. We here present structure-correlation NMR spectroscopy to analyze the correlation between polymorphic macromolecular structures driven by photoisomerization of azobenzene. The structural conversion of azobenzene was induced within the mixing time of a NOESY experiment using a colored light source, and the reverse structural conversion was induced during the relaxation delay using a light source of another color. The correlation spectrum between trans- and cis-azobenzene was then obtained. To maximize the efficiency of the bidirectional photoisomerization of azobenzene-containing macromolecules, we developed a novel light-irradiation NMR sample tube and method for irradiating target molecules in an NMR radio frequency (rf) coil. When this sample tube was used for photoisomerization of an azobenzene derivative at a concentration of 0.2 mM, data collection with reasonable sensitivity applicable to macromolecules was achieved. We performed isomerization of an azobenzene-cross-linked peptide within the mixing time of a NOESY experiment that produced cross-peaks between helix and random-coil forms of the peptide. Thus, these results indicate that macromolecular structure manipulation can be incorporated into an NMR pulse sequence using an azobenzene derivative and irradiation with light of two types of wavelengths, providing a new method for structural analysis of metastable states of macromolecules. PMID:26479462

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

    PubMed

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

    2007-07-01

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

  9. Evanescent polarization holographic recording of sub-200-nm gratings in an azobenzene polyester.

    PubMed

    Ramanujam, P S

    2003-12-01

    I demonstrate high-resolution polarization holographic recording with evanescent waves in a thin film of an azobenzene polyester deposited directly on the hypotenuse of a highly refractive prism. A spatial frequency greater than 7000 lines/mm and diffraction efficiency greater than 1% have been achieved. It was found that diffraction efficiency increases in the dark after the writing beams have been switched off. The biphotonic effect found in other azobenzene polymers, which converts cis states of the azobenzene to trans states followed by an ordering process that is due to aggregation, is proposed as the reason for this increase in diffraction efficiency. PMID:14680187

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

    PubMed

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

    2015-10-16

    A new azobenzene-based photoswitch, 2, has been designed to enable optical control of ionotropic glutamate receptors in neurons via sensitized two-photon excitation with NIR light. In order to develop an efficient and versatile synthetic route for this molecule, a modular strategy is described which relies on the use of a new linear fully protected glutamate derivative stable in basic media. The resulting compound undergoes one-photon trans-cis photoisomerization via two different mechanisms: direct excitation of its azoaromatic unit and irradiation of the pyrene sensitizer, a well-known two-photon sensitive chromophore. Moreover, 2 presents large thermal stability of its cis isomer, in contrast to other two-photon responsive switches relying on the intrinsic nonlinear optical properties of push-pull substituted azobenzenes. As a result, the molecular system developed herein is a very promising candidate for evoking large photoinduced biological responses during the multiphoton operation of neuronal glutamate receptors with NIR light, which require accumulation of the protein-bound cis state of the switch upon repeated illumination. PMID:26414427

  11. Rapid transport of polyacrylates in dextran matrix

    SciTech Connect

    Maeda, H.; Nakamura, K.; Sasaki, S.

    1993-12-31

    The authors have observed the rapid transport of polyacrylate(PA) in the matrix of dextran. (1) In the salt-free media, the transport of PA depended on the kind of its couterions. The rates were in the following order: tetramethylammonium > Li+ > tetrabutylammonium > Na+ > NH{sub 4}+ > Cs+. (2) The transport rate of PAA in buffer solutions of about 30mM ionic strength increased with the degree of ionization {alpha} but remained constant in the range of {alpha} greater than about 0.4. The effect of the counterion condensation on the transport rate was thus clearly demonstrated. (3) The transport rate of NaPA was nearly identical in the presence of 0.1 M NaCl and no added salt. It decreased to less than half in 0.2 M NaCl and in 0.5 M NaCl no rapid transport was observed any more and ordinary diffusion behavior was observed instead.

  12. Fabrication of silver nanoparticles embedded into polyvinyl alcohol (Ag/PVA) composite nanofibrous films through electrospinning for antibacterial and surface-enhanced Raman scattering (SERS) activities.

    PubMed

    Zhang, Zhijie; Wu, Yunping; Wang, Zhihua; Zou, Xueyan; Zhao, Yanbao; Sun, Lei

    2016-12-01

    Silver nanoparticle-embedded polyvinyl alcohol (PVA) nanofibers were prepared through electrospinning technique, using as antimicrobial agents and surface-enhanced Raman scattering (SERS) substrates. Ag nanoparticles (NPs) were synthesized in liquid phase, followed by evenly dispersing in PVA solution. After electrospinning of the mixed solution at room temperature, the PVA embedded with Ag NPs (Ag/PVA) composite nanofibers were obtained. The morphologies and structures of the as-synthesized Ag nanoparticles and Ag/PVA fibers were characterized by the techniques of transmission electron microscopy (TEM), X-ray diffraction (XRD), ultraviolet-visible absorption spectroscopy (UV-vis), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). Ag NPs have an average diameter of 13.8nm, were found to be uniformly dispersed in PVA nanofibers. The Ag/PVA nanofibers provided robust antibacterial activities against both Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli) microorganisms. It's also found that Ag/PVA nanofibers make a significant contribution to the high sensitivity of SERS to 4-mercaptophenol (4-MPh) molecules. PMID:27612736

  13. Performance of an optimized Zr-based nanoparticle-embedded PSF blend hollow fiber membrane in treatment of fluoride contaminated water.

    PubMed

    He, Jinsong; Siah, Tiong-Shie; Paul Chen, J

    2014-06-01

    Consumption of water that has excessive fluoride can cause adverse health impacts on human beings. A Zr-based nanoparticle-embedded PSF blend hollow fiber membrane was successfully prepared and optimized for removal of fluoride from the aqueous solution. Both static and dynamic adsorption of fluoride on the membrane was investigated. It was showed that the membrane could effectively remove fluoride within a wide pH ranging from 3 to 10. At neutral pH, the adsorption equilibrium was reached within 24 h. The maximum adsorption capacity of the optimized membrane was 60.65 mg/g, much higher than many commercial adsorbents. The presence of NO3(-), SiO3(2-) or HA has insignificant effects on the fluoride removal. However, the removal was retarded as the concentration of HCO3(-) or PO4(3-) was increased. Furthermore, the membrane could remove fluoride efficiently through the continuous filtration, even in presence of natural organic matters. The spent membrane could be regenerated and then reused for the removal of fluoride with great efficiency. The adsorption history could be well described by an intraparticle diffusion model. The XPS analysis showed that the adsorption of fluoride was mainly associated with the ion-exchange between SO4(2-) and F(-) ions. Finally, the toxicity analysis revealed that the treated water was safe for human consumption. PMID:24657326

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

    PubMed

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

    2016-12-01

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

  15. A ferrocene-azobenzene derivative showing unprecedented phase transition and better solubility upon UV irradiation.

    PubMed

    Zhang, Rui; Ji, Ya-Jian; Yang, Lan; Zhang, Yi; Kuang, Gui-Chao

    2016-04-21

    The ferrocene-aspartic acid-azobenzene derivative 1 showing an unprecedented photoinduced crystal-liquid phase transition at an elevated temperature and better solubility in organic solvents has been successfully reported. PMID:27025392

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

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

    PubMed

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

    2011-06-20

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

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2016-08-16

    Liquid crystal polymer networks respond with an anisotropic deformation to a range of external stimuli. When doped with molecular photoswitches, these materials undergo complex shape modifications under illumination. As the deformations are reversed when irradiation stops, applications where the activated shape is required to have thermal stability have been precluded. Previous attempts to incorporate molecular switches into thermally stable photoisomers were unsuccessful at photogenerating macroscopic shapes that are retained over time. Herein, we show that to preserve photoactivated molecular deformation on the macroscopic scale, it is important not only to engineer the thermal stability of the photoswitch but also to adjust the cross-linking density in the polymer network and to optimize the molecular orientations in the material. Our strategy resulted in materials containing fluorinated azobenzenes that retain their photochemical shape for more than eight days, which constitutes the first demonstration of long-lived photomechanical deformation in liquid-crystal polymer networks. PMID:27430357

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

    PubMed

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

    2016-01-01

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

  1. Antimicrobial azobenzene compounds and their potential use in biomaterials

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  3. Azobenzene-based supramolecular polymers for processing MWCNTs

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  4. Glycosylated polyacrylate nanoparticles by emulsion polymerization.

    PubMed

    Abeylath, Sampath C; Turos, Edward

    2007-08-01

    A selection of glycosylated polyacrylate nanoparticles has been prepared by radical-initiated emulsion polymerization in aqueous media. Using ethyl acrylate as a co-monomer, carbohydrate acrylates were incorporated into the poly(ethyl acrylate) framework to give stable emulsions of glyconanoparticles with an average particle size of around 40 nm. Using this technique a variety of glyconanoparticles were prepared from 3-O-acryloyl-1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose, 1-O-acryloyl-2,3:5,6-di-O-isopropylidene-alpha-D-mannofuranose, 6-O-acryloyl-1,2:3,4-di-O-isopropylidene-alpha-D-galactopyranose, 2-N-acryloyl-1,3,4,6-tetra-O-acetyl-beta-D-glucosamine, 5-O-acryloyl-2,3-isopropylidene-1-methoxy-beta-D-ribofuranose and 4-N-acetyl-5'-O-acryloyl-2',3'-O-isopropylidene cytidine. Scanning electron microscopy, dynamic light scattering and proton NMR analysis of the emulsions indicated essentially 100% incorporation of the carbohydrate acrylate monomer into the polymer with the exception of O-benzyl- and O-benzoyl-protected carbohydrate acrylates, which gave incomplete incorporation. Formation of larger glyconanoparticles of ~80nm with (unprotected) 3-O-acryloyl-D-glucose and 5-O-acryloyl-1-methoxy-beta-D-ribofuranose revealed the influence of free hydroxyl groups in the monomer on the particle size during polymerization, a feature which is also apparently dependent on the amount of carbohydrate in the matrix. This methodology allows for a new, simple route to the synthesis of polymeric glyconanoparticles with potential applications in targeted drug delivery and materials development. PMID:18677404

  5. Physicochemical and structural studies of clathrate hydrates of tetrabutylammonium polyacrylates.

    PubMed

    Terekhova, Irina S; Manakov, Andrey Yu; Komarov, Vladislav Yu; Villevald, Galina V; Burdin, Alexander A; Karpova, Tamara D; Aladko, Eugeny Ya

    2013-03-01

    In this work, physicochemical and structural studies have been carried out for semiclathrate hydrates of linear (un-cross-linked) and cross-linked tetrabutylammonium polyacrylates with different degrees of cross-linking of the polymeric guest molecules (n = 0.5, 1, 2, 3%) and different degrees of substitution of proton ions of carboxylic groups in poly(acrylic acid) for TBA cations (x = 1, 0.8, 0.6). The changes in the hydrates' stability and composition depending on the outlined parameters were examined in the course of phase diagram studies of the binary systems water-tetrabutylammonium polyacrylates using differential thermal analysis method and calorimetric measurements of fusion enthalpies of the hydrates. Phase diagram studies of the binary system water-linear tetrabutylammonium polyacrylate revealed the formation of four hydrates. Based on the data of chemical analysis of hydrate crystals the compositions of all hydrates have been determined. Single-crystal X-ray diffraction studies revealed a tetragonal structure, space group 4/m, and unit cell parameters are close for different hydrates and lie in the ranges a = 23.4289-23.4713 Å and c = 12.3280-12.3651 Å (150 K). The structure can be related to tetragonal structure I typical for the clathrate hydrates of tetraalkylammonium salts with monomeric anions. Powder X-ray diffraction analyses confirmed the identity of the above crystal structure to that of the hydrates with cross-linked tetrabutylammonium polyacrylates. The behavior of TBA polyacrylate hydrates under the pressure of methane was studied and quantitative assessment of the gas content in the hydrates was made using volumetric analysis method. PMID:23383955

  6. [Polyacrylates of noble metals as potential antitumor drugs].

    PubMed

    Ostrovskaia, L A; Voronkov, M G; Korman, D B; Bliukhterova, N V; Fomina, M M; Rykova, V A; Abzaeva, K A; Zhilitskaia, L V

    2014-01-01

    The antitumor activity of polyacrylates of the noble metals containing argentum (argacryl), aurum (auracryl) and platinum (platacryl) has been studied using experimental murine solid tumor models (Lewis lung carcinoma and Acatol adenocarcinoma). It has been found that polyacrylates of the noble metals are capable of inhibiting tumor development by 50-90% compared to control. Auracryl that inhibites the growth of Lewis lung carcinoma and Acatol adenocarcinoma by 80 and 90%, respectively, compared to control is the most efficient among the tested compounds and can be recommended for the further profound preclinical studies. PMID:25707247

  7. A cationic azobenzene-surfactant-modified graphene hybrid: unique photoresponse and electrochemical behavior

    NASA Astrophysics Data System (ADS)

    Chen, Shu; Bao, Lin; Ou, Encai; Peng, Chang; Wang, Weimao; Xu, Weijian

    2015-11-01

    Surfactant-modified graphene hybrids containing azobenzene groups were for the first time prepared, and the electrochemical performance was investigated. The hybrids were obtained by electrostatic interactions between cationic azobenzene-surfactants and negatively charged graphene oxide in water. The electrostatic interactions, chemical structure and photoresponse of the hybrids were measured by using zeta potential values, fluorescence spectra, FTIR, XPS, XRD, SEM, UV-Vis absorption, AFM and Raman spectra. The electrochemical performance was estimated using cyclic voltammetry. The results show that strong electrostatic interactions exist between the azobenzene surfactants and graphene oxide. Notably, this azobenzene-graphene hybrid can self-assemble into aggregation structures in aqueous solution. Besides, the self-assembly can be reversibly controlled by ultraviolet light (365 nm) and blue light (455 nm) irradiation. This process is driven by the photoinduced polarity change of the cationic azobenzene surfactant and is responsible for the graphene hybrids' electrochemical performance. It is the first example of the reversible self-assembly of graphene driven by light irradiation.Surfactant-modified graphene hybrids containing azobenzene groups were for the first time prepared, and the electrochemical performance was investigated. The hybrids were obtained by electrostatic interactions between cationic azobenzene-surfactants and negatively charged graphene oxide in water. The electrostatic interactions, chemical structure and photoresponse of the hybrids were measured by using zeta potential values, fluorescence spectra, FTIR, XPS, XRD, SEM, UV-Vis absorption, AFM and Raman spectra. The electrochemical performance was estimated using cyclic voltammetry. The results show that strong electrostatic interactions exist between the azobenzene surfactants and graphene oxide. Notably, this azobenzene-graphene hybrid can self-assemble into aggregation structures in aqueous

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

    PubMed

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

    2016-06-01

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

  9. A one-pot synthetic approach to prepare palladium nanoparticles embedded hierarchically porous TiO{sub 2} hollow spheres for hydrogen peroxide sensing

    SciTech Connect

    Kong Lirong; Lu Xiaofeng; Bian Xiujie; Zhang Wanjin; Wang Ce

    2010-10-15

    A simple one-step method to fabricate hierarchically porous TiO{sub 2}/Pd composite hollow spheres without any template was developed by using solvothermal treatment. Pd nanoparticles (2-5 nm) were well dispersed in the mesopores of the TiO{sub 2} hollow spheres via in-situ reduction. In our experiment, polyvinylpyrrolidone played an important role in the synthetic process as the reducing agent and the connective material between TiO{sub 2} and Pd nanoparticles. HF species generated from solvothermal reaction leaded to the formation of TiO{sub 2} hollow spheres and Ostwald ripening was another main factor that affected the size and structure of the hollow spheres. The as-prepared TiO{sub 2}/Pd composite hollow spheres exhibited high electrocatalytic activity towards the reduction of H{sub 2}O{sub 2}. The sensitivity was about 226.72 {mu}A mM{sup -1} cm{sup -2} with a detection limit of 3.81 {mu}M at a signal-to-noise ratio of 3. These results made the hierarchically porous TiO{sub 2}/Pd composite a promising platform for fabricating new nonenzymic biosensors. - Graphical Abstract: A new one-step solvothermal method was developed to prepare Pd nanoparticles embedded hierarchically porous TiO{sub 2} hollow spheres. Due to its unique nanostructure, the prepared TiO{sub 2}/Pd modified GC electrode exhibit a high sensitivity (226.72 {mu}A mM{sup -1} cm{sup -2}), a relatively low reduction potential (-0.2 V), a fast response time (<3 s) and a relatively low detection limit of 3.81 {mu}M (S/N=3) towards H{sub 2}O{sub 2}.

  10. Spontaneous gradual accumulation of hexagonally-aligned nano-silica on gold nanoparticles embedded in stabilized zirconia: a pathway from catalytic to NH3-sensing performance

    NASA Astrophysics Data System (ADS)

    Plashnitsa, Vladimir V.; Elumalai, Perumal; Fujio, Yuki; Kawaguchi, Toshikazu; Miura, Norio

    2011-05-01

    The present study highlights the influence of nano-impurities on the catalytic/sensing performance of nano-structured Au sensing-electrodes (SEs) housed in a quartz reactor and operated at high temperature over a long period of time. The planar sensor, made from a nano-structured Au-SE on a polished-polycrystalline (pp) yttria-stabilized zirconia (YSZ) substrate exhibited initially negligible electromotive force (emf) response to each of the examined gases (CO, CH4, C3H8, C3H6, NOx and NH3; 400 ppm each) at 700 °C in the presence of 5 vol.% oxygen and 5 vol.% water vapor. Such a poor emf response was attributed to the excellent gas-phase oxidation/reduction ability of Au nanoparticles embedded in the YSZ substrate at high temperature. The response of the planar sensor made up of nano-structured Au-SE was monitored for about 75 days at 700 °C. As a result of this long-term monitoring, we detected the appearance of highly sensitive and selective NH3 gas-sensing properties after 45-75 days of sensor operation. Detailed observation of the morphology and composition of the as-fabricated nano-structured Au-SE after 75 days operation at 700 °C revealed the gradual accumulation of hexagonally-aligned SiO2 nano-impurities on the surface of the Au nanoparticles. The NH3 sensing mechanism of the YSZ-based sensor using the spontaneously-formed composite (nano-Au + nano-SiO2)-SE is therefore proposed to be based on a strong acid-base interaction between gaseous NH3 and SiO2 nano-impurities, followed by spillover of adsorbed NH3 towards the nano-Au/pp-YSZ interface.

  11. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...). The solvent used shall be at least 60 milliliters aqueous sodium chloride solution per gram of... grafted copolymer of cross-linked sodium polyacrylate identified as 2-propenoic acid, polymers with N,N-di-2-propenyl-2-propen-1-amine and hydrolyzed polyvinyl acetate, sodium salts, graft (CAS Reg....

  12. Preparation and icephobic properties of polymethyltrifluoropropylsiloxane-polyacrylate block copolymers

    NASA Astrophysics Data System (ADS)

    Li, Xiaohui; Zhao, Yunhui; Li, Hui; Yuan, Xiaoyan

    2014-10-01

    Five polymethyltrifluoropropylsiloxane (PMTFPS)-polyacrylate block copolymers (PMTFPS-b-polyacrylate) were synthesized by free radical polymerization of methyl methacrylate, n-butyl acrylate and hydroxyethyl methacrylate using PMTFPS macroazoinitiator (PMTFPS-MAI) in range of 10-50 mass percentages. The morphology, surface chemical composition and wettability of the prepared copolymer films were investigated by transmission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and water contact angle measurement. Delayed icing time and ice shear strength of the films were also detected for the icephobic purpose. The surface morphologies of the copolymers were different from those of the bulk because of the migration of the PMTFPS segments to the air interface during the film formation. Maximal delayed icing time (186 s at -15 °C) and reduction of the ice shear strength (301 ± 10 kPa) which was significantly lower than that of polyacrylates (804 ± 37 kPa) were achieved when the content of PMTFPS-MAI was 20 wt%. The icephobicity of the copolymers was attributed primarily to the enrichment of PMTFPS on the film surface and synergistic effect of both silicone and fluorine. Thus, the results show that the PMTFPS-b-polyacrylate copolymer can be used as icephobic coating materials potentially.

  13. Induction of E/Z isomerization in a pendant metal-bound azobenzene: a synthetic, spectroscopic and theoretical study.

    PubMed

    Hasheminasab, A; Wang, L; Dawadi, M B; Bass, J; Herrick, R S; Rack, J J; Ziegler, C J

    2015-09-21

    Re(CO)3 conjugates 1 and 2 that incorporate azobenzenes can be readily generated via one-pot reactions using Schiff base reaction forming conditions. Excitation of the MLCT bands in 1 and 2 results in isomerization of the azobenzene moiety, and this process has been investigated via time-resolved photophysics and TDDFT calculations. PMID:26252161

  14. Fluorescence from an azobenzene-containing diblock copolymer micelle in solution.

    PubMed

    Bo, Qi; Zhao, Yue

    2007-05-01

    We report the observation of unusual fluorescence emission from an azobenzene-containing polymer micellar solution. An amphiphilic diblock copolymer composed of the hydrophilic quaternized poly(4-vinyl pyridine) (QP4VP) and a hydrophobic liquid crystalline polymethacrylate bearing azobenzene side groups (PAzoMA) is nonfluorescent in molecularly dissolved state in N,N-dimethyl formamide (DMF) but becomes fluorescent as a result of the micellization upon addition of water, which confines azobenzene groups into the core region of micellar aggregates. Experimental results suggest that the micellization-enhanced fluorescence was caused by a slowdown, due to the confinement effect, in the rate of the trans-to-cis photoisomerization that is the main nonradiative relaxation process for excited azobenzene groups in the trans form. Furthermore, it was found that the fluorescence intensity of aqueous micellar solution is sensitive to changes in pH (reversible fluorescence variation) and to illumination (irreversible fluorescence variation). The results indicate that a subtle change in the state of polymer micellar association may alter the confining state of azobenzene groups responsible for the fluorescence emission. PMID:17407334

  15. A cationic azobenzene-surfactant-modified graphene hybrid: unique photoresponse and electrochemical behavior.

    PubMed

    Chen, Shu; Bao, Lin; Ou, Encai; Peng, Chang; Wang, Weimao; Xu, Weijian

    2015-12-14

    Surfactant-modified graphene hybrids containing azobenzene groups were for the first time prepared, and the electrochemical performance was investigated. The hybrids were obtained by electrostatic interactions between cationic azobenzene-surfactants and negatively charged graphene oxide in water. The electrostatic interactions, chemical structure and photoresponse of the hybrids were measured by using zeta potential values, fluorescence spectra, FTIR, XPS, XRD, SEM, UV-Vis absorption, AFM and Raman spectra. The electrochemical performance was estimated using cyclic voltammetry. The results show that strong electrostatic interactions exist between the azobenzene surfactants and graphene oxide. Notably, this azobenzene-graphene hybrid can self-assemble into aggregation structures in aqueous solution. Besides, the self-assembly can be reversibly controlled by ultraviolet light (365 nm) and blue light (455 nm) irradiation. This process is driven by the photoinduced polarity change of the cationic azobenzene surfactant and is responsible for the graphene hybrids' electrochemical performance. It is the first example of the reversible self-assembly of graphene driven by light irradiation. PMID:26553111

  16. The photoisomerization of a peptidic derivative of azobenzene: A nonadiabatic dynamics simulation of a supramolecular system

    NASA Astrophysics Data System (ADS)

    Ciminelli, Cosimo; Granucci, Giovanni; Persico, Maurizio

    2008-06-01

    The aim of this work is to investigate the mechanism of photoisomerization of an azobenzenic chromophore in a supramolecular environment, where the primary photochemical act produces important changes in the whole system. We have chosen a derivative of azobenzene, with two cyclopeptides attached in the para positions, linked by hydrogen bonds when the chromophore is in the cis geometry. We have run computational simulations of the cis → trans photoisomerization of such derivative of azobenzene, by means of a surface hopping method. The potential energy surfaces and nonadiabatic couplings are computed "on the fly" with a hybrid QM/MM strategy, in which the quantum mechanical subsystem is treated semiempirically. The simulations show that the photoisomerization is fast (about 200 fs) and occurs with high quantum yields, as in free azobenzene. However, the two cyclopeptides are not promptly separated, and the breaking of the hydrogen bonds requires longer times (at least several picoseconds), with the intervention of the solvent molecules (water). As a consequence, the resulting trans-azobenzene is severely distorted, and we show how its approach to the equilibrium geometry could be monitored by time-resolved absorption spectroscopy.

  17. Red-Shifting Azobenzene Photoswitches for in Vivo Use.

    PubMed

    Dong, Mingxin; Babalhavaeji, Amirhossein; Samanta, Subhas; Beharry, Andrew A; Woolley, G Andrew

    2015-10-20

    Recently, there has been a great deal of interest in using the photoisomerization of azobenzene compounds to control specific biological targets in vivo. These azo compounds can be used as research tools or, in principle, could act as optically controlled drugs. Such "photopharmaceuticals" offer the prospect of targeted drug action and an unprecedented degree of temporal control. A key feature of azo compounds designed to photoswitch in vivo is the wavelength of light required to cause the photoisomerization. To pass through tissue such as the human hand, wavelengths in the red, far-red, or ideally near infrared region are required. This Account describes our attempts to produce such azo compounds. Introducing electron-donating or push/pull substituents at the para positions delocalizes the azobenzene chromophore and leads to long wavelength absorption but usually also lowers the thermal barrier to interconversion of the isomers. Fast thermal relaxation means it is difficult to produce a large steady state fraction of the cis isomer. Thus, specifically activating or inhibiting a biological process with the cis isomer would require an impractically bright light source. We have found that introducing substituents at all four ortho positions leads to azo compounds with a number of unusual properties that are useful for in vivo photoswitching. When the para substituents are amide groups, these tetra-ortho substituted azo compounds show unusually slow thermal relaxation rates and enhanced separation of n-π* transitions of cis and trans isomers compared to analogues without ortho substituents. When para positions are substituted with amino groups, ortho methoxy groups greatly stabilize the azonium form of the compounds, in which the azo group is protonated. Azonium ions absorb strongly in the red region of the spectrum and can reach into the near-IR. These azonium ions can exhibit robust cis-trans isomerization in aqueous solutions at neutral pH. By varying the nature

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  19. Facile synthesis of ultrafine SnO2 nanoparticles embedded in carbon networks as a high-performance anode for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Wang, Fei; Jiao, Hongxing; He, Erkang; Yang, Shaoan; Chen, Yongmei; Zhao, Mingshu; Song, Xiaoping

    2016-09-01

    SnO2@C nanocomposites are easily synthesized in a large scale by the hydrolysis of Sn4+ ions in a polyacrylic acid (PAA) hydrogel system, followed by the decomposition of Sn(OH)4 and carbonization of PAA by heat treatment in one-system. The SnO2@C nanocomposites contain uniform ultrafine SnO2 nanoparticles (≈4.3 nm) homogenously embedded in a three-dimensional carbon matrix. This unique structure efficiently suppresses the particle pulverization and aggregation of SnO2, thus maintaining the electrode integrity during long-term lithiation/delithiation process. The discharge capacity of SnO2@C nanocomposites is maintained at ∼597.3 mAh g-1 after 220 cycles. This scalable approach has great potential in the applications of high-capacity anodes in Li-ion batteries.

  20. Stimulus-responsive azobenzene supramolecules: fibers, gels, and hollow spheres.

    PubMed

    Lee, Sumi; Oh, Seungwhan; Lee, Joosub; Malpani, Yashwardhan; Jung, Young-Sik; Kang, Baotao; Lee, Jin Yong; Ozasa, Kazunari; Isoshima, Takashi; Lee, Sang Yun; Hara, Masahiko; Hashizume, Daisuke; Kim, Jong-Man

    2013-05-14

    Novel, stimulus-responsive supramolecular structures in the form of fibers, gels, and spheres, derived from an azobenzene-containing benzenetricarboxamide derivative, are described. Self-assembly of tris(4-((E)-phenyldiazenyl)phenyl)benzene-1,3,5-tricarboxamide (Azo-1) in aqueous organic solvent systems results in solvent dependent generation of microfibers (aq DMSO), gels (aq DMF), and hollow spheres (aq THF). The results of a single crystal X-ray diffraction analysis of Azo-1 (crystallized from a mixture of DMSO and H2O) reveal that it possesses supramolecular columnar packing along the b axis. Data obtained from FTIR analysis and density functional theory (DFT) calculation suggest that multiple hydrogen bonding modes exist in the Azo-1 fibers. UV irradiation of the microfibers, formed in aq DMSO, causes complete melting while regeneration of new fibers occurs upon visible light irradiation. In addition to this photoinduced and reversible phase transition, the Azo-1 supramolecules display a reversible, fiber-to-sphere morphological transition upon exposure to pure DMSO or aq THF. The role played by amide hydrogen bonds in the morphological changes occurring in Azo-1 is demonstrated by the behavior of the analogous, ester-containing tris(4-((E)-phenyldiazenyl)phenyl)benzene-1,3,5-tricarboxylate (Azo-2) and by the hydrogen abstraction in the presence of fluoride anions. PMID:23597134

  1. Mechanical Motion of Chiral Azobenzene Crystals with Twisting upon Photoirradiation.

    PubMed

    Taniguchi, Takuya; Fujisawa, Juri; Shiro, Motoo; Koshima, Hideko; Asahi, Toru

    2016-06-01

    The photomechanical motion of chiral crystals of trans-azobenzene derivatives with an (S)- and (R)-phenylethylamide group was investigated and compared with a racemic crystal. Changes in the UV/Vis absorption spectra of the powdered crystals before and after UV irradiation were measured by using an optical waveguide spectrometer, showing that the lifetime of the cis-to-trans thermal back-isomerization of the chiral crystals was faster than that of the racemic crystals. Upon UV irradiation, a long plate-like chiral microcrystal bent away from the light source with a twisting motion. A square-like chiral microcrystal curled toward the light with some twisting. Reversible bending of a rod-like chiral microcrystal was repeatable over twenty-five cycles. In contrast, bending of a plate-like racemic microcrystal was small. A possible mechanism for the bending and twisting motion was discussed based on the optimized cis conformer determined by using calculations, showing that the bending motion with twisting is caused by elongation along the b axis and shrinkage along the a axis. PMID:27097760

  2. Nonadiabatic ab initio molecular dynamics of photoisomerization in bridged azobenzene

    SciTech Connect

    Gao Aihua; Li Bin; Zhang Peiyu; Han Keli

    2012-11-28

    The photoisomerization mechanisms of bridged azobenzene are investigated by means of surface hopping dynamics simulations based on the Zhu-Nakamura theory. In the geometry optimizations and potential energy surface calculations, four minimum-energy conical intersections between the ground state and the lowest excited state are found to play important roles in the trans-cis and cis-trans isomerization processes. The trans-cis photoisomerization proceeds through two minimum-energy conical intersections. Ultrafast pedal motion of the N atoms and twisting of phenyl rings around their N-C bonds allows the molecule to move to a minimum-energy conical intersection, after which surface hopping from S{sub 1} to S{sub 0} occurs. In the S{sub 0} state, further rotation occurs around the N=N bond and two N-C bonds until the azo moiety and phenyl rings complete their isomerization. Finally, the cis form is achieved by subsequent adjustment of the ethylene bridge. In the cis-trans photodynamics, there is one rotational pathway, in the middle of which two CIs are responsible for the surface hopping to the S{sub 0} state. After the nonadiabatic transition, the molecule reaches the trans form through a barrierless pathway and the two phenyl rings and the additional bridge complete their reorientation almost at the same time.

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

    PubMed Central

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

    2013-01-01

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

  4. Photomechanical response of azobenzene/organophilic mica complexes

    SciTech Connect

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

    2003-12-10

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

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

    PubMed Central

    Bin, Jonghoon; Oates, William S.

    2015-01-01

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

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

    PubMed

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

    2015-12-18

    A series of red-shifted azobenzene amino acids were synthesized in moderate-to-excellent yields via a two-step procedure in which tyrosine derivatives were first oxidized to the corresponding quinonoidal spirolactones followed by ceric ammonium nitrate-catalyzed azo formation with the substituted phenylhydrazines. The resulting azobenzene-alanine derivatives exhibited efficient trans/cis photoswitching upon irradiation with a blue (448 nm) or green (530 nm) LED light. Moreover, nine superfolder green fluorescent protein (sfGFP) mutants carrying the azobenzene-alanine analogues were expressed in E. coli in good yields via amber codon suppression with an orthogonal tRNA/PylRS pair, and one of the mutants showed durable photoswitching with the LED light. PMID:26650435

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

    NASA Astrophysics Data System (ADS)

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

    2004-03-01

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

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

    DOE PAGESBeta

    Jiang, Xingmao; Liu, Nanguo; Assink, Roger A.; Jiang, Yingbing; Brinker, C. Jeffrey

    2011-01-01

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

  9. Charge-transfer dynamics in azobenzene alkanethiolate self-assembled monolayers on gold

    NASA Astrophysics Data System (ADS)

    Gahl, Cornelius; Schmidt, Roland; Brete, Daniel; Paarmann, Stephanie; Weinelt, Martin

    2016-01-01

    We have studied the charge-transfer dynamics in azobenzene-functionalized alkanethiolate self-assembled monolayers. We compare the core-hole-clock technique, i.e., resonant vs. non-resonant contributions in the azobenzene autoionization of the Cls-π* core exciton, with the lifetime of a molecular resonance determined by two-photon photoemission spectroscopy using femtosecond laser pulses. Both techniques yield comparable charge-transfer times of 80 ± 20 fs for a linker consisting of three CH2 groups and one oxygen unit. Thus the quenching of the excitation is about one order of magnitude faster than the time required for the trans to cis isomerization of the azobenzene photoswitch in solution.

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

    PubMed

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

    2016-08-01

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

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

    NASA Astrophysics Data System (ADS)

    Bin, Jonghoon; Oates, William S.

    2015-10-01

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

  12. Theoretical study of intramolecular interactions on H-shape azobenzenes' first-order hyperpolarizabilities

    NASA Astrophysics Data System (ADS)

    Chu, Feng; Zhu, Jing; Lu, Changgui; Cui, Yiping; Zhang, Chaozhi; Lu, Guoyuan

    2008-01-01

    First-order hyperpolarizabilities of H-shape azobenzenes in gas and in THF have been theoretically studied by Hartree-Fock method and basis set sto-3g with Onsager model, including 4,5-bis((E)-(4-nitrophenyl)diazenyl)anthracene-1,8-diol, 4,5-bis((E)-(4-(trifluoromethyl)phenyl)diazenyl)anthracene-1,8-diol, 4,5-bis((E)-(3-chloro-4-fluorophenyl)diazenyl) anthracene-1,8-diol and 4,5-bis((E)-(4-chlorophenyl)diazenyl)anthracene-1,8-diol. Compared with corresponding azobenzene monomers, H-shape azobenzenes had much larger first-order hyperpolarizabilities. There were four factors which could obviously influence their first-order hyperpolarizabilities. Firstly, H-shape azobenzenes possessed dihedral angles of approximate ten degrees caused by coulomb repulsions with weakening dipole's changes between ground states and excited states. Meanwhile, dihedral angle induced energy gap between HOMO and LUMO to increase. Secondly, dipole-dipole interaction was considered as perturbation which caused strong energy splitting of each molecular orbital with the lessening of energy gap. Thirdly, hyper-conjugated effect existed in H-shape azobenzene and it induced energy gap to decline. Fourthly, solvent effects could obviously enhance their first-order hyperpolarizabilities by comparing results in gas with results in THF. These factors competed and affected each other. The latter three factors lastly overcame coulomb repulsion, which explained that H-shape azobenzenes' first-order hyperpolarizabilities were much larger than corresponding monomers'.

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

    PubMed

    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. PMID:25369943

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

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

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

  15. Azobenzene-functionalized cage silsesquioxanes as inorganic-organic hybrid, photoresponsive, nanoscale, building blocks.

    PubMed

    Liu, Yun; Yang, Wenyan; Liu, Hongzhi

    2015-03-16

    Mono- and octa-azobenzene-functionalized cage silsesquioxanes were easily synthesized by the reaction of 4-bromoazobenzene with monovinyl-substituted octasilsesquioxane and cubic octavinylsilsesquioxane through the Heck coupling reaction. Excited-state energies obtained from time-dependent density functional theory (TDDFT) and the CAM-B3LYP functional correlate very well with experimental trans-cis photoisomerization results from UV/Vis spectroscopy. These azobenzene-functionalized cages exhibit good thermal stability and are fluorescent with maximum emission at approximately 400 nm, making them potential materials for blue-light emission. PMID:25663005

  16. Ion exchange selectivity for cross-linked polyacrylic acid

    NASA Technical Reports Server (NTRS)

    May, C. E.; Philipp, W. H.

    1983-01-01

    The ion separation factors for 21 common metal ions with cross-linked polyacrylic acid were determined as a function of pH and the percent of the cross-linked polyacrylic acid neutralized. The calcium ion was used as a reference. At a pH of 5 the decreasing order of affinity of the ions for the cross-linked polyacrylic acid was found to be: Hg++, Fe+++, Pb++, Cr+++, Cu++, Cd++, Al+++, Ag+, Zn++, Ni++, Mn++, Co++, Ca++, Sr++, Ba++, Mg++, K+, Rb+, Cs+, Na+, and Li+. Members of a chemical family exhibited similar selectivities. The Hg++ ion appeared to be about a million times more strongly bound than the alkali metal ions. The relative binding of most of the metal ions varied with pH; the very tightly and very weakly bound ions showed the largest variations with pH. The calcium ion-hydrogen ion equilibrium was perturbed very little by the presence of the other ions. The separation factors and selectivity coefficients are discussed in terms of equilibrium and thermodynamic significance.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  18. Pinning effect for photoisomerization of a dicationic azobenzene derivative by anionic sites of the clay surface.

    PubMed

    Umemoto, Tetsuro; Ohtani, Yuta; Tsukamoto, Takamasa; Shimada, Tetsuya; Takagi, Shinsuke

    2014-01-11

    The photoisomerization behaviour of a dicationic azobenzene derivative on the inorganic surface was examined. The isomerization reaction was controlled by the charged array of the inorganic surface due to the "pinning effect" because of the electrostatic interaction between anionic charged sites on the inorganic surface and cationic charged sites in dye molecules. PMID:24226932

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

    SciTech Connect

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

    2014-08-04

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

  20. An azobenzene-based photochromic liquid crystalline amphiphile for a remote-controllable light shutter.

    PubMed

    Kim, Dae-Yoon; Lee, Sang-A; Kim, Huisu; Min Kim, Soo; Kim, Namil; Jeong, Kwang-Un

    2015-07-14

    By considering intramolecular conformations and intermolecular interactions, an azobenzene-based photochromic liquid crystalline amphiphile is synthesized for demonstrating a remote-controllable light shutter by the photo-induced isothermal phase transition between the highly ordered crystal phase and the isotropic liquid phase. PMID:26067781

  1. Photoswitched Cell Adhesion on Azobenzene-Containing Self-Assembled Films.

    PubMed

    Bian, Qing; Wang, Wenshuo; Han, Guoxiang; Chen, Yupeng; Wang, Shutao; Wang, Guojie

    2016-08-18

    Stimuli-responsive surfaces that can regulate and control cell adhesion have attracted much attention for their great potential in diverse biomedical applications. Unlike for pH- and temperature-responsive surfaces, the process of photoswitching requires no additional input of chemicals or thermal energy. In this work, two different photoresponsive azobenzene films are synthesized by chemisorption and electrostatic layer-by-layer (LbL) assembly techniques. The LbL film exhibits a relatively loose packing of azobenzene chromophores compared with the chemisorbed film. The changes in trans/cis isomer ratio of the azobenzene moiety and the corresponding wettability of the LbL films are larger than those of the chemisorbed films under UV light irradiation. The tendency for cell adhesion on the LbL films decreases markedly after UV light irradiation, whereas adhesion on the chemisorbed films decreases only slightly, because the azobenzene chromophores stay densely packed. Interestingly, the tendency for cell adhesion can be considerably increased on rough substrates, the roughness being introduced by use of photolithography and inductively coupled plasma deep etching techniques. For the chemisorbed films on rough substrates, the amount of cells that adhere also changes slightly after UV light irradiation, whereas, the amount of cells that adhere to LbL films on rough substrates decreases significantly. PMID:27146320

  2. Photocontrolled reversible morphology conversion of protein nanowires mediated by an azobenzene-cored dendrimer.

    PubMed

    Sun, Hongcheng; Zhao, Linlu; Wang, Tingting; An, Guo; Fu, Shuang; Li, Xiumei; Deng, Xiaoli; Liu, Junqiu

    2016-05-21

    A novel strategy to construct photocontrolled protein nanowires with reversible morphology was reported through photoisomerizable azobenzene-cored dendrimer evoked protein self-assembly. Furthermore, the curvature of the protein nanowires could be switched by alternatively irradiating with visible light and ultraviolet light. PMID:27062988

  3. Reversible photoswitching of RNA hybridization at room temperature with an azobenzene C-nucleoside.

    PubMed

    Goldau, Thomas; Murayama, Keiji; Brieke, Clara; Steinwand, Sabrina; Mondal, Padmabati; Biswas, Mithun; Burghardt, Irene; Wachtveitl, Josef; Asanuma, Hiroyuki; Heckel, Alexander

    2015-02-01

    Photoregulation of RNA remains a challenging task as the introduction of a photoswitch entails changes in the shape and the stability of the duplex that strongly depend on the chosen linker strategy. Herein, the influence of a novel nucleosidic linker moiety on the photoregulation efficiency of azobenzene is investigated. To this purpose, two azobenzene C-nucleosides were stereoselectively synthesized, characterized, and incorporated into RNA oligonucleotides. Spectroscopic characterization revealed a reversible and fast switching process, even at 20 °C, and a high thermal stability of the respective cis isomers. The photoregulation efficiency of RNA duplexes upon trans-to-cis isomerization was investigated by using melting point studies and compared with the known D-threoninol-based azobenzene system, revealing a photoswitching amplitude of the new residues exceeding 90 % even at room temperature. Structural changes in the duplexes upon photoisomerization were investigated by using MM/MD calculations. The excellent photoswitching performance at room temperature and the high thermal stability make these new azobenzene residues promising candidates for in-vivo and nanoarchitecture photoregulation applications of RNA. PMID:25537843

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

    NASA Astrophysics Data System (ADS)

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

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

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

    PubMed

    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. PMID:27165777

  6. Synthesis and Non-Resonant Nonlinear Optical Properties of Push-Pull Side-Chain Azobenzene Polymers

    NASA Astrophysics Data System (ADS)

    Fedus, K.; Smokal, V.; Krupka, O.; Boudebs, G.

    In this work, we report preliminary results obtained for methacrylic polymers incorporating azobenzene side-group as nonlinear optical (NLO) active molecule. The trans-cis isomerization properties are discussed. The third-order non-resonant nonlinear refractive index (n2) and nonlinear absorption coefficient (β) are measured using the Z-scan technique at 1064 nm in the picosecond regime. The influence of different electron-acceptor groups in azobenzene moieties on the nonlinear properties is investigated.

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

    PubMed

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

    2014-07-01

    Cross-linked azobenzene liquid-crystalline polymer films with a poly(oxyethylene) backbone are synthesized by photoinitiated cationic copolymerization. Azobenzene moieties in the film surface toward the light source are simultaneously photoaligned during photopolymerization with unpolarized 436 nm light and thus form a splayed alignment in the whole film. The prepared films show reversible photoinduced bending behavior with opposite bending directions when different surfaces of one film face to ultraviolet light irradiation. PMID:24771514

  8. Sensitized Two-NIR-Photon Z→E Isomerization of a Visible-Light-Addressable Bistable Azobenzene Derivative.

    PubMed

    Moreno, Javier; Gerecke, Mario; Grubert, Lutz; Kovalenko, Sergey A; Hecht, Stefan

    2016-01-22

    Two-NIR-photon-triggered Z→E isomerization of an azobenzene was accomplished by covalently linking a two-photon-harvesting triarylamine antenna to a thermally stable ortho-fluorinated azobenzene derivative. The obtained photoswitch is fully addressable with visible and NIR light by using one-photon and two-photon excitation, respectively, with the latter offering enhanced penetration depth and improved spatial resolution. PMID:26679769

  9. Microencapsulation of human fibroblasts in a water-insoluble polyacrylate.

    PubMed

    Boag, A H; Sefton, M V

    1987-12-01

    Viable human diploid fibroblasts have been micro-encapsulated in EUDRAGIT RL, a commercially available water-insoluble polyacrylate, by an interfacial precipitation technique. Cells in medium and polymer solution (in diethyl phthalate) were coextruded and formed into droplets by a coaxial air stream. The droplets fell into a corn-oil/mineral-oil mixture to extract the solvent to precipitate the polymer around the cells. Capsules were ca. 500 mum in diameter depending on the air flowrate with a ca. 10-mum thick wall. When collagen (1 mg/mL) was added to the cell suspension prior to encapsulation and base-washed corn oil was used, cell growth occurred with one doubling achieved after five to six days as the collagen gel contracted inside the capsule. In the absence of collagen, cells spread on the inner wall of the capsule but did not grow, presumably because the surface charge on the capsule was inadequate. In similar fashion fibroblasts spread but did not grow on films of EUDRAGIT RL but did grow on blends of EUDRAGIT RL and EUDRAGIT E containing 10-30% of the latter more highly aminated polyacrylate. Although not suitable for anchorage-dependent cell growth by itself, EUDRAGIT RL has been suitable as a model polymer to demonstrate the feasibility of using water insoluble polyacrylates and organic solvents and nonsolvents for the micro-encapsulation of fibroblasts. Such microcapsules are of potential interest as a mode of large scale tissue culture for the production of novel therapeutic agents. PMID:18581534

  10. Characterization of linear and branched polyacrylates by tandem mass spectrometry.

    PubMed

    Chaicharoen, Kittisak; Polce, Michael J; Singh, Anirudha; Pugh, Coleen; Wesdemiotis, Chrys

    2008-10-01

    The unimolecular degradation of alkali-metal cationized polyacrylates with the repeat unit CH(2)CH(COOR) and a variety of ester pendants has been examined by tandem mass spectrometry. The fragmentation patterns resulting from collisionally activated dissociation depend sensitively on the size of the ester alkyl substituent (R). With small alkyl groups, as in poly(methyl acrylate), lithiated or sodiated oligomers (M) decompose via free-radical chemistry, initiated by random homolytic C-C bond cleavages along the polymer chain. The radical ions formed this way dissociate further by backbiting rearrangements and beta scissions to yield a distribution of terminal fragments with one of the original end groups and internal fragments with 2-3 repeat units. If the ester alkyl group bears three or more carbon atoms, cleavages within the ester moieties become the predominant decomposition channel. This distinct reactivity is observed if R = t-butyl, n-butyl, or the mesogenic group (CH(2))(11)-O-C(6)H(4)-C(6)H(4)-CN. The [M+alkali metal](+) ions of the latter polyacrylates dissociate largely by charge-remote 1,5-H rearrangements that convert COOR to COOH groups by expulsion of 1-alkenes. The acid groups may displace an alcohol unit from a neighboring ester pendant to form a cyclic anhydride, unless hindered by steric effects. Using atom transfer radical polymerization, hyperbranched polyacrylates were prepared carrying ester groups both within and between the branches. Unique alkenes and alcohols are cleaved from ester groups at the branching points, enabling determination of the branching architecture. PMID:18373231

  11. Precipitation of biomimetic fluorhydroxyapatite/polyacrylic acid nanostructures

    NASA Astrophysics Data System (ADS)

    Roche, Kevin J.; Stanton, Kenneth T.

    2015-01-01

    Ordered structures of fluorhydroxyapatite (FHA) nanoparticles that resemble the nanostructure of natural human enamel have been prepared. Wet precipitation in the presence of polyacrylic acid (PAA) was used, and the particle morphology was altered by varying several reaction conditions. High molecular weight PAA increased particle length from around 54 nm to several hundred nanometres, while maintaining particle width at 15 nm. PAA concentration and the order of mixing the reactants also influenced crystal morphology. Optimum conditions produced dense, aligned bundles of highly elongated nanorods, which are very similar to the hierarchical nanostructure of human tooth enamel.

  12. Nickel adsorption by sodium polyacrylate-grafted activated carbon.

    PubMed

    Ewecharoen, A; Thiravetyan, P; Wendel, E; Bertagnolli, H

    2009-11-15

    A novel sodium polyacrylate grafted activated carbon was produced by using gamma radiation to increase the number of functional groups on the surface. After irradiation the capacity for nickel adsorption was studied and found to have increased from 44.1 to 55.7 mg g(-1). X-ray absorption spectroscopy showed that the adsorbed nickel on activated carbon and irradiation-grafted activated carbon was coordinated with 6 oxygen atoms at 2.04-2.06 A. It is proposed that this grafting technique could be applied to other adsorbents to increase the efficiency of metal adsorption. PMID:19576692

  13. Degradation of Sodium-Polyacrylate in Dilute Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Saita, Takao

    1980-12-01

    It is shown using a capillary viscometer that the viscosity of a dilute aqueous solution of sodium-polyacrylate at 20°C decreases gradually for each flow time measurement and also decreases with the time of rest. Assuming that the polymer degradation is caused by shearing stress and oxidation, their effects are discussed with the data obtained using a closed-type capillary viscometer derived for this investigation. It is proved from the results that rupture of the Na-PAA molecule is caused by mechanochemical degradation, and also photo-degradation under the usual illumination and sunlight in a laboratory.

  14. Synthesis of polyacrylic-acid-based thermochromic polymers

    NASA Astrophysics Data System (ADS)

    Srivastava, Jyoti; Alam, Sarfaraz; Mathur, G. N.

    2003-10-01

    Smart materials respond to environmental stimuli with particular changes in some variables (for example temperature, pressure and electric field etc), for that reason they are often called responsive materials. In the present work, we have synthesized thermochromic polymer based on poly acrylic acid cobalt chloride (CoCl2) and phosphoric acid (H3PO4) that visually and reversibly changes color in the temperature range (70 - 130°C). These thermochromic materials can be used as visual sensors of temperature. Thermochromic polymers are based on polyacrylic acid and CoCl2 complex.

  15. Core-shell Co@Co3O4 nanoparticle-embedded bamboo-like nitrogen-doped carbon nanotubes (BNCNTs) as a highly active electrocatalyst for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Xiao, Junwu; Chen, Chen; Xi, Jiangbo; Xu, Yangyang; Xiao, Fei; Wang, Shuai; Yang, Shihe

    2015-04-01

    The current bottleneck for fuel cells and metal-air batteries lies in the sluggish oxygen reduction reaction (ORR) on the cathode side. Despite tremendous efforts, to develop a highly efficient ORR catalyst at low cost remains a great challenge. Herein, we have synthesized core-shell Co@Co3O4 nanoparticles embedded in the bamboo-like N-doped carbon tubes (BNCNTs) by a simple approach comprising thermal treatment of cobalt carbonate hydroxide and urea and oxidization. The ORR catalytic activities of the Co@Co3O4/BNCNT composites are closely dependent on the oxidization degree of the Co nanoparticles and the N content in the BNCNTs. When oxidized at 300 °C, the as-formed Co@Co3O4/BNCNTs-300 composite catalyst with an N/C molar ratio of ~1.6% achieves the maximum ORR catalytic activity. The composite catalyst also exhibits a higher ORR catalytic activity than the Co3O4/carbon nanotube (CNT) catalyst. The tolerance for methanol molecules and the cycle stability performance of the composite catalyst are even superior to those of the highly efficient Pt/C catalyst. Such an excellent ORR catalytic activity can be ascribed to (1) the core-shell Co@Co3O4 nanoparticles embedded in BNCNTs, (2) the N-doping in BNCNTs, and (3) the synergetic effect of (1) and (2) on Co3O4 firmly attached to both Co nanoparticles and BNCNTs, resulting in accelerated electron transport and enhanced charge delocalization.The current bottleneck for fuel cells and metal-air batteries lies in the sluggish oxygen reduction reaction (ORR) on the cathode side. Despite tremendous efforts, to develop a highly efficient ORR catalyst at low cost remains a great challenge. Herein, we have synthesized core-shell Co@Co3O4 nanoparticles embedded in the bamboo-like N-doped carbon tubes (BNCNTs) by a simple approach comprising thermal treatment of cobalt carbonate hydroxide and urea and oxidization. The ORR catalytic activities of the Co@Co3O4/BNCNT composites are closely dependent on the oxidization degree of

  16. Core-shell Co@Co3O4 nanoparticle-embedded bamboo-like nitrogen-doped carbon nanotubes (BNCNTs) as a highly active electrocatalyst for the oxygen reduction reaction.

    PubMed

    Xiao, Junwu; Chen, Chen; Xi, Jiangbo; Xu, Yangyang; Xiao, Fei; Wang, Shuai; Yang, Shihe

    2015-04-28

    The current bottleneck for fuel cells and metal-air batteries lies in the sluggish oxygen reduction reaction (ORR) on the cathode side. Despite tremendous efforts, to develop a highly efficient ORR catalyst at low cost remains a great challenge. Herein, we have synthesized core-shell Co@Co3O4 nanoparticles embedded in the bamboo-like N-doped carbon tubes (BNCNTs) by a simple approach comprising thermal treatment of cobalt carbonate hydroxide and urea and oxidization. The ORR catalytic activities of the Co@Co3O4/BNCNT composites are closely dependent on the oxidization degree of the Co nanoparticles and the N content in the BNCNTs. When oxidized at 300 °C, the as-formed Co@Co3O4/BNCNTs-300 composite catalyst with an N/C molar ratio of ∼ 1.6% achieves the maximum ORR catalytic activity. The composite catalyst also exhibits a higher ORR catalytic activity than the Co3O4/carbon nanotube (CNT) catalyst. The tolerance for methanol molecules and the cycle stability performance of the composite catalyst are even superior to those of the highly efficient Pt/C catalyst. Such an excellent ORR catalytic activity can be ascribed to (1) the core-shell Co@Co3O4 nanoparticles embedded in BNCNTs, (2) the N-doping in BNCNTs, and (3) the synergetic effect of (1) and (2) on Co3O4 firmly attached to both Co nanoparticles and BNCNTs, resulting in accelerated electron transport and enhanced charge delocalization. PMID:25465620

  17. Induction of mesenchymal stem cell chondrogenesis by polyacrylate substrates

    PubMed Central

    Glennon-Alty, Laurence; Williams, Rachel; Dixon, Simon; Murray, Patricia

    2013-01-01

    Mesenchymal stem cells (MSCs) can generate chondrocytes in vitro, but typically need to be cultured as aggregates in the presence of transforming growth factor beta (TGF-β), which makes scale-up difficult. Here we investigated if polyacrylate substrates modelled on the functional group composition and distribution of the Arg-Gly-Asp (RGD) integrin-binding site could induce MSCs to undergo chondrogenesis in the absence of exogenous TGF-β. Within a few days of culture on the biomimetic polyacrylates, both mouse and human MSCs, and a mesenchymal-like mouse-kidney-derived stem cell line, began to form multi-layered aggregates and started to express the chondrocyte-specific markers, Sox9, collagen II and aggrecan. Moreover, collagen II tended to be expressed in the centre of the aggregates, similarly to developing limb buds in vivo. Surface analysis of the substrates indicated that those with the highest surface amine content were most effective at promoting MSC chondrogenesis. These results highlight the importance of surface group functionality and the distribution of those groups in the design of substrates to induce MSC chondrogenesis. PMID:23237986

  18. Induction of mesenchymal stem cell chondrogenesis by polyacrylate substrates.

    PubMed

    Glennon-Alty, Laurence; Williams, Rachel; Dixon, Simon; Murray, Patricia

    2013-04-01

    Mesenchymal stem cells (MSCs) can generate chondrocytes in vitro, but typically need to be cultured as aggregates in the presence of transforming growth factor beta (TGF-β), which makes scale-up difficult. Here we investigated if polyacrylate substrates modelled on the functional group composition and distribution of the Arg-Gly-Asp (RGD) integrin-binding site could induce MSCs to undergo chondrogenesis in the absence of exogenous TGF-β. Within a few days of culture on the biomimetic polyacrylates, both mouse and human MSCs, and a mesenchymal-like mouse-kidney-derived stem cell line, began to form multi-layered aggregates and started to express the chondrocyte-specific markers, Sox9, collagen II and aggrecan. Moreover, collagen II tended to be expressed in the centre of the aggregates, similarly to developing limb buds in vivo. Surface analysis of the substrates indicated that those with the highest surface amine content were most effective at promoting MSC chondrogenesis. These results highlight the importance of surface group functionality and the distribution of those groups in the design of substrates to induce MSC chondrogenesis. PMID:23237986

  19. Waterborne polyacrylic/PEDOT nanocomposites for conductive transparent adhesives.

    PubMed

    Kim, Byeonggwan; Park, Teahoon; Kim, Jeonghun; Kim, Eunkyoung

    2013-11-01

    A new nanocomposite for conductive transparent adhesives (CTAs) was synthesized by emulsion polymerization of acrylate monomers dispersed with poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). Polymer particles of waterborne CTAs were uniform, and the average size of the particles was 330 nm. The conductive transparent adhesive nanocomposites (CTANs) were casted onto various substrates including slide glass, indium tin oxide (ITO) glass, and PET film. Upon thermal processing at 80 degrees C, highly transparent adhesive films were obtained with surface uniformity. The stress of the CTANs was affected by the contents of PEDOT:PSS, and a 7.5 wt% CTAN film had the highest maximum stress of 0.33 MPa. Importantly, polyacrylic nanoparticles were well dispersed with conductive filler PEDOT:PSS in water because of their high dispersity in water. Therefore, the polyacrylic/PEDOT nanocomposite had a low percolation threshold of approximately 8% due to the enhanced connection between conductive channels. The CTANs with an optimum content (10 wt%) of PEDOT:PSS had high electromagnetic interference shielding effectiveness (36 dB) and transparency (75%) for application to electronics including displays and solar cells. PMID:24245305

  20. Mechanism of Concentration Dependence of Water Diffusivity in Polyacrylate Gels

    NASA Astrophysics Data System (ADS)

    Mani, Sriramvignesh; Khabaz, Fardin; Khare, Rajesh

    Membrane based separation processes offer an energy efficient alternative to traditional distillation based separation processes. In this work, we focus on the molecular mechanisms underlying the process of separation of dilute ethanol-water mixture using polyacrylate gels as pervaporation membranes. The diffusivities of the components in swollen gels exhibit concentration dependence. We have used molecular dynamics (MD) simulations to study the correlation between the dynamics of solvent (water and ethanol) molecules, polymer dynamics and solvent structure in the swollen gel systems as a function of solvent concentration. Three different polyacrylate gels were studied: (1) poly n-butyl acrylate (PBA), (2) copolymer of butyl acrylate and 2-hydroxyethyl acrylate P(BA50-HEA50), and (3) poly 2-hydroxyethyl acrylate (PHEA). Simulation results show that solvent concentration has a significant effect on local structure of the solvent molecules and chain dynamics; these factors (local structure and chain dynamics), in turn, affect the diffusivity of these molecules. At low concentration, solvent molecules are well dispersed in the gel matrix and form hydrogen bonds with the polymer. Solvent mobility is correlated with polymer mobility in this configuration and consequently water and ethanol molecules exhibit slower dynamics, this effect is especially significant in PHEA gel. At high solvent concentration, water molecules form large clusters in the system accompanied by enhancement in mobility of both the gel network and the solvent molecules.

  1. A Mononuclear Uranium(IV) Single-Molecule Magnet with an Azobenzene Radical Ligand.

    PubMed

    Antunes, Maria A; Coutinho, Joana T; Santos, Isabel C; Marçalo, Joaquim; Almeida, Manuel; Baldoví, José J; Pereira, Laura C J; Gaita-Ariño, Alejandro; Coronado, Eugenio

    2015-12-01

    A tetravalent uranium compound with a radical azobenzene ligand, namely, [{(SiMe2 NPh)3 -tacn}U(IV) (η(2) -N2 Ph2 (.) )] (2), was obtained by one-electron reduction of azobenzene by the trivalent uranium compound [U(III) {(SiMe2 NPh)3 -tacn}] (1). Compound 2 was characterized by single-crystal X-ray diffraction and (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(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. PMID:26536849

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

    PubMed

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

    2016-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

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

    PubMed

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

    2014-09-01

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

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    Eljabu, Fatma; Dhruval, Joshi; Yan, Hongbin

    2015-12-01

    Cyclic azobenzene carboxylic acid was synthesized using a shortened route. After reaction with D-threolinol, the resulting cyclic azobenzene-D-threolinol (cAB-Thr) building block was transformed into the corresponding DMTr-protected phosphoramidite, and incorporated into oligodeoxynucleotides at various positions and frequencies by solid phase synthesis. The melting temperatures of these modified oligonucleotides were determined by UV spectrometry. Photo-regulation of cAB-Thr-modified oligonucleotides with their complementary sequence was evaluated by Fluorescence Resonance Energy Transfer experiments using a fluorescein-Black Hole Quencher pair. Results suggest that while cis-cAB destabilizes DNA duplexes, trans-cAB can be accommodated in double stranded DNA. PMID:26592170

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

    PubMed

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

    2015-11-01

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

  8. Red light holographic recording and readout on an azobenzene-LC polymer hybrid composite system

    NASA Astrophysics Data System (ADS)

    Mao, Weidong; Sun, Qunhui; Baig, Sarfaraz; Lu, Hui; Wang, Michael R.

    2015-11-01

    We present for the first time stable red light two-dimensional image holographic recording in azobenzene-containing polymer-liquid crystal material following a pre-illumination process. The red light hologram recording is based on cis-to-trans transition of the azobenzene and surrounding LC reorientation. The diffraction efficiency of about 2% has been achieved and clear holograms of a commercial 2D USAF resolution target have been recorded. Using the same readout wavelength as the recording wavelength, color distortion that exists in most hologram researches with azo-containing materials is naturally eliminated. Long-time stabilities such as one-day continuous non-destructive readout and up to 10 weeks hologram storage have been demonstrated. The holographic recording material remains erasable and rewritable.

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

    PubMed Central

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

    2016-01-01

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

  10. Bioorthogonal cleavage and exchange of major histocompatibility complex ligands by employing azobenzene-containing peptides.

    PubMed

    Choo, Joanna A L; Thong, Sock Yue; Yap, Jiawei; van Esch, Wim J E; Raida, Manfred; Meijers, Rob; Lescar, Julien; Verhelst, Steven H L; Grotenbreg, Gijsbert M

    2014-12-01

    Bioorthogonal cleavable linkers are attractive building blocks for compounds that can be manipulated to study biological and cellular processes. Sodium dithionite sensitive azobenzene-containing (Abc) peptides were applied for the temporary stabilization of recombinant MHC complexes, which can then be employed to generate libraries of MHC tetramers after exchange with a novel epitope. This technology represents an important tool for high-throughput studies of disease-specific T cell responses. PMID:25348595

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

    PubMed

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

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1995-10-01

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

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

    PubMed Central

    2015-01-01

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

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

    PubMed

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

    2014-03-11

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

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

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

    SciTech Connect

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

    2014-12-15

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

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

    PubMed

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

    2016-01-01

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

  18. Photon-Manipulated Drug Release from Mesoporous Nanocontainer Controlled by Azobenzene-Modified Nucleic Acid

    PubMed Central

    Yuan, Quan; Zhang, Yunfei; Chen, Tao; Lu, Danqing; Zhao, Zilong; Zhang, Xiaobing; Li, Zhenxing; Yan, Chun-Hua; Tan, Weihong

    2012-01-01

    Herein a photon manipulated mesoporous release system was constructed based on azobenzene-modified nucleic acids. In this system, the azobenzene-incorporated DNA double strands were immobilized at the pore mouth of meso-porous silica nanoparticles. The photo-isomerization of azobenzene induced dehybridization/hybridization switch of complementary DNA, causing uncapping/capping of pore gates of mesoporous silica. This nanoplatform permits holding of guest molecules within the nanopores under visible light but release them when light wavelength turns to UV range. These DNA/mesoporous silica hybrid nanostructures were exploited as carriers for cancer cell chemotherapy drug doxorubicin (DOX) due to its stimuli-responsive property as well as good biocompatibility via MTT assay. It is found that the drug release behavior is light wavelength sensitive. Switching of the light from visible to UV range uncapped the pores causes the release of DOX from the mesoporous silica nanospheres and an obvious cytotoxic effect on cancer cells. We envision that this photo-controlled drug release system could find potential applications in cancer therapy. PMID:22670595

  19. Holographic studies of azobenzene-containing low-molecular-weight organic glasses

    NASA Astrophysics Data System (ADS)

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

    2009-02-01

    The formation of phase and surface relief gratings in low-molecular-weight organic glasses containing azobenzene moieties has been studied with holographic methods. Advantages of this class of materials are the simple synthesis, the perfectly amorphous phase, and the possibility of blending them with polymers. Surface relief gratings are formed very efficiently in molecular glasses, and this process can be explained by the gradient force model. Heights up to 610 nm were measured; the temporal evolution of the diffraction efficiency could be reproduced in computer simulations. For technical applications, the surface relief gratings can easily be duplicated by replica molding. Since surface gratings are detrimental to holographic data storage at high densities, it is also possible to suppress their formation by using proper polarizations of the writing beams. Reorientation of the azobenzene groups in the bulk of the glasses and angular multiplexing was demonstrated and the thermal stability of the corresponding phase gratings was studied. Different combinations of molecular cores and substituents at the azobenzene moieties were investigated to find the best systems which yield a high sensitivity and fast grating build-up.

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

    SciTech Connect

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

    2012-07-01

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

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

    NASA Astrophysics Data System (ADS)

    Floß, Gereon; Granucci, Giovanni; Saalfrank, Peter

    2012-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    PubMed

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

    2016-03-01

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

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2016-03-01

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

  6. Copper-Promoted Tandem Reaction of Azobenzenes with Allyl Bromides via N═N Bond Cleavage for the Regioselective Synthesis of Quinolines.

    PubMed

    Yi, Xiangli; Xi, Chanjuan

    2015-12-01

    A copper-promoted tandem reaction of a variety of azobenzenes and allyl bromides via N═N bond cleavage to regioselectively construct quinoline derivatives has been developed. The azobenzenes act as not only construction units but also an oxidant for quinoline formation. PMID:26580318

  7. Polyacrylic acids-bovine serum albumin complexation: Structure and dynamics.

    PubMed

    Othman, Mohamed; Aschi, Adel; Gharbi, Abdelhafidh

    2016-01-01

    The study of the mixture of BSA with polyacrylic acids at different masses versus pH allowed highlighting the existence of two regimes of weak and strong complexation. These complexes were studied in diluted regime concentration, by turbidimetry, dynamic light scattering (DLS), zeta-potential measurements and nuclear magnetic resonance (NMR). We have followed the pH effect on the structure and properties of the complex. This allowed refining the interpretation of the phase diagram and understanding the observed phenomena. The NMR measurements allowed probing the dynamics of the constituents versus the pH. The computational method was used to precisely determine the electrostatic potential of BSA and how the polyelectrolyte binds to it at different pH. PMID:26478316

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

    PubMed

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

    2015-03-01

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

  9. Research on the chemical mechanism in the polyacrylate latex modified cement system

    SciTech Connect

    Wang, Min; Wang, Rumin; Zheng, Shuirong; Farhan, Shameel; Yao, Hao; Jiang, Hao

    2015-10-15

    In this paper, the chemical mechanism in the polyacrylate latex modified cement system was investigated by Fourier transform infrared spectra (FT-IR), X-ray photoelectron spectroscopy (XPS), gel permeation chromatography (GPC) and compact pH meter. All results have shown that the chemical reactions in the polyacrylate modified system can be divided into three stages. The hydration reactions of cement can produce large amounts of Ca(OH){sub 2} (calcium hydroxide) and lead the whole system to be alkali-rich and exothermic at the first stage. Subsequently, this environment can do great contributions to the hydrolysis of ester groups in the polyacrylate chains, resulting in the formation of carboxyl groups at the second stage. At the third stage, the final crosslinked network structure of the product was obtained by the reaction between the carboxyl groups in the polyacrylate latex chains and Ca(OH){sub 2}.

  10. Kinetics of chromium ion absorption by cross-linked polyacrylate films

    NASA Technical Reports Server (NTRS)

    May, C. E.

    1984-01-01

    Three cross-linked ion exchange membranes were studied as to their ability to absorb chromium ion from aqueous chromium III nitrate solutions. Attention was given to the mechanism of absorption, composition of the absorbed product, and the chemical bonding. The membranes were: calcium polyacrylate, polyacrylic acid, and a copolymer of acrylic acid and vinyl alcohol. For the calcium polyacrylate and the copolymer, parabolic kinetics were observed, indicating the formation of a chromium polyacrylate phase as a coating on the membrane. The rate of absorption is controlled by the diffusion of the chromium ion through this coating. The product formed in the copolymer involves the formation of a coordination complex of a chromium ion with 6 carboxylic acid groups from the same molecule. The absorption of the chromium ion by the polyacrylic acid membranes appears to be more complicated, involving cross-linking. This is due to the coordination of the chromium ion with carboxylic acid groups from more than one polymer molecule. The absorption rate of the chromium ion by the calcium salt membrane was found to be more rapid than that by the free polyacrylic acid membrane.

  11. Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface

    NASA Astrophysics Data System (ADS)

    Ylikantola, A.; Linnanto, J.; Knuutinen, J.; Oravilahti, A.; Toivakka, M.

    2013-07-01

    The interactions between calcite pigment and sodium polyacrylate dispersing agent, widely used in papermaking as paper coating components, were investigated using classical force field and quantum chemical approaches. The objective was to understand interactions between the calcite surface and sodium polyacrylate polymer at 300 K using molecular dynamics simulations. A quantum mechanical ab initio Hartree-Fock method was also used to obtain detailed information about the sodium polyacrylate polymer structure. The effect of water molecules (moisture) on the interactions was also examined. Calculations showed that molecular weight, branching and the orientation of sodium polyacrylate polymers influence the interactions between the calcite surface and the polymer. The force field applied, and also water molecules, were found to have an impact on all systems studied. Ab initio Hartree-Fock calculations indicated that there are two types of coordination between sodium atoms and carboxylate groups of the sodium polyacrylate polymer, inter- and intra-carboxylate group coordination. In addition, ab initio Hartree-Fock calculations of the structure of the sodium polyacrylate polymer produced important information regarding interactions between the polymers and carboxylated styrene-butadiene latex particles.

  12. Reversible work function changes induced by photoisomerization of asymmetric azobenzene dithiol self-assembled monolayers on gold

    SciTech Connect

    Ah Qune, Lloyd F. N.; Wee, Andrew T. S.; Akiyama, H.; Nagahiro, T.; Tamada, K.

    2008-08-25

    We measured reversible changes in the work function ({delta}{phi}{sub Au}) of gold substrates modified by asymmetric azobenzene dithiol self-assembled monolayers (SAMs) following photoisomerization and thermal recovery of the azo unit. The azobenzene derivative SAMs were photoisomerized to cis form by UV irradiation. {delta}{phi}{sub Au} was monitored in real time during thermal recovery to trans form by ultraviolet photoelectron spectroscopy using a synchrotron light source. Changing the substituted functional group in the p{sup '} position of the azobenzene from electron donating to electron withdrawing resulted in opposite responses of {delta}{phi}{sub Au} against photoisomerization. Hence, a direct correlation between {delta}{phi}{sub Au} and changes in molecular dipole moments was obtained.

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

    USGS Publications Warehouse

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

    2003-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  15. Mn(x)O(y)/NC and Co(x)O(y)/NC nanoparticles embedded in a nitrogen-doped carbon matrix for high-performance bifunctional oxygen electrodes.

    PubMed

    Masa, Justus; Xia, Wei; Sinev, Ilya; Zhao, Anqi; Sun, Zhenyu; Grützke, Stefanie; Weide, Philipp; Muhler, Martin; Schuhmann, Wolfgang

    2014-08-01

    Reversible interconversion of water into H2 and O2, and the recombination of H2 and O2 to H2O thereby harnessing the energy of the reaction provides a completely green cycle for sustainable energy conversion and storage. The realization of this goal is however hampered by the lack of efficient catalysts for water splitting and oxygen reduction. We report exceptionally active bifunctional catalysts for oxygen electrodes comprising Mn3O4 and Co3O4 nanoparticles embedded in nitrogen-doped carbon, obtained by selective pyrolysis and subsequent mild calcination of manganese and cobalt N4 macrocyclic complexes. Intimate interaction was observed between the metals and nitrogen suggesting residual M-N(x) coordination in the catalysts. The catalysts afford remarkably lower reversible overpotentials in KOH (0.1 M) than those for RuO2, IrO2, Pt, NiO, Mn3O4, and Co3O4, thus placing them among the best non-precious-metal catalysts for reversible oxygen electrodes reported to date. PMID:24975388

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

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    PubMed Central

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

    2014-01-01

    The efficient removal of trace carcinogenic organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs) and ionic dyes, from water is an important technical challenge. We report a highly effective recyclable multifunctional azobenzene (AZ)-based silica-supported polymeric adsorbent which can simultaneously remove both PAHs and anionic dyes from water to below parts per billion (ppb) level based on multiple interactions such as the hydrophobic effect, π–π stacking and electrostatic interactions, thus providing a new strategy for designer water remediation materials. PMID:25465671

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

    PubMed

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

    2016-03-01

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

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

    SciTech Connect

    Nakano, Hideyuki; Tanino, Takahiro; Shirota, Yasuhiko

    2005-08-08

    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.

  1. Optical control of structural morphology in azobenzene containing polymeric liquid crystals.

    PubMed

    Camorani, Paolo; Fontana, Marco P

    2006-01-01

    We present a study of photoinduced transitions occurring in a low T(G) liquid crystalline polymer containing the azobenzene group in the side chain. The structural phase of this material can be optically switched between the glassy, nematic and isotropic states. We show the equivalence of light and temperature in causing these effects, promoting this material as a tool in the investigation of structural relaxation at transitions in confined geometry and fast temperature variation as in the case of the optically induced quenching that we report. The results allow us to propose also alternative writing methods for the application of these materials to high density optical memories. PMID:16486165

  2. Adsorption of carboxymethylester-azobenzene on copper and gold single crystal surfaces

    NASA Astrophysics Data System (ADS)

    Piantek, M.; Miguel, J.; Bernien, M.; Navío, C.; Krüger, A.; Priewisch, B.; Rück-Braun, K.; Kuch, W.

    2008-11-01

    The adsorption of 3,3'-di(methoxycarbonyl)azobenzene (CMA) on Au(111) and on Cu(001) substrates was studied by X-ray absorption spectroscopy measurements at the C, N, and O K edges. We find the molecules physisorbed in a planar conformation flat on the Au(111) surface. At higher coverages, a molecular crystal is formed wherein the molecules have the same flat geometry. On Cu(001), additional chemical bonds are formed between the molecules and the surface via the nitrogen atoms. Here the methyl benzoate moieties are tilted out of the surface plane.

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

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

    SciTech Connect

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

    2005-01-10

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

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

    PubMed Central

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

    2015-01-01

    Incorporating the photoisomerizable azobenzene into imidacloprid produced a photoswitchable insecticidal molecule as the first neonicotinoid example of remote control insecticide performance with spatiotemporal resolution. The designed photoswitchable insecticides showed distinguishable activity against Musca both in vivo and in vitro upon irradiation. Molecular docking study further suggested the binding difference of the two photoisomers. The generation of these photomediated insecticides provides novel insight into the insecticidal activity facilitating further investigation on the functions of insect nicotinic acetylcholine receptors and opens a novel way to control and study insect behavior on insecticide poisoning using light. PMID:26434681

  6. Impact of sodium polyacrylate on the amorphous calcium carbonate formation from supersaturated solution.

    PubMed

    Liu, J; Pancera, S; Boyko, V; Gummel, J; Nayuk, R; Huber, K

    2012-02-21

    A detailed in situ scattering study has been carried out on the formation of amorphous calcium carbonate (ACC) particles modulated by the presence of small amounts of sodium polyacrylate chains. The work is aiming at an insight into the modulation of ACC formation by means of two polyacrylate samples differing in their molecular weight by a factor of 50. The ACC formation process was initiated by an in situ generation of CO(3)(2-) ions via hydrolysis of 10 mM dimethylcarbonate in the presence of 10 mM CaCl(2). Analysis of the formation process by means of time-resolved small-angle X-ray and light scattering in the absence of any additives provided evidence for a monomer addition mechanism for the growth of ACC particles. ACC formation under these conditions sets in after a lag-period of some 350 s. In the presence of sodium polyacrylate chains, calcium polyacrylate aggregates are formed during the lag-period, succeeded by a modulated ACC growth in a second step. The presence of anionic polyacrylate chains changed the shape of the growing particles toward loose and less homogeneous entities. In the case of low amounts (1.5-7.5 mg/L) of the long chain additive with 97 kDa, the size of the aggregates is comparable to the size of the successively formed hybrid particles. No variation of the lag-period has been observed in this case. Use of the short chain additive with 2 kDa enabled increase of the additive concentration up to 100 mg/L and resulted in a significant increase of the lag-period. This fact, together with the finding that the resulting hybrid particles remained stable in the latter case, identified short chain sodium polyacrylates as more efficient modulators than long chain polyacrylates. PMID:22256962

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

    PubMed

    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

  8. Vesicles prepared with the complex salts dioctadecyldimethylammonium polyacrylates.

    PubMed

    Alves, Fernanda Rosa; Loh, Watson

    2012-02-15

    The effect of a polymeric counterion on the thermotropic behavior of sonicated vesicles formed by complex salts in aqueous solution and with decanol (C(10)OH) and tetradecanol (C(14)OH) was investigated. The complex salts were prepared with dioctadecyldimethylammonium bromide (DODAB) and polyacrylic acids (PAA, containing 30 or 6000 repeating units), being referred to as DODAPA(30) and DODAPA(6000). Vesicles containing polymeric counterions presented higher contents of multilamellar vesicles that were dependent on the complex salt concentration and on the counterion chain length. For comparison, studies were performed with DODAAc, with the counterion acetate, resulting in the formation of mostly unilamellar vesicles, as expected due greater dissociation, leading to greater electrical repulsion between bilayers. Mixtures of these complex salts and DODAX (where X=acetate or bromide) were also investigated with respect to their vesicles thermotropic behavior and size. This study opens the possibility of applying the methodology of direct complex salt preparation (as opposed to mixing the surfactant and polymeric components) to produce vesicles with controlled composition and properties. PMID:22172692

  9. Patterned biofunctional poly(acrylic acid) brushes on silicon surfaces.

    PubMed

    Dong, Rong; Krishnan, Sitaraman; Baird, Barbara A; Lindau, Manfred; Ober, Christopher K

    2007-10-01

    Protein patterning was carried out using a simple procedure based on photolithography wherein the protein was not subjected to UV irradiation and high temperatures or contacted with denaturing solvents or strongly acidic or basic solutions. Self-assembled monolayers of poly(ethylene glycol) (PEG) on silicon surfaces were exposed to oxygen plasma through a patterned photoresist. The etched regions were back-filled with an initiator for surface-initiated atom transfer radical polymerization (ATRP). ATRP of sodium acrylate was readily achieved at room temperature in an aqueous medium. Protonation of the polymer resulted in patterned poly(acrylic acid) (PAA) brushes. A variety of biomolecules containing amino groups could be covalently tethered to the dense carboxyl groups of the brush, under relatively mild conditions. The PEG regions surrounding the PAA brush greatly reduced nonspecific adsorption. Avidin was covalently attached to PAA brushes, and biotin-tagged proteins could be immobilized through avidin-biotin interaction. Such an immobilization method, which is based on specific interactions, is expected to better retain protein functionality than direct covalent binding. Using biotin-tagged bovine serum albumin (BSA) as a model, a simple strategy was developed for immobilization of small biological molecules using BSA as linkages, while BSA can simultaneously block nonspecific interactions. PMID:17880179

  10. Collapse of sodium polyacrylate chains in calcium salt solutions

    NASA Astrophysics Data System (ADS)

    Schweins, R.; Huber, K.

    The sodium salt of polyacrylic acid (NaPA) precipitates in the presence of Ca^{2+}-ions. This phase behaviour can be represented by a phase diagram where the critical NaPA concentration is plotted versus the critical Ca^{2+} concentration resulting in a straight line as a phase boundary. The location of this phase boundary is influenced by the presence of an inert monovalent salt like NaCl. The present contribution focuses on the coil dimensions of NaPA chains in dilute aqueous solution corresponding to the one phase region of such a phase diagram. A variety of parameters with which the size and shape of the polyelectrolyte chains can be modulated are revealed. Approaching the phase boundary by decreasing the NaPA concentration at a constant Ca^{2+} content leads to a collapse of the NaPA chains. Combined static and dynamic light scattering suggests a compact spherical shape as the final state of this transition, both in 0.1 M NaCl and in 0.01 M NaCl. In the lower NaCl concentration, indication is presented for the existence of a cigar or pearl necklace like intermediate. Most strikingly, the collapsed chains can be reexpanded by increasing the concentration of inert NaCl at constant content of NaPA and Ca^{2+}. Clearly, excessive Na+-ions displace the Ca^{2+}-ions from the NaPA chains.

  11. Iron oxohydroxide-polyacrylic acid magnetic composite materials

    NASA Astrophysics Data System (ADS)

    Mata-Zamora, M. E.; Arriola, H.; Nava, N.; Saniger, J. M.

    1996-08-01

    Powdered nanometer-sized precipitates of Fe(II)Fe(III) 2O x(OH) y were obtained by reacting solutions of ferrous-ferric salts with a Fe(III)/Fe(II) ratio < 2, with an excess of ammonium hydroxide. These precipitates were then mixed at room temperature with a solution of polyacrylic acid (PAA) in order to obtain a composite material. The XRD analysis showed that the iron oxohydroxide precipitates, with an average size around 10 nm, were crystalline and had a spinel structure resembling to either magnetite or maghemite. The Mössbauer spectra of the iron oxohydroxide particles presented a major magnetic phase with the double Zeeman splitting characteristic of magnetite and a minor paramagnetic phase probably originated by the nanometer size of the particles. Its structure was found to correspond to a disordered spinel, as result of the analysis of the intrinsic magnetic field and its splitting parameters. The composite material PAA-Fe(II)Fe(III) 2O x(OH) y presented a diffractogram close to the original oxohydroxide, but its Mössbauer spectrum showed a major paramagnetic phase. This change was explained as a consequence of the chemical coordination of the nanometer sized iron oxohydroxides particles with the PAA carboxylate groups.

  12. Omniphobic low moisture permeation transparent polyacrylate/silica nanocomposite.

    PubMed

    Hsu, Sheng-Hao; Chang, Yuan-Ling; Tu, Yu-Chieh; Tsai, Chieh-Ming; Su, Wei-Fang

    2013-04-24

    We report the development of low moisture permeation and transparent dense polyacrylate/silica nanocomposite material that can exhibit both superhydrophobic and oleophobic (omniphobic) properties. The material was prepared by a three-step process. The first step involved the preparation of UV polymerizable solventless hybrid resin and the fabrication of nanocomposite. The hybrid resin consisted of a mixture of acrylate monomer, initiator, and acrylate-modified different size silica nanoparticles. The second step was to roughen the surface of the nanocomposite with unique nanotexture by oxygen plasma. In the third step, we applied a low surface tension fluoro monolayer on the treated surface. The nanocomposite exhibits desired superhydrophobicity and oleophobicity with a water contact angle of 158.2° and n-1-octadecene contact angle of 128.5°, respectively; low moisture permeation of 1.44 g·mm/m(2)·day; and good transparency (greater than 82% at 450-800 nm for ~60 μm film). The material has potential applications in optoelectronic encapsulation, self-cleaning coating, etc. PMID:23496768

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

    PubMed

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

    2016-05-01

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

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

    PubMed

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

    2015-06-18

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

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

    EPA Science Inventory

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

  16. A novel single-side azobenzene-grafted Anderson-type polyoxometalate for recognition-induced chiral migration.

    PubMed

    Zhang, Bin; Yue, Liang; Wang, Yang; Yang, Yang; Wu, Lixin

    2014-09-25

    A three-component supramolecular hybrid system based on host-guest recognition and electrostatic interaction has been developed for a consecutive chiral transfer from an alpha-cyclodextrin to cationic dyes via the bridge of a new azobenzene-grafted Anderson-type polyoxometalate cluster. PMID:25089807

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

    PubMed

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

    2010-01-21

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

  18. A Visible-Light-Triggered Conformational Diastereomer Photoswitch in a Bridged Azobenzene.

    PubMed

    Deo, Claire; Bogliotti, Nicolas; Métivier, Rémi; Retailleau, Pascal; Xie, Juan

    2016-06-27

    Ketal-substituted bridged azobenzenes have been synthesized; these display a symmetrical boat conformation with the ketal in pseudo-equatorial positions. These bridged Z-azobenzenes (Z1 ) readily photoisomerize to the E-isomer as well as another Z-conformer (Z2 ) with ketal function on the pseudo-axial position upon irradiation at 406 nm. The two diastereomeric conformers display distinct physicochemical characteristics. Spectroscopic and NMR investigations supported that interconversion of two conformers occurs via the E-isomer, with good photochemical quantum yield (ΦZ1→E =0.45±0.03, ΦE→Z1 =0.33±0.05, ΦE→Z2 =0.37±0.06 and ΦZ2→E =0.36±0.04). The system shows high photostability and no thermal equilibrium between the two stable Z1 and Z2 conformers. PMID:27145736

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  20. Supramolecular architecture in Langmuir and Langmuir-Blodgett films incorporating a chiral azobenzene.

    PubMed

    Haro, Marta; del Barrio, Jesús; Villares, Ana; Oriol, Luis; Cea, Pilar; López, M Carmen

    2008-09-16

    This article describes the synthesis and fabrication of Langmuir and Langmuir-Blodgett (LB) films incorporating a chiral azobenzene derivative, namely, ( S)-4- sec-butyloxy-4'-[5''-(methyloxycarbonyl)pentyl-1''-oxy]azobenzene, abbreviated as AZO-C4(S). Appropriate conditions for the fabrication of monolayers of AZO-C4(S) at the air-water interface have been established, and the resulting Langmuir films have been characterized by a combination of surface pressure and surface potential versus area per molecule isotherms, Brewster angle microscopy, and UV-vis reflection spectroscopy. The results indicate the formation of an ordered trilayer at the air-water interface with UV-vis reflection spectroscopy showing a new supramolecular architecture for multilayered films as well as the formation of J aggregates. Films were transferred onto solid substrates, with AFM revealing well-ordered multilayered films without 3D defects. Infrared and UV-vis absorption spectroscopy indicate that the supramolecular architecture may be favored by the formation of H bonds between acid groups in neighboring layers and pi-pi intermolecular interactions. Circular dichroism spectra reveal chiro-optical activity in multilayered LB films. PMID:18686982

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

    PubMed

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

    2015-08-01

    The development of solid materials that can be reversibly interconverted by light between forms with different physico-chemical properties is of great interest for separation, catalysis, optoelectronics, holography, mechanical actuation and solar energy conversion. Here, we describe a series of shape-persistent azobenzene tetramers that form porous molecular crystals in their E-configuration, the porosity of which can be tuned by changing the peripheral substituents on the molecule. Efficient E→Z photoisomerization of the azobenzene units takes place in the solid state and converts the crystals into a non-porous amorphous melt phase. Crystallinity and porosity are restored upon Z→E isomerization promoted by visible light irradiation or heating. We demonstrate that the photoisomerization enables reversible on/off switching of optical properties such as birefringence as well as the capture of CO2 from the gas phase. The linear design, structural versatility and synthetic accessibility make this new family of materials potentially interesting for technological applications. PMID:26201739

  2. Electronic and transport properties of azobenzene monolayer junctions as molecular switches

    NASA Astrophysics Data System (ADS)

    Wang, Yan; Cheng, Hai-Ping

    2012-07-01

    We investigate from first principles the change in transport properties of a two-dimensional azobenzene monolayer sandwiched between two Au electrodes that undergoes molecular switching. We focus on transport differences between a chemisorbed and physisorbed top monolayer-electrode contact. The conductance of the monolayer junction with a chemisorbed top contact is higher in the trans configuration, in agreement with the previous theoretical predictions of one-dimensional single-molecule junctions. However, with a physisorbed top contact, the ON state, with larger conductance, is associated with the cis configuration due to a reduced effective tunneling pathway, which successfully explains recent experimental measurements on azobenzene monolayer junctions. A simple model is developed to explain electron transmission across subsystems in the molecular junction. We also discuss the effects of monolayer packing density, molecule tilt angle, and contact geometry on the calculated transmission functions. In particular, we find that a tip-like contact with chemisorption significantly affects the electric current through the cis monolayer, leading to highly asymmetric current-voltage characteristics as well as large negative differential resistance behavior.

  3. Graphene Calisthenics: Straintronics of Graphene with Light-Reactive Azobenzene Polymer

    NASA Astrophysics Data System (ADS)

    Meaker, Kacey; Cao, Peigen; Huo, Mandy; Crommie, Michael

    2014-03-01

    Although a promising target for next-generation electronics, graphene's lack of a band gap is a severe hindrance. There are many ways of opening a gap, and one controllable way is through application of specific non-uniform strains which can produce extremely large pseudomagnetic fields. This effect was predicted and verified experimentally, but so far there have been few methods developed that reliably control the size, location, separation and amount of strain in graphene. We have used a layer of light-reactive azobenzene polymer beneath the graphene to produce strained monolayer graphene with light exposure. Using Raman spectroscopy, we have measured a shift of up to 20 cm-1 in the 2D peak when the graphene and polymer sample was exposed to 532 nm laser illumination indicating that the graphene is undergoing a strain from deformation of the azobenzene layer below. AFM topographic measurements and COMSOL simulations were used to verify this assertion. Use of polymeric materials to reliably strain graphene in non-uniform ways could result in controllable production of large pseudomagnetic fields in graphene and more control over graphene's low-energy charge carriers.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

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

    PubMed

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

    2016-01-01

    The discovery of photoswitchable azobenzene-systems that undergo trans-to-cis photoisomerisation was a milestone in supramolecular chemistry. Such photoswitches have possible applications in data storage, stimuli responsive delivery systems, and molecular machines due to fast and selective switching. However, the light induced cis isomer of azobenzene is rather unstable and reverts thermally and photochemically to the thermodynamically stable trans configuration. We report, for the first time, controlled photoswitching of an azo-naphthalenediimide (azo-NDI) which can be achieved upon binding of fluoride ions through anion-π interaction. This NDI-F-NDI "sandwich" stabilises the cis configuration through the generation of an NDI(•-) radical anion, and a dianionic, NDI(2-) species that becomes unusually stable in the cis form. The sandwiched cis form reverts to the trans form only upon decomplexation of F(-). A model pollutant was successfully degraded using the photogenerated NDI-F-NDI sandwich. This opens a wide range of applications in molecular and supramolecular nanotechnology. PMID:26953168

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

    PubMed Central

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

    2016-01-01

    The discovery of photoswitchable azobenzene-systems that undergo trans-to-cis photoisomerisation was a milestone in supramolecular chemistry. Such photoswitches have possible applications in data storage, stimuli responsive delivery systems, and molecular machines due to fast and selective switching. However, the light induced cis isomer of azobenzene is rather unstable and reverts thermally and photochemically to the thermodynamically stable trans configuration. We report, for the first time, controlled photoswitching of an azo-naphthalenediimide (azo-NDI) which can be achieved upon binding of fluoride ions through anion-π interaction. This NDI-F–NDI “sandwich” stabilises the cis configuration through the generation of an NDI•− radical anion, and a dianionic, NDI2− species that becomes unusually stable in the cis form. The sandwiched cis form reverts to the trans form only upon decomplexation of F−. A model pollutant was successfully degraded using the photogenerated NDI-F–NDI sandwich. This opens a wide range of applications in molecular and supramolecular nanotechnology. PMID:26953168

  7. Kinetics of copper ion absorption by cross-linked calcium polyacrylate membranes

    NASA Technical Reports Server (NTRS)

    Philipp, W. H.; May, C. E.

    1983-01-01

    The absorption of copper ions from aqueous copper acetate solutions by cross-linked calcium acrylate membranes was found to obey parabolic kinetics similar to that found for oxidation of metals that form protective oxide layers. For pure calcium polyacrylate membranes the rate constant was essentially independent of copper acetate concentration and film thickness. For a cross-linked copolymer film of polyvinyl alcohol and calcium polyacrylate, the rate constant was much greater and dependent on the concentration of copper acetate. The proposed mechanism in each case involves the formation of a copper polyacrylate phase on the surface of the membrane. The diffusion of the copper ion through this phase appears to be the rate controlling step for the copolymer film. The diffusion of the calcium ion is apparently the rate controlling step for the calcium polyacrylate. At low pH, the copper polyacrylate phase consists of the normal copper salt; at higher pH, the phase appears to be the basic copper salt.

  8. The effect of TiO2/aluminosilicate nanocomposite additives on the mechanical and thermal properties of polyacrylic coatings

    NASA Astrophysics Data System (ADS)

    Nosrati, Rahimeh; Olad, Ali

    2015-12-01

    The commercial grade polyacrylic latex was modified in order to prepare a mechanical and thermal improved coating. TiO2/Ag-exchanged-aluminosilicate nanocomposites with montmorillonite, zeolite-A and clinoptilolite aluminosilicates were prepared and used as additive in the matrix of polyacrylic latex to achieve a coating with proper mechanical and thermal properties. X-ray diffraction patterns and FESEM were used to characterize the composition, structure, and morphology of the nanocomposite additives. Polyacrylic coatings modified by TiO2/Ag-exchanged-aluminosilicate nanocomposite additives showed higher adhesion strength and hardness compared to unmodified commercial grade polyacrylic coatings. Differential Scanning Calorimetry (DSC) analysis showed lower glass transition temperature for modified polyacrylic coatings than that of unmodified polyacrylic coatings. The tensile tests were also carried out for unmodified and modified polyacrylic coatings. According to the results, the modified polyacrylic based coating with TiO2/Ag-exchanged-clinoptilolite nanocomposite additive was the best coating considering most of useful properties.

  9. Nano electrochemical reactors of Fe2O3 nanoparticles embedded in shells of nitrogen-doped hollow carbon spheres as high-performance anodes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Zheng, Fangcai; He, Mengni; Yang, Yang; Chen, Qianwang

    2015-02-01

    Iron oxides are extensively investigated as anode materials for lithium-ion batteries (LIBs) because of their large specific capacities. However, they undergo huge volume changes during cycling that result in anode pulverization and loss of electrical connectivity. As a result, the capacity retention of the iron oxide anodes is poor and should be improved for commercial applications. Herein, we report the preparation of ultrasmall Fe2O3 nanoparticles embedded in nitrogen-doped hollow carbon sphere shells (Fe2O3@N-C) by the direct pyrolysis of Fe-based zeolitic imidazolate frameworks (Fe-ZIF) at 620 °C in air. As an anode material for LIBs, the capacity retained was 1573 mA h g-1 after 50 cycles at a current density of 0.1 C (1 C = 1000 mA g-1). Even undergoing the high-rate capability test twice, it can still deliver a remarkably reversible and stable capacity of 1142 mA h g-1 after 100 cycles at a current density of 1 C. The excellent electrochemical performance is attributed to the unique structure of ultrasmall Fe2O3 nanoparticles uniformly distributed in the shell of nitrogen-doped carbon spheres, which simultaneously solve the major problems of pulverization, facilitate rapid electrochemical kinetics, and effectively avoid the aggregation of Fe2O3 nanoparticles during de/lithiation. The novel method developed in this work for the synthesis of functional hybrid materials can be extended to the preparation of various MOFs-derived functional nanocomposites owing to the versatility of links and metal centers in MOFs.Iron oxides are extensively investigated as anode materials for lithium-ion batteries (LIBs) because of their large specific capacities. However, they undergo huge volume changes during cycling that result in anode pulverization and loss of electrical connectivity. As a result, the capacity retention of the iron oxide anodes is poor and should be improved for commercial applications. Herein, we report the preparation of ultrasmall Fe2O3 nanoparticles

  10. Nano electrochemical reactors of Fe2O3 nanoparticles embedded in shells of nitrogen-doped hollow carbon spheres as high-performance anodes for lithium-ion batteries.

    PubMed

    Zheng, Fangcai; He, Mengni; Yang, Yang; Chen, Qianwang

    2015-02-28

    Iron oxides are extensively investigated as anode materials for lithium-ion batteries (LIBs) because of their large specific capacities. However, they undergo huge volume changes during cycling that result in anode pulverization and loss of electrical connectivity. As a result, the capacity retention of the iron oxide anodes is poor and should be improved for commercial applications. Herein, we report the preparation of ultrasmall Fe2O3 nanoparticles embedded in nitrogen-doped hollow carbon sphere shells (Fe2O3@N-C) by the direct pyrolysis of Fe-based zeolitic imidazolate frameworks (Fe-ZIF) at 620 °C in air. As an anode material for LIBs, the capacity retained was 1573 mA h g(-1) after 50 cycles at a current density of 0.1 C (1 C = 1000 mA g(-1)). Even undergoing the high-rate capability test twice, it can still deliver a remarkably reversible and stable capacity of 1142 mA h g(-1) after 100 cycles at a current density of 1 C. The excellent electrochemical performance is attributed to the unique structure of ultrasmall Fe2O3 nanoparticles uniformly distributed in the shell of nitrogen-doped carbon spheres, which simultaneously solve the major problems of pulverization, facilitate rapid electrochemical kinetics, and effectively avoid the aggregation of Fe2O3 nanoparticles during de/lithiation. The novel method developed in this work for the synthesis of functional hybrid materials can be extended to the preparation of various MOFs-derived functional nanocomposites owing to the versatility of links and metal centers in MOFs. PMID:25631451