Solids precipitation and polymerization of asphaltenes in coal-derived liquids

DOEpatents

Kydd, Paul H.

1984-01-01

The precipitation and removal of particulate solids from coal-derived liquids by adding a process-derived anti-solvent liquid fraction and continuing the precipitation process at a temperature above the melting point of the mixed liquids for sufficient time to allow the asphaltenes to polymerize and solids to settle at atmospheric pressure conditions. The resulting clarified light hydrocarbon overflow liquid contains less than about 0.02 W % ash and is suitable as turbine fuel or as boiler fuel for burning without particulate emission control equipment. An underflow liquid fraction containing less than about 0.1 W % solids along with low sulfur and nitrogen concentrations is suitable as a boiler fuel with emission control equipment.

Innovative Poly(Ionic Liquid)s by the Polymerization of Deep Eutectic Monomers.

PubMed

Isik, Mehmet; Ruiperez, Fernando; Sardon, Haritz; Gonzalez, Alba; Zulfiqar, Sonia; Mecerreyes, David

2016-07-01

The incorporation of ionic liquid (IL) chemistry into functional polymers has extended the properties and applications of polyelectrolytes. However, ILs are expensive due to the presence of fluorinated anions or complicated synthetic steps which limit their technological viability. Here, we show a new family of poly(ionic liquid)s (PILs) which are based in cheap and renewable chemicals and involves facile synthetic approaches. Thus, deep eutectic monomers (DEMs) are prepared for the first time by using quaternary ammonium compounds and various hydrogen bond donors such as citric acid, terephthalic acid or an amidoxime. The deep eutectic formation is made through a simple mixing of the ingredients. Differential scanning calorimetry, nuclear magnetic resonance (NMR) and computational studies reveal the formation of the DEMs due to the ionic interactions. The resulting DEMs are liquid which facilitates their polymerization using mild photopolymerization or polycondensation strategies. Spectroscopic characterizations reveal the successful formation of the polymers. By this way, a new family of PILs can be synthesized which can be used for different applications. As an example, the polymers show promising performance as solid CO2 sorbents. Altogether the deep eutectic monomer route can lead to non-toxic, cheap and easy-to-prepare alternatives to current PILs for different applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microjets and coated wheels: versatile tools for exploring collisions and reactions at gas-liquid interfaces.

PubMed

Faust, Jennifer A; Nathanson, Gilbert M

2016-07-07

This tutorial review describes experimental aspects of two techniques for investigating collisions and reactions at the surfaces of liquids in vacuum. These gas-liquid scattering experiments provide insights into the dynamics of interfacial processes while minimizing interference from vapor-phase collisions. We begin with a historical survey and then compare attributes of the microjet and coated-wheel techniques, developed by Manfred Faubel and John Fenn, respectively, for studies of high- and low-vapor pressure liquids in vacuum. Our objective is to highlight the strengths and shortcomings of each technique and summarize lessons we have learned in using them for scattering and evaporation experiments. We conclude by describing recent microjet studies of energy transfer between O2 and liquid hydrocarbons, HCl dissociation in salty water, and super-Maxwellian helium evaporation.

Polymeric ionic liquid bucky gels as sorbent coatings for solid-phase microextraction.

PubMed

Zhang, Cheng; Anderson, Jared L

2014-05-30

Novel cross-linked polymeric ionic liquid (PIL) bucky gels were formed by free-radical polymerization of polymerizable ionic liquids gelled with multi-walled carbon nanotubes (MWCNT) and used as sorbent coatings for solid-phase microextraction (SPME). The combination of PIL with MWCNTs significantly enhanced the π-π interaction between the sorbent coatings and the aromatic analytes. Compared to the neat PIL-based sorbent coating, the PIL bucky gel sorbent coatings demonstrated higher extraction efficiency for the extraction of polycyclic aromatic hydrocarbons (PAHs). A partitioning extraction mechanism was observed for the PIL/MWCNT-based sorbent coatings indicating that the addition of MWCNTs did not seem to affect the extraction mechanism of the sorbent coating. The analyte-to-coating partition coefficients (logKfs) were estimated and the limits of detection (LOD) for selected PIL bucky gel sorbent coating were determined to be in the range of 1-2.5 ng L(-1). Recovery studies were also performed for PAHs in river and tap water to validate the applicability of the developed method. Copyright © 2014 Elsevier B.V. All rights reserved.

Enhanced linearly polarized lasing emission from nanoimprinted surface-emitting distributed feedback laser based on polymeric liquid crystals

NASA Astrophysics Data System (ADS)

Jeong, Soon Moon; Ha, Na Young; Chee, Mu Guen; Araoka, Fumito; Ishikawa, Ken; Takezoe, Hideo; Nishimura, Suzushi; Suzaki, Goro

2008-12-01

The authors have demonstrated the enhancement of linearly polarized lasing emission intensity using a structure made by a simple fabrication process. The enhanced lasing is achieved using a nanoimprinted distributed feedback structure together with spin-coated polymeric liquid crystals. The backward linearly TE-polarized lasing emission is transformed to left-handed circularly polarized light (L-CPL) by employing a dye-doped polymeric nematic liquid crystal (PNLC) film as a (-1/4)λ[=(3/4)λ] plate. The L-CPL is effectively reflected by a L-polymeric cholesteric liquid crystal film as a reflector and transformed back to TE-polarized light by the PNLC film; as a result one-directional emission intensity is enhanced.

Effect of Molecular Weight on the Ion Transport Mechanism in Polymerized Ionic Liquids

DOE PAGES

Fan, Fei; Wang, Weiyu; Holt, Adam P.; ...

2016-06-07

The unique properties of ionic liquids (ILs) have made them promising candidates for electrochemical applications. Polymerization of the corresponding ILs results in a new class of materials called polymerized ionic liquids (PolyILs). Though PolyILs offer the possibility to combine the high conductivity of ILs and the high mechanical strength of polymers, their conductivities are typically much lower than that of the corresponding small molecule ILs. In this study, seven PolyILs were synthesized having degrees of polymerization ranging from 1 to 333, corresponding to molecular weights (MW) from 482 to 160 400 g/mol. Depolarized dynamic light scattering, broadband dielectric spectroscopy, rheology,more » and differential scanning calorimetry were employed to systematically study the influence of MW on the mechanism of ionic transport and segmental dynamics in these materials. Finally, the modified Walden plot analysis reveals that the ion conductivity transforms from being closely coupled with structural relaxation to being strongly decoupled from it as MW increases.« less

Effect of Molecular Weight on the Ion Transport Mechanism in Polymerized Ionic Liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fan, Fei; Wang, Weiyu; Holt, Adam P.

The unique properties of ionic liquids (ILs) have made them promising candidates for electrochemical applications. Polymerization of the corresponding ILs results in a new class of materials called polymerized ionic liquids (PolyILs). Though PolyILs offer the possibility to combine the high conductivity of ILs and the high mechanical strength of polymers, their conductivities are typically much lower than that of the corresponding small molecule ILs. In this study, seven PolyILs were synthesized having degrees of polymerization ranging from 1 to 333, corresponding to molecular weights (MW) from 482 to 160 400 g/mol. Depolarized dynamic light scattering, broadband dielectric spectroscopy, rheology,more » and differential scanning calorimetry were employed to systematically study the influence of MW on the mechanism of ionic transport and segmental dynamics in these materials. Finally, the modified Walden plot analysis reveals that the ion conductivity transforms from being closely coupled with structural relaxation to being strongly decoupled from it as MW increases.« less

Recent advances of ionic liquids and polymeric ionic liquids in capillary electrophoresis and capillary electrochromatography.

PubMed

Tang, Sheng; Liu, Shujuan; Guo, Yong; Liu, Xia; Jiang, Shengxiang

2014-08-29

Ionic liquids (ILs) and polymeric ionic liquids (PILs) with unique and fascinating properties have drawn considerable interest for their use in separation science, especially in chromatographic techniques. In this article, significant contributions of ILs and PILs in the improvement of capillary electrophoresis and capillary electrochromatography are described, and a specific overview of the most relevant examples of their applications in the last five years is also given. Accordingly, some general conclusions and future perspectives in these areas are discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

Molecular engineering of side-chain liquid crystalline polymers by living cationic polymerization using Webster`s initiating system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Percec, V.

1993-12-31

Webster`s cationic initiating system (HO{sub 3}SCF{sub 3}/SMe{sub 2}) (Macromolecules, 23, 1918 (1990)) was shown by us (for a review see Adv. Mater., 4, 548 (1992)) to polymerize, via a living mechanism, mesogenic vinyl ethers which contain a large variety of functional groups. This is mostly because SMe{sub 2} is a softer nucleophile than any of the functional groups available in these monomers. The molecular engineering of side-chain liquid crystalline polymers with conventional and complex architectures via this polymerization technique will be discussed.

Electrodeposition of Polymer Nanostructures using Three Diffuse Double Layers: Polymerization beyond the Liquid/Liquid Interfaces

NASA Astrophysics Data System (ADS)

Divya, Velpula; Sangaranarayanan, M. V.

2018-04-01

Nanostructured conducting polymers have received immense attention during the past few decades on account of their phenomenal usefulness in diverse contexts, while the interface between two immiscible liquids is of great interest in chemical and biological applications. Here we propose a novel Electrode(solid)/Electrolyte(aqueous)/Electrolyte(organic) Interfacial assembly for the synthesis of polymeric nanostructures using a novel concept of three diffuse double layers. There exist remarkable differences between the morphologies of the polymers synthesized using the conventional electrode/electrolyte method and that of the new approach. In contrast to the commonly employed electrodeposition at liquid/liquid interfaces, these polymer modified electrodes can be directly employed in diverse applications such as sensors, supercapacitors etc.

Photoinitiated polymerization of PEG-diacrylate with lithium phenyl-2,4,6-trimethylbenzoylphosphinate: polymerization rate and cytocompatibility

PubMed Central

Fairbanks, Benjamin D.; Schwartz, Michael P.; Bowman, Christopher N.; Anseth, Kristi S.

2009-01-01

Due to mild reaction conditions and temporal and spatial control over material formation, photopolymerization has become a valuable technique for the encapsulation of living cells in three dimensional, hydrated, biomimetic materials. For such applications,2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-propanone (I2959) is the most commonly used photoinitiator (by virtue of its moderate water solubility), yet this initiator has an absorption spectrum that is poorly matched with wavelengths of light generally regarded as benign to living cells, limiting the rate at which it may initiate polymerization in their presence. In contrast, acylphosphine oxide photoinitiators, generally exhibit absorption spectra at wavelengths suitable for cell encapsulation, yet commercially available initiators of this class have low water solubility. Here, a water soluble lithium acylphosphinate salt is evaluated for its ability to polymerize diacrylated poly(ethylene glycol) (PEGDA) monomers rapidly into hydrogels, while maintaining high viability during direct encapsulation of cells. Through rheometric measurements, the time to reach gelation of a PEGDA solution with the phosphinate initiator is one tenth the time for that using I2959 at similar concentrations, when exposed to 365 nm light. Further, polymerization with the phosphinate initiator at 405 nm visible light exposure is achieved with low initiator concentrations and light intensities, precluded in polymerizations initiated with I2959 by its absorbance profile. When examined 24 hours after encapsulation, survival rates of human neonatal fibroblasts encapsulated in hydrogels polymerized with the phosphinate initiator exceed 95%, demonstrating the cytocompatibility of this initiating system. PMID:19783300

Dispersion polymerization of L-lactide utilizing ionic liquids as reaction medium

NASA Astrophysics Data System (ADS)

Fahmiati, Sri; Minami, Hideto; Haryono, Agus; Adilina, Indri B.

2017-11-01

Dispersion polymerization of L-lactide was proceeded in various ionic liquids. Ionic liquids as 1-Hexyl-3-methylimidazolium bis (trifluormethylsulfonyl) imide, [HMIM] [TFSI], 1-Butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, [BMP] [TFSI], and N,N,N-Trimethyl-N-Propylammonium Bis (trifloromethanesulfonyl) imide, [TMPA] [TFSI], were employed as reaction medium that dissolved both of lactide and stabilizer (polyvinylprrolidone). Sn-supported on bentonite was used as a ring opening catalyst of L-lactide. Gel Permeation Chromatography result showed that poly-(L-lactic acid) were formed in ionic liquids [HMIM] [TFSI] and [BMP] [TFSI] with molecular weight as 19390 and 20844, respectively.

Readiness of the ATLAS liquid argon calorimeter for LHC collisions

NASA Astrophysics Data System (ADS)

Aad, G.; Abbott, B.; Abdallah, J.; Abdelalim, A. A.; Abdesselam, A.; Abdinov, O.; Abi, B.; Abolins, M.; Abramowicz, H.; Abreu, H.; Acharya, B. S.; Adams, D. L.; Addy, T. N.; Adelman, J.; Adorisio, C.; Adragna, P.; Adye, T.; Aefsky, S.; Aguilar-Saavedra, J. A.; Aharrouche, M.; Ahlen, S. P.; Ahles, F.; Ahmad, A.; Ahmed, H.; Ahsan, M.; Aielli, G.; Akdogan, T.; Åkesson, T. P. A.; Akimoto, G.; Akimov, A. V.; Aktas, A.; Alam, M. S.; Alam, M. A.; Albert, J.; Albrand, S.; Aleksa, M.; Aleksandrov, I. N.; Alessandria, F.; Alexa, C.; Alexander, G.; Alexandre, G.; Alexopoulos, T.; Alhroob, M.; Aliev, M.; Alimonti, G.; Alison, J.; Aliyev, M.; Allport, P. P.; Allwood-Spiers, S. E.; Almond, J.; Aloisio, A.; Alon, R.; Alonso, A.; Alviggi, M. G.; Amako, K.; Amelung, C.; Ammosov, V. V.; Amorim, A.; Amorós, G.; Amram, N.; Anastopoulos, C.; Andeen, T.; Anders, C. F.; Anderson, K. J.; Andreazza, A.; Andrei, V.; Anduaga, X. S.; Angerami, A.; Anghinolfi, F.; Anjos, N.; Antonaki, A.; Antonelli, M.; Antonelli, S.; Antunovic, B.; Anulli, F.; Aoun, S.; Arabidze, G.; Aracena, I.; Arai, Y.; Arce, A. T. H.; Archambault, J. P.; Arfaoui, S.; Arguin, J.-F.; Argyropoulos, T.; Arik, E.; Arik, M.; Armbruster, A. J.; Arnaez, O.; Arnault, C.; Artamonov, A.; Arutinov, D.; Asai, M.; Asai, S.; Asfandiyarov, R.; Ask, S.; Åsman, B.; Asner, D.; Asquith, L.; Assamagan, K.; Astbury, A.; Astvatsatourov, A.; Atoian, G.; Auerbach, B.; Auge, E.; Augsten, K.; Aurousseau, M.; Austin, N.; Avolio, G.; Avramidou, R.; Axen, D.; Ay, C.; Azuelos, G.; Azuma, Y.; Baak, M. A.; Baccaglioni, G.; Bacci, C.; Bach, A.; Bachacou, H.; Bachas, K.; Backes, M.; Badescu, E.; Bagnaia, P.; Bai, Y.; Bailey, D. C.; Bain, T.; Baines, J. T.; Baker, O. K.; Baker, M. D.; Dos Santos Pedrosa, F. Baltasar; Banas, E.; Banerjee, P.; Banerjee, S.; Banfi, D.; Bangert, A.; Bansal, V.; Baranov, S. P.; Baranov, S.; Barashkou, A.; Barber, T.; Barberio, E. L.; Barberis, D.; Barbero, M.; Bardin, D. Y.; Barillari, T.; Barisonzi, M.; Barklow, T.; Barlow, N.; Barnett, B. M.; Barnett, R. M.; Baron, S.; Baroncelli, A.; Barr, A. J.; Barreiro, F.; Barreiro Guimarães da Costa, J.; Barrillon, P.; Barros, N.; Bartoldus, R.; Bartsch, D.; Bastos, J.; Bates, R. L.; Bathe, S.; Batkova, L.; Batley, J. R.; Battaglia, A.; Battistin, M.; Bauer, F.; Bawa, H. S.; Bazalova, M.; Beare, B.; Beau, T.; Beauchemin, P. H.; Beccherle, R.; Becerici, N.; Bechtle, P.; Beck, G. A.; Beck, H. P.; Beckingham, M.; Becks, K. H.; Bedajanek, I.; Beddall, A. J.; Beddall, A.; Bednár, P.; Bednyakov, V. A.; Bee, C.; Begel, M.; Behar Harpaz, S.; Behera, P. K.; Beimforde, M.; Belanger-Champagne, C.; Bell, P. J.; Bell, W. H.; Bella, G.; Bellagamba, L.; Bellina, F.; Bellomo, M.; Belloni, A.; Belotskiy, K.; Beltramello, O.; Ben Ami, S.; Benary, O.; Benchekroun, D.; Bendel, M.; Benedict, B. H.; Benekos, N.; Benhammou, Y.; Benincasa, G. P.; Benjamin, D. P.; Benoit, M.; Bensinger, J. R.; Benslama, K.; Bentvelsen, S.; Beretta, M.; Berge, D.; Bergeaas Kuutmann, E.; Berger, N.; Berghaus, F.; Berglund, E.; Beringer, J.; Bernardet, K.; Bernat, P.; Bernhard, R.; Bernius, C.; Berry, T.; Bertin, A.; Besson, N.; Bethke, S.; Bianchi, R. M.; Bianco, M.; Biebel, O.; Biesiada, J.; Biglietti, M.; Bilokon, H.; Bindi, M.; Binet, S.; Bingul, A.; Bini, C.; Biscarat, C.; Bitenc, U.; Black, K. M.; Blair, R. E.; Blanchard, J.-B.; Blanchot, G.; Blocker, C.; Blocki, J.; Blondel, A.; Blum, W.; Blumenschein, U.; Bobbink, G. J.; Bocci, A.; Boehler, M.; Boek, J.; Boelaert, N.; Böser, S.; Bogaerts, J. A.; Bogouch, A.; Bohm, C.; Bohm, J.; Boisvert, V.; Bold, T.; Boldea, V.; Boldyrev, A.; Bondarenko, V. G.; Bondioli, M.; Boonekamp, M.; Booth, J. R. A.; Bordoni, S.; Borer, C.; Borisov, A.; Borissov, G.; Borjanovic, I.; Borroni, S.; Bos, K.; Boscherini, D.; Bosman, M.; Bosteels, M.; Boterenbrood, H.; Bouchami, J.; Boudreau, J.; Bouhova-Thacker, E. V.; Boulahouache, C.; Bourdarios, C.; Boyd, J.; Boyko, I. R.; Bozovic-Jelisavcic, I.; Bracinik, J.; Braem, A.; Branchini, P.; Brandenburg, G. W.; Brandt, A.; Brandt, G.; Brandt, O.; Bratzler, U.; Brau, B.; Brau, J. E.; Braun, H. M.; Brelier, B.; Bremer, J.; Brenner, R.; Bressler, S.; Breton, D.; Brett, N. D.; Britton, D.; Brochu, F. M.; Brock, I.; Brock, R.; Brodbeck, T. J.; Brodet, E.; Broggi, F.; Bromberg, C.; Brooijmans, G.; Brooks, W. K.; Brown, G.; Brubaker, E.; Bruckman de Renstrom, P. A.; Bruncko, D.; Bruneliere, R.; Brunet, S.; Bruni, A.; Bruni, G.; Bruschi, M.; Buanes, T.; Bucci, F.; Buchanan, J.; Buchholz, P.; Buckley, A. G.; Budagov, I. A.; Budick, B.; Büscher, V.; Bugge, L.; Bulekov, O.; Bunse, M.; Buran, T.; Burckhart, H.; Burdin, S.; Burgess, T.; Burke, S.; Busato, E.; Bussey, P.; Buszello, C. P.; Butin, F.; Butler, B.; Butler, J. M.; Buttar, C. M.; Butterworth, J. M.; Byatt, T.; Caballero, J.; Cabrera Urbán, S.; Caforio, D.; Cakir, O.; Calafiura, P.; Calderini, G.; Calfayan, P.; Calkins, R.; Caloba, L. P.; Caloi, R.; Calvet, D.; Camarri, P.; Cambiaghi, M.; Cameron, D.; Campabadal Segura, F.; Campana, S.; Campanelli, M.; Canale, V.; Canelli, F.; Canepa, A.; Cantero, J.; Capasso, L.; Capeans Garrido, M. D. M.; Caprini, I.; Caprini, M.; Capua, M.; Caputo, R.; Caracinha, D.; Caramarcu, C.; Cardarelli, R.; Carli, T.; Carlino, G.; Carminati, L.; Caron, B.; Caron, S.; Carrillo Montoya, G. D.; Carron Montero, S.; Carter, A. A.; Carter, J. R.; Carvalho, J.; Casadei, D.; Casado, M. P.; Cascella, M.; Caso, C.; Castaneda Hernadez, A. M.; Castaneda-Miranda, E.; Castillo Gimenez, V.; Castro, N.; Cataldi, G.; Catinaccio, A.; Catmore, J. R.; Cattai, A.; Cattani, G.; Caughron, S.; Cauz, D.; Cavalleri, P.; Cavalli, D.; Cavalli-Sforza, M.; Cavasinni, V.; Ceradini, F.; Cerqueira, A. S.; Cerri, A.; Cerrito, L.; Cerutti, F.; Cetin, S. A.; Cevenini, F.; Chafaq, A.; Chakraborty, D.; Chan, K.; Chapman, J. D.; Chapman, J. W.; Chareyre, E.; Charlton, D. G.; Chavda, V.; Cheatham, S.; Chekanov, S.; Chekulaev, S. V.; Chelkov, G. A.; Chen, H.; Chen, S.; Chen, T.; Chen, X.; Cheng, S.; Cheplakov, A.; Chepurnov, V. F.; Cherkaoui El Moursli, R.; Tcherniatine, V.; Chesneanu, D.; Cheu, E.; Cheung, S. L.; Chevalier, L.; Chevallier, F.; Chiarella, V.; Chiefari, G.; Chikovani, L.; Childers, J. T.; Chilingarov, A.; Chiodini, G.; Chizhov, M.; Choudalakis, G.; Chouridou, S.; Chren, D.; Christidi, I. A.; Christov, A.; Chromek-Burckhart, D.; Chu, M. L.; Chudoba, J.; Ciapetti, G.; Ciftci, A. K.; Ciftci, R.; Cinca, D.; Cindro, V.; Ciobotaru, M. D.; Ciocca, C.; Ciocio, A.; Cirilli, M.; Citterio, M.; Clark, A.; Cleland, W.; Clemens, J. C.; Clement, B.; Clement, C.; Clements, D.; Coadou, Y.; Cobal, M.; Coccaro, A.; Cochran, J.; Coelli, S.; Coggeshall, J.; Cogneras, E.; Cojocaru, C. D.; Colas, J.; Cole, B.; Colijn, A. P.; Collard, C.; Collins, N. J.; Collins-Tooth, C.; Collot, J.; Colon, G.; Coluccia, R.; Conde Muiño, P.; Coniavitis, E.; Consonni, M.; Constantinescu, S.; Conta, C.; Conventi, F.; Cook, J.; Cooke, M.; Cooper, B. D.; Cooper-Sarkar, A. M.; Cooper-Smith, N. J.; Copic, K.; Cornelissen, T.; Corradi, M.; Corriveau, F.; Corso-Radu, A.; Cortes-Gonzalez, A.; Cortiana, G.; Costa, G.; Costa, M. J.; Costanzo, D.; Costin, T.; Côté, D.; Coura Torres, R.; Courneyea, L.; Cowan, G.; Cowden, C.; Cox, B. E.; Cranmer, K.; Cranshaw, J.; Cristinziani, M.; Crosetti, G.; Crupi, R.; Crépé-Renaudin, S.; Cuenca Almenar, C.; Cuhadar Donszelmann, T.; Curatolo, M.; Curtis, C. J.; Cwetanski, P.; Czyczula, Z.; D'Auria, S.; D'Onofrio, M.; D'Orazio, A.; da Silva, P. V. M.; da Via, C.; Dabrowski, W.; Dai, T.; Dallapiccola, C.; Dallison, S. J.; Daly, C. H.; Dam, M.; Danielsson, H. O.; Dannheim, D.; Dao, V.; Darbo, G.; Darlea, G. L.; Davey, W.; Davidek, T.; Davidson, N.; Davidson, R.; Davison, A. R.; Dawson, I.; Dawson, J. W.; Daya, R. K.; de, K.; de Asmundis, R.; de Castro, S.; de Castro Faria Salgado, P. E.; de Cecco, S.; de Graat, J.; de Groot, N.; de Jong, P.; de La Cruz-Burelo, E.; de La Taille, C.; de Mora, L.; de Oliveira Branco, M.; de Pedis, D.; de Salvo, A.; de Sanctis, U.; de Santo, A.; de Vivie de Regie, J. B.; de Zorzi, G.; Dean, S.; Deberg, H.; Dedes, G.; Dedovich, D. V.; Defay, P. O.; Degenhardt, J.; Dehchar, M.; Del Papa, C.; Del Peso, J.; Del Prete, T.; Dell'Acqua, A.; Dell'Asta, L.; Della Pietra, M.; Della Volpe, D.; Delmastro, M.; Delruelle, N.; Delsart, P. A.; Deluca, C.; Demers, S.; Demichev, M.; Demirkoz, B.; Deng, J.; Deng, W.; Denisov, S. P.; Dennis, C.; Derkaoui, J. E.; Derue, F.; Dervan, P.; Desch, K.; Deviveiros, P. O.; Dewhurst, A.; Dewilde, B.; Dhaliwal, S.; Dhullipudi, R.; di Ciaccio, A.; di Ciaccio, L.; di Domenico, A.; di Girolamo, A.; di Girolamo, B.; di Luise, S.; di Mattia, A.; di Nardo, R.; di Simone, A.; di Sipio, R.; Diaz, M. A.; Diblen, F.; Diehl, E. B.; Dietrich, J.; Diglio, S.; Dindar Yagci, K.; Dingfelder, D. J.; Dionisi, C.; Dita, P.; Dita, S.; Dittus, F.; Djama, F.; Djilkibaev, R.; Djobava, T.; Do Vale, M. A. B.; Do Valle Wemans, A.; Dobbs, M.; Dobos, D.; Dobson, E.; Dobson, M.; Dodd, J.; Dogan, O. B.; Doherty, T.; Doi, Y.; Dolejsi, J.; Dolenc, I.; Dolezal, Z.; Dolgoshein, B. A.; Dohmae, T.; Donega, M.; Donini, J.; Dopke, J.; Doria, A.; Dos Anjos, A.; Dotti, A.; Dova, M. T.; Doxiadis, A.; Doyle, A. T.; Drasal, Z.; Driouichi, C.; Dris, M.; Dubbert, J.; Duchovni, E.; Duckeck, G.; Dudarev, A.; Dudziak, F.; Dührssen, M.; Duflot, L.; Dufour, M.-A.; Dunford, M.; Duperrin, A.; Duran Yildiz, H.; Dushkin, A.; Duxfield, R.; Dwuznik, M.; Düren, M.; Ebenstein, W. L.; Ebke, J.; Eckert, S.; Eckweiler, S.; Edmonds, K.; Edwards, C. A.; Eerola, P.; Egorov, K.; Ehrenfeld, W.; Ehrich, T.; Eifert, T.; Eigen, G.; Einsweiler, K.; Eisenhandler, E.; Ekelof, T.; El Kacimi, M.; Ellert, M.; Elles, S.; Ellinghaus, F.; Ellis, K.; Ellis, N.; Elmsheuser, J.; Elsing, M.; Ely, R.; Emeliyanov, D.; Engelmann, R.; Engl, A.; Epp, B.; Eppig, A.; Epshteyn, V. S.; Ereditato, A.; Eriksson, D.; Ermoline, I.; Ernst, J.; Ernst, M.; Ernwein, J.; Errede, D.; Errede, S.; Ertel, E.; Escalier, M.; Escobar, C.; Espinal Curull, X.; Esposito, B.; Etienne, F.; Etienvre, A. I.; Etzion, E.; Evans, H.; Fabbri, L.; Fabre, C.; Faccioli, P.; Facius, K.; Fakhrutdinov, R. M.; Falciano, S.; Falou, A. C.; Fang, Y.; Fanti, M.; Farbin, A.; Farilla, A.; Farley, J.; Farooque, T.; Farrington, S. M.; Farthouat, P.; Fassi, F.; Fassnacht, P.; Fassouliotis, D.; Fatholahzadeh, B.; Fayard, L.; Fayette, F.; Febbraro, R.; Federic, P.; Fedin, O. L.; Fedorko, I.; Fedorko, W.; Feligioni, L.; Felzmann, C. U.; Feng, C.; Feng, E. J.; Fenyuk, A. B.; Ferencei, J.; Ferland, J.; Fernandes, B.; Fernando, W.; Ferrag, S.; Ferrando, J.; Ferrari, A.; Ferrari, P.; Ferrari, R.; Ferrer, A.; Ferrer, M. L.; Ferrere, D.; Ferretti, C.; Fiascaris, M.; Fiedler, F.; Filipčič, A.; Filippas, A.; Filthaut, F.; Fincke-Keeler, M.; Fiolhais, M. C. N.; Fiorini, L.; Firan, A.; Fischer, G.; Fisher, M. J.; Flechl, M.; Fleck, I.; Fleckner, J.; Fleischmann, P.; Fleischmann, S.; Flick, T.; Flores Castillo, L. R.; Flowerdew, M. J.; Föhlisch, F.; Fokitis, M.; Fonseca Martin, T.; Forbush, D. A.; Formica, A.; Forti, A.; Fortin, D.; Foster, J. M.; Fournier, D.; Foussat, A.; Fowler, A. J.; Fowler, K.; Fox, H.; Francavilla, P.; Franchino, S.; Francis, D.; Franklin, M.; Franz, S.; Fraternali, M.; Fratina, S.; Freestone, J.; French, S. T.; Froeschl, R.; Froidevaux, D.; Frost, J. A.; Fukunaga, C.; Fullana Torregrosa, E.; Fuster, J.; Gabaldon, C.; Gabizon, O.; Gadfort, T.; Gadomski, S.; Gagliardi, G.; Gagnon, P.; Galea, C.; Gallas, E. J.; Gallas, M. V.; Gallop, B. 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O.; Osculati, B.; Osuna, C.; Otec, R.; P Ottersbach, J.; Ould-Saada, F.; Ouraou, A.; Ouyang, Q.; Owen, M.; Owen, S.; Ozcan, V. E.; Ozone, K.; Ozturk, N.; Pacheco Pages, A.; Padhi, S.; Padilla Aranda, C.; Paganis, E.; Pahl, C.; Paige, F.; Pajchel, K.; Pal, A.; Palestini, S.; Pallin, D.; Palma, A.; Palmer, J. D.; Pan, Y. B.; Panagiotopoulou, E.; Panes, B.; Panikashvili, N.; Panitkin, S.; Pantea, D.; Panuskova, M.; Paolone, V.; Papadopoulou, Th. D.; Park, S. J.; Park, W.; Parker, M. A.; Parker, S. I.; Parodi, F.; Parsons, J. A.; Parzefall, U.; Pasqualucci, E.; Passardi, G.; Passeri, A.; Pastore, F.; Pastore, Fr.; Pásztor, G.; Pataraia, S.; Pater, J. R.; Patricelli, S.; Patwa, A.; Pauly, T.; Peak, L. S.; Pecsy, M.; Pedraza Morales, M. I.; Peleganchuk, S. V.; Peng, H.; Penson, A.; Penwell, J.; Perantoni, M.; Perez, K.; Perez Codina, E.; Pérez García-Estañ, M. T.; Perez Reale, V.; Perini, L.; Pernegger, H.; Perrino, R.; Perrodo, P.; Persembe, S.; Perus, P.; Peshekhonov, V. D.; Petersen, B. A.; Petersen, J.; Petersen, T. C.; Petit, E.; Petridou, C.; Petrolo, E.; Petrucci, F.; Petschull, D.; Petteni, M.; Pezoa, R.; Pfeifer, B.; Phan, A.; Phillips, A. W.; Piacquadio, G.; Piccinini, M.; Piegaia, R.; Pilcher, J. E.; Pilkington, A. D.; Pina, J.; Pinamonti, M.; Pinfold, J. L.; Ping, J.; Pinto, B.; Pirotte, O.; Pizio, C.; Placakyte, R.; Plamondon, M.; Plano, W. G.; Pleier, M.-A.; Poblaguev, A.; Poddar, S.; Podlyski, F.; Poffenberger, P.; Poggioli, L.; Pohl, M.; Polci, F.; Polesello, G.; Policicchio, A.; Polini, A.; Poll, J.; Polychronakos, V.; Pomarede, D. M.; Pomeroy, D.; Pommès, K.; Pontecorvo, L.; Pope, B. G.; Popovic, D. S.; Poppleton, A.; Popule, J.; Portell Bueso, X.; Porter, R.; Pospelov, G. E.; Pospichal, P.; Pospisil, S.; Potekhin, M.; Potrap, I. N.; Potter, C. J.; Potter, C. T.; Potter, K. P.; Poulard, G.; Poveda, J.; Prabhu, R.; Pralavorio, P.; Prasad, S.; Pravahan, R.; Preda, T.; Pretzl, K.; Pribyl, L.; Price, D.; Price, L. E.; Prichard, P. M.; Prieur, D.; Primavera, M.; Prokofiev, K.; Prokoshin, F.; Protopopescu, S.; Proudfoot, J.; Prudent, X.; Przysiezniak, H.; Psoroulas, S.; Ptacek, E.; Puigdengoles, C.; Purdham, J.; Purohit, M.; Puzo, P.; Pylypchenko, Y.; Qi, M.; Qian, J.; Qian, W.; Qian, Z.; Qin, Z.; Qing, D.; Quadt, A.; Quarrie, D. R.; Quayle, W. B.; Quinonez, F.; Raas, M.; Radeka, V.; Radescu, V.; Radics, B.; Rador, T.; Ragusa, F.; Rahal, G.; Rahimi, A. M.; Rahm, D.; Rajagopalan, S.; Rammes, M.; Ratoff, P. N.; Rauscher, F.; Rauter, E.; Raymond, M.; Read, A. L.; Rebuzzi, D. M.; Redelbach, A.; Redlinger, G.; Reece, R.; Reeves, K.; Reinherz-Aronis, E.; Reinsch, A.; Reisinger, I.; Reljic, D.; Rembser, C.; Ren, Z. L.; Renkel, P.; Rescia, S.; Rescigno, M.; Resconi, S.; Resende, B.; Reznicek, P.; Rezvani, R.; Richards, A.; Richards, R. A.; Richter, D.; Richter, R.; Richter-Was, E.; Ridel, M.; Rieke, S.; Rijpstra, M.; Rijssenbeek, M.; Rimoldi, A.; Rinaldi, L.; Rios, R. R.; Riu, I.; Rivoltella, G.; Rizatdinova, F.; Rizvi, E. R.; Roa Romero, D. A.; Robertson, S. H.; Robichaud-Veronneau, A.; Robinson, D.; Robinson, M.; Robson, A.; Rocha de Lima, J. G.; Roda, C.; Rodriguez, D.; Rodriguez Garcia, Y.; Roe, S.; Røhne, O.; Rojo, V.; Rolli, S.; Romaniouk, A.; Romanov, V. M.; Romeo, G.; Romero Maltrana, D.; Roos, L.; Ros, E.; Rosati, S.; Rosenbaum, G. A.; Rosenberg, E. I.; Rosselet, L.; Rossi, L. P.; Rotaru, M.; Rothberg, J.; Rottländer, I.; Rousseau, D.; Royon, C. R.; Rozanov, A.; Rozen, Y.; Ruan, X.; Ruckert, B.; Ruckstuhl, N.; Rud, V. I.; Rudolph, G.; Rühr, F.; Ruggieri, F.; Ruiz-Martinez, A.; Rumyantsev, L.; Rusakovich, N. A.; Rutherfoord, J. P.; Ruwiedel, C.; Ruzicka, P.; Ryabov, Y. F.; Ryadovikov, V.; Ryan, P.; Rybkin, G.; Rzaeva, S.; Saavedra, A. F.; Sadrozinski, H. F.-W.; Sadykov, R.; Sakamoto, H.; Salamanna, G.; Salamon, A.; Saleem, M.; Salihagic, D.; Salnikov, A.; Salt, J.; Salvachua Ferrando, B. M.; Salvatore, D.; Salvatore, F.; Salvucci, A.; Salzburger, A.; Sampsonidis, D.; Samset, B. H.; Sanchis Lozano, M. A.; Sandaker, H.; Sander, H. G.; Sanders, M. P.; Sandhoff, M.; Sandstroem, R.; Sandvoss, S.; Sankey, D. P. C.; Sanny, B.; Sansoni, A.; Santamarina Rios, C.; Santi, L.; Santoni, C.; Santonico, R.; Santos, D.; Santos, J.; Saraiva, J. G.; Sarangi, T.; Sarkisyan-Grinbaum, E.; Sarri, F.; Sasaki, O.; Sasaki, T.; Sasao, N.; Satsounkevitch, I.; Sauvage, G.; Savard, P.; Savine, A. Y.; Savinov, V.; Sawyer, L.; Saxon, D. H.; Says, L. P.; Sbarra, C.; Sbrizzi, A.; Scannicchio, D. A.; Schaarschmidt, J.; Schacht, P.; Schäfer, U.; Schaetzel, S.; Schaffer, A. C.; Schaile, D.; Schamberger, R. D.; Schamov, A. G.; Schegelsky, V. A.; Scheirich, D.; Schernau, M.; Scherzer, M. I.; Schiavi, C.; Schieck, J.; Schioppa, M.; Schlenker, S.; Schlereth, J. L.; Schmid, P.; Schmidt, M. P.; Schmieden, K.; Schmitt, C.; Schmitz, M.; Schott, M.; Schouten, D.; Schovancova, J.; Schram, M.; Schreiner, A.; Schroeder, C.; Schroer, N.; Schroers, M.; Schuler, G.; Schultes, J.; Schultz-Coulon, H.-C.; Schumacher, J.; Schumacher, M.; Schumm, B. A.; Schune, Ph.; Schwanenberger, C.; Schwartzman, A.; Schwemling, Ph.; Schwienhorst, R.; Schwierz, R.; Schwindling, J.; Scott, W. G.; Searcy, J.; Sedykh, E.; Segura, E.; Seidel, S. C.; Seiden, A.; Seifert, F.; Seixas, J. M.; Sekhniaidze, G.; Seliverstov, D. M.; Sellden, B.; Seman, M.; Semprini-Cesari, N.; Serfon, C.; Serin, L.; Seuster, R.; Severini, H.; Sevior, M. E.; Sfyrla, A.; Shamim, M.; Shan, L. Y.; Shank, J. T.; Shao, Q. T.; Shapiro, M.; Shatalov, P. B.; Shaver, L.; Shaw, C.; Shaw, K.; Sherman, D.; Sherwood, P.; Shibata, A.; Shimojima, M.; Shin, T.; Shmeleva, A.; Shochet, M. J.; Shupe, M. A.; Sicho, P.; Sidoti, A.; Siebel, A.; Siegert, F.; Siegrist, J.; Sijacki, Dj.; Silbert, O.; Silva, J.; Silver, Y.; Silverstein, D.; Silverstein, S. B.; Simak, V.; Simic, Lj.; Simion, S.; Simmons, B.; Simonyan, M.; Sinervo, P.; Sinev, N. B.; Sipica, V.; Siragusa, G.; Sisakyan, A. N.; Sivoklokov, S. Yu.; Sjoelin, J.; Sjursen, T. B.; Skubic, P.; Skvorodnev, N.; Slater, M.; Slavicek, T.; Sliwa, K.; Sloper, J.; Sluka, T.; Smakhtin, V.; Smirnov, S. Yu.; Smirnov, Y.; Smirnova, L. N.; Smirnova, O.; Smith, B. C.; Smith, D.; Smith, K. M.; Smizanska, M.; Smolek, K.; Snesarev, A. A.; Snow, S. W.; Snow, J.; Snuverink, J.; Snyder, S.; Soares, M.; Sobie, R.; Sodomka, J.; Soffer, A.; Solans, C. A.; Solar, M.; Solfaroli Camillocci, E.; Solodkov, A. A.; Solovyanov, O. V.; Soluk, R.; Sondericker, J.; Sopko, V.; Sopko, B.; Sosebee, M.; Sosnovtsev, V. V.; Sospedra Suay, L.; Soukharev, A.; Spagnolo, S.; Spanò, F.; Speckmayer, P.; Spencer, E.; Spighi, R.; Spigo, G.; Spila, F.; Spiwoks, R.; Spousta, M.; Spreitzer, T.; Spurlock, B.; Denis, R. D. St.; Stahl, T.; Stamen, R.; Stancu, S. N.; Stanecka, E.; Stanek, R. W.; Stanescu, C.; Stapnes, S.; Starchenko, E. A.; Stark, J.; Staroba, P.; Starovoitov, P.; Stastny, J.; Staude, A.; Stavina, P.; Stavropoulos, G.; Steinbach, P.; Steinberg, P.; Stekl, I.; Stelzer, B.; Stelzer, H. J.; Stelzer-Chilton, O.; Stenzel, H.; Stevenson, K.; Stewart, G.; Stockton, M. C.; Stoerig, K.; Stoicea, G.; Stonjek, S.; Strachota, P.; Stradling, A.; Straessner, A.; Strandberg, J.; Strandberg, S.; Strandlie, A.; Strauss, M.; Strizenec, P.; Ströhmer, R.; Strom, D. M.; Strong, J. A.; Stroynowski, R.; Strube, J.; Stugu, B.; Stumer, I.; Soh, D. A.; Su, D.; Suchkov, S. I.; Sugaya, Y.; Sugimoto, T.; Suhr, C.; Suk, M.; Sulin, V. V.; Sultansoy, S.; Sumida, T.; Sun, X.; Sundermann, J. E.; Suruliz, K.; Sushkov, S.; Susinno, G.; Sutton, M. R.; Suzuki, T.; Suzuki, Y.; Sviridov, Yu. M.; Sykora, I.; Sykora, T.; Szymocha, T.; Sánchez, J.; Ta, D.; Tackmann, K.; Taffard, A.; Tafirout, R.; Taga, A.; Takahashi, Y.; Takai, H.; Takashima, R.; Takeda, H.; Takeshita, T.; Talby, M.; Talyshev, A.; Tamsett, M. C.; Tanaka, J.; Tanaka, R.; Tanaka, S.; Tanaka, S.; Tappern, G. P.; Tapprogge, S.; Tardif, D.; Tarem, S.; Tarrade, F.; Tartarelli, G. F.; Tas, P.; Tasevsky, M.; Tassi, E.; Taylor, C.; Taylor, F. E.; Taylor, G. N.; Taylor, R. P.; Taylor, W.; Teixeira-Dias, P.; Ten Kate, H.; Teng, P. K.; Terada, S.; Terashi, K.; Terron, J.; Terwort, M.; Testa, M.; Teuscher, R. J.; Tevlin, C. M.; Thadome, J.; Thananuwong, R.; Thioye, M.; Thoma, S.; Thomas, J. P.; Thomas, T. L.; Thompson, E. N.; Thompson, P. D.; Thompson, P. D.; Thompson, R. J.; Thompson, A. S.; Thomson, E.; Thun, R. P.; Tic, T.; Tikhomirov, V. O.; Tikhonov, Y. A.; Timmermans, C. J. W. P.; Tipton, P.; Tique Aires Viegas, F. J.; Tisserant, S.; Tobias, J.; Toczek, B.; Todorov, T.; Todorova-Nova, S.; Toggerson, B.; Tojo, J.; Tokár, S.; Tokushuku, K.; Tollefson, K.; Tomasek, L.; Tomasek, M.; Tomasz, F.; Tomoto, M.; Tompkins, D.; Tompkins, L.; Toms, K.; Tong, G.; Tonoyan, A.; Topfel, C.; Topilin, N. D.; Torrence, E.; Torró Pastor, E.; Toth, J.; Touchard, F.; Tovey, D. R.; Tovey, S. N.; Trefzger, T.; Tremblet, L.; Tricoli, A.; Trigger, I. M.; Trincaz-Duvoid, S.; Trinh, T. N.; Tripiana, M. F.; Triplett, N.; Trivedi, A.; Trocmé, B.; Troncon, C.; Trzupek, A.; Tsarouchas, C.; Tseng, J. C.-L.; Tsiafis, I.; Tsiakiris, M.; Tsiareshka, P. V.; Tsionou, D.; Tsipolitis, G.; Tsiskaridze, V.; Tskhadadze, E. G.; Tsukerman, I. I.; Tsulaia, V.; Tsung, J.-W.; Tsuno, S.; Tsybychev, D.; Turala, M.; Turecek, D.; Turk Cakir, I.; Turlay, E.; Tuts, P. M.; Twomey, M. S.; Tylmad, M.; Tyndel, M.; Tzanakos, G.; Uchida, K.; Ueda, I.; Uhlenbrock, M.; Uhrmacher, M.; Ukegawa, F.; Unal, G.; Underwood, D. G.; Undrus, A.; Unel, G.; Unno, Y.; Urbaniec, D.; Urkovsky, E.; Urquijo, P.; Urrejola, P.; Usai, G.; Uslenghi, M.; Vacavant, L.; Vacek, V.; Vachon, B.; Vahsen, S.; Valenta, J.; Valente, P.; Valentinetti, S.; Valkar, S.; Valladolid Gallego, E.; Vallecorsa, S.; Valls Ferrer, J. A.; van Berg, R.; van der Graaf, H.; van der Kraaij, E.; van der Poel, E.; van der Ster, D.; van Eldik, N.; van Gemmeren, P.; van Kesteren, Z.; van Vulpen, I.; Vandelli, W.; Vandoni, G.; Vaniachine, A.; Vankov, P.; Vannucci, F.; Varela Rodriguez, F.; Vari, R.; Varnes, E. W.; Varouchas, D.; Vartapetian, A.; Varvell, K. E.; Vasilyeva, L.; Vassilakopoulos, V. I.; Vazeille, F.; Vegni, G.; Veillet, J. J.; Vellidis, C.; Veloso, F.; Veness, R.; Veneziano, S.; Ventura, A.; Ventura, D.; Venturi, M.; Venturi, N.; Vercesi, V.; Verducci, M.; Verkerke, W.; Vermeulen, J. C.; Vetterli, M. C.; Vichou, I.; Vickey, T.; Viehhauser, G. H. A.; Villa, M.; Villani, E. G.; Villaplana Perez, M.; Villate, J.; Vilucchi, E.; Vincter, M. G.; Vinek, E.; Vinogradov, V. B.; Viret, S.; Virzi, J.; Vitale, A.; Vitells, O. V.; Vivarelli, I.; Vives Vaques, F.; Vlachos, S.; Vlasak, M.; Vlasov, N.; Vogt, H.; Vokac, P.; Volpi, M.; Volpini, G.; von der Schmitt, H.; von Loeben, J.; von Radziewski, H.; von Toerne, E.; Vorobel, V.; Vorobiev, A. P.; Vorwerk, V.; Vos, M.; Voss, R.; Voss, T. T.; Vossebeld, J. H.; Vranjes, N.; Vranjes Milosavljevic, M.; Vrba, V.; Vreeswijk, M.; Vu Anh, T.; Vudragovic, D.; Vuillermet, R.; Vukotic, I.; Wagner, P.; Wahlen, H.; Walbersloh, J.; Walder, J.; Walker, R.; Walkowiak, W.; Wall, R.; Wang, C.; Wang, H.; Wang, J.; Wang, J. C.; Wang, S. M.; Ward, C. P.; Warsinsky, M.; Wastie, R.; Watkins, P. M.; Watson, A. T.; Watson, M. F.; Watts, G.; Watts, S.; Waugh, A. T.; Waugh, B. M.; Webel, M.; Weber, J.; Weber, M. D.; Weber, M.; Weber, M. S.; Weber, P.; Weidberg, A. R.; Weingarten, J.; Weiser, C.; Wellenstein, H.; Wells, P. S.; Wen, M.; Wenaus, T.; Wendler, S.; Wengler, T.; Wenig, S.; Wermes, N.; Werner, M.; Werner, P.; Werth, M.; Werthenbach, U.; Wessels, M.; Whalen, K.; Wheeler-Ellis, S. J.; Whitaker, S. P.; White, A.; White, M. J.; White, S.; Whiteson, D.; Whittington, D.; Wicek, F.; Wicke, D.; Wickens, F. J.; Wiedenmann, W.; Wielers, M.; Wienemann, P.; Wiglesworth, C.; Wiik, L. A. M.; Wildauer, A.; Wildt, M. A.; Wilhelm, I.; Wilkens, H. G.; Williams, E.; Williams, H. H.; Willis, W.; Willocq, S.; Wilson, J. A.; Wilson, M. G.; Wilson, A.; Wingerter-Seez, I.; Winklmeier, F.; Wittgen, M.; Wolter, M. W.; Wolters, H.; Wosiek, B. K.; Wotschack, J.; Woudstra, M. J.; Wraight, K.; Wright, C.; Wright, D.; Wrona, B.; Wu, S. L.; Wu, X.; Wulf, E.; Xella, S.; Xie, S.; Xie, Y.; Xu, D.; Xu, N.; Yamada, M.; Yamamoto, A.; Yamamoto, S.; Yamamura, T.; Yamanaka, K.; Yamaoka, J.; Yamazaki, T.; Yamazaki, Y.; Yan, Z.; Yang, H.; Yang, U. K.; Yang, Y.; Yang, Z.; Yao, W.-M.; Yao, Y.; Yasu, Y.; Ye, J.; Ye, S.; Yilmaz, M.; Yoosoofmiya, R.; Yorita, K.; Yoshida, R.; Young, C.; Youssef, S. P.; Yu, D.; Yu, J.; Yu, M.; Yu, X.; Yuan, J.; Yuan, L.; Yurkewicz, A.; Zaidan, R.; Zaitsev, A. M.; Zajacova, Z.; Zambrano, V.; Zanello, L.; Zarzhitsky, P.; Zaytsev, A.; Zeitnitz, C.; Zeller, M.; Zema, P. F.; Zemla, A.; Zendler, C.; Zenin, O.; Zenis, T.; Zenonos, Z.; Zenz, S.; Zerwas, D.; Zevi Della Porta, G.; Zhan, Z.; Zhang, H.; Zhang, J.; Zhang, Q.; Zhang, X.; Zhao, L.; Zhao, T.; Zhao, Z.; Zhemchugov, A.; Zheng, S.; Zhong, J.; Zhou, B.; Zhou, N.; Zhou, Y.; Zhu, C. G.; Zhu, H.; Zhu, Y.; Zhuang, X.; Zhuravlov, V.; Zilka, B.; Zimmermann, R.; Zimmermann, S.; Zimmermann, S.; Ziolkowski, M.; Zitoun, R.; Živković, L.; Zmouchko, V. V.; Zobernig, G.; Zoccoli, A.; Zur Nedden, M.; Zutshi, V.

2010-12-01

The ATLAS liquid argon calorimeter has been operating continuously since August 2006. At this time, only part of the calorimeter was readout, but since the beginning of 2008, all calorimeter cells have been connected to the ATLAS readout system in preparation for LHC collisions. This paper gives an overview of the liquid argon calorimeter performance measured in situ with random triggers, calibration data, cosmic muons, and LHC beam splash events. Results on the detector operation, timing performance, electronics noise, and gain stability are presented. High energy deposits from radiative cosmic muons and beam splash events allow to check the intrinsic constant term of the energy resolution. The uniformity of the electromagnetic barrel calorimeter response along η (averaged over φ) is measured at the percent level using minimum ionizing cosmic muons. Finally, studies of electromagnetic showers from radiative muons have been used to cross-check the Monte Carlo simulation. The performance results obtained using the ATLAS readout, data acquisition, and reconstruction software indicate that the liquid argon calorimeter is well-prepared for collisions at the dawn of the LHC era.

Ion Transport and Structural Properties of Polymeric Electrolytes and Ionic Liquids from Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Borodin, Oleg

2010-03-01

Molecular dynamics simulations are well suited for exploring electrolyte structure and ion transport mechanisms on the nanometer length scale and the nanosecond time scales. In this presentation we will describe how MD simulations assist in answering fundamental questions about the lithium transport mechanisms in polymeric electrolytes and ionic liquids. In particular, in the first part of the presentation the extent of ion aggregation, the structure of ion aggregates and the lithium cation diffusion in binary polymeric electrolytes will be compared with that of single-ion conducting polymers. In the second part of the talk, the lithium transport in polymeric electrolytes will be compared with that of three ionic liquids ( [emim][FSI] doped with LiFSI , [pyr13][FSI] doped with LiFSI, [emim][BF4] doped with LiBF4). The relation between ionic liquid self-diffusion, conductivity and thermodynamic properties will be discussed in details. A number of correlations between heat of vaporization Hvap, cation-anion binding energy (E+/-), molar volume (Vm), self-diffusion coefficient (D) and ionic conductivity for 29 ionic liquids have been investigated using MD simulations. A significant correlation between D and Hvap has been found, while best correlation was found for -log((D Vm)) vs. Hvap+0.28E+/-. A combination of enthalpy of vaporization and a fraction of the cation-anion binding energy was suggested as a measure of the effective cohesive energy for ionic liquids.

Purification of inkjet ink from water using liquid phase, electric discharge polymerization and cellulosic membrane filtration.

PubMed

Jordan, Alexander T; Hsieh, Jeffery S; Lee, Daniel T

2013-01-01

A method to separate inkjet ink from water was developed using a liquid phase, electric discharge process. The liquid phase, electric discharge process with filtration or sedimentation was shown to remove 97% of inkjet ink from solutions containing between 0.1-0.8 g/L and was consistent over a range of treatment conditions. Additionally, particle size analysis of treated allyl alcohol and treated propanol confirmed the electric discharge treatment has a polymerization mechanism, and small molecule analysis of treated methanol using gas chromatography and mass spectroscopy confirmed the mechanism was free radical initiated polymerization.

Multiscale Simulation of Gas Film Lubrication During Liquid Droplet Collision

NASA Astrophysics Data System (ADS)

Chen, Xiaodong; Khare, Prashant; Ma, Dongjun; Yang, Vigor

2012-02-01

Droplet collision plays an elementary role in dense spray combustion process. When two droplets approach each other, a gas film forms in between. The pressure generated within the film prevents motion of approaching droplets. This fluid mechanics is fluid film lubrication that occurs when opposing bearing surfaces are completely separated by fluid film. The lubrication flow in gas film decides the collision outcome, coalescence or bouncing. Present study focuses on gas film drainage process over a wide range of Weber numbers during equal- and unequal-sized droplet collision. The formulation is based on complete set of conservation equations for both liquid and surrounding gas phases. An improved volume-of-fluid technique, augmented by an adaptive mesh refinement algorithm, is used to track liquid/gas interfaces. A unique thickness-based refinement algorithm based on topology of interfacial flow is developed and implemented to efficiently resolve the multiscale problem. The grid size on interface is up O(10-4) of droplet size with a max resolution of 0.015 μm. An advanced visualization technique using the Ray-tracing methodology is used to gain direct insights to detailed physics. Theories are established by analyzing the characteristics of shape changing and flow evolution.

Reducing the risk of rear-end collisions with infrastructure-to-vehicle (I2V) integration of variable speed limit control and adaptive cruise control system.

PubMed

Li, Ye; Wang, Hao; Wang, Wei; Liu, Shanwen; Xiang, Yun

2016-08-17

Adaptive cruise control (ACC) has been investigated recently to explore ways to increase traffic capacity, stabilize traffic flow, and improve traffic safety. However, researchers seldom have studied the integration of ACC and roadside control methods such as the variable speed limit (VSL) to improve safety. The primary objective of this study was to develop an infrastructure-to-vehicle (I2V) integrated system that incorporated both ACC and VSL to reduce rear-end collision risks on freeways. The intelligent driver model was firstly modified to simulate ACC behavior and then the VSL strategy used in this article was introduced. Next, the I2V system was proposed to integrate the 2 advanced techniques, ACC and VSL. Four scenarios of no control, VSL only, ACC only, and the I2V system were tested in simulation experiments. Time exposed time to collision (TET) and time integrated time to collision (TIT), 2 surrogate safety measures derived from time to collision (TTC), were used to evaluate safety issues associated with rear-end collisions. The total travel times of each scenario were also compared. The simulation results indicated that both the VSL-only and ACC-only methods had a positive impact on reducing the TET and TIT values (reduced by 53.0 and 58.6% and 59.0 and 65.3%, respectively). The I2V system combined the advantages of both ACC and VSL to achieve the most safety benefits (reduced by 71.5 and 77.3%, respectively). Sensitivity analysis of the TTC threshold also showed that the I2V system obtained the largest safety benefits with all of the TTC threshold values. The impact of different market penetration rates of ACC vehicles in I2V system indicated that safety benefits increase with an increase in ACC proportions. Compared to VSL-only and ACC-only scenarios, this integrated I2V system is more effective in reducing rear-end collision risks. The findings of this study provide useful information for traffic agencies to implement novel techniques to improve

Fabrication of core-shell structured magnetic nanocellulose base polymeric ionic liquid for effective biosorption of Congo red dye.

PubMed

Beyki, Mostafa Hossein; Bayat, Mehrnoosh; Shemirani, Farzaneh

2016-10-01

Ionic liquids are considered to be a class of environmentally friendly compounds as combination of them with bioresource polymeric substances such as; cellulose, constitute emerging coating materials. Biosorption by polymeric ionic liquids exhibits an attractive green way that involves low cost and irrespective of toxicity. As a result, a novel polymeric ionic liquid has been developed by the reaction of one step synthesized Fe3O4-cellulose nanohybrid, epichlorohydrin and 1-methylimidazole and employed as a green sorbent for efficient biosorption of Congo red dye. Effective parameters on dye removing as well as their interactions were determined with response surface methodology (RSM). Congo red adsorption showed fast equilibrium time (11min) with maximum uptake of 131mgg(-1). Isotherm study revealed that Langmuir adsorption model can better describe dye adsorption behavior. Regeneration of the sorbent was performed with a mixture of methanol-acetone-NaOH (3.0molL(-1)) solution. Copyright © 2016 Elsevier Ltd. All rights reserved.

ENZYMATIC POLYMERIZATION OF PHENOLS IN ROOM TEMPERATURE IONIC LIQUIDS

PubMed Central

Eker, Bilge; Zagorevski, Dmitri; Zhu, Guangyu; Linhardt, Robert J.; Dordick, Jonathan S.

2009-01-01

Soybean peroxidase (SBP) was used to catalyze the polymerization of phenols in room-temperature ionic liquids (RTILs). Phenolic polymers with number average molecular weights ranging from 1200 to 4100 D were obtained depending on the composition of the reaction medium and the nature of the phenol. Specifically, SBP was highly active in methylimidazolium-containing RTILs, including 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM(BF4)), and 1-butyl-3-methylpyridinium tetrafluoroborate (BMPy(BF4)) with the ionic liquid content as high as 90% (v/v); the balance being aqueous buffer. Gel permeation chromatography and MALDI-TOF analysis indicated that higher molecular weight polymers can be synthesized in the presence of higher RTIL concentrations, with selective control over polymer size achieved by varying the RTIL concentration. The resulting polyphenols exhibited high thermostability and possessed thermosetting properties. PMID:20161409

Functional Nanostructured Materials Based on Polymerized Surfactant Liquid Crystal Assemblies Liquid Crystal Assemblies

NASA Astrophysics Data System (ADS)

Gin, Douglas

2003-03-01

The development of materials with controlled nanostructures is one of the most important new areas of scientific research in chemistry and engineering. Our research group has developed a novel approach for making nanostructured polymer materials with unique functional properties using liquid crystals as starting materials. In this approach, we design polymerizable organic building blocks based on lyotropic liquid crystals (LLCs) (i.e., amphiphiles or surfactants) that carry, or can accommodate, a functional property of general interest. Through appropriate molecular design, these monomers self-assemble in the presence of water into fluid, yet ordered phase-separated, water-hydrocarbon assemblies with predictable nanoscale geometries. The architectures of these LLC phases can range from stacked two-dimensional lamellae to hexagonally ordered cylindrical channels with uniform feature sizes in the 1-10 nm range. These LLC phases are then photopolymerized into robust polymer networks with preservation of their small-scale structures. This approach allows us to investigate the effect of nanometer-scale architecture on important bulk properties, as well as to engineer chemical environments on the nanometer-scale for several areas of application. In this talk, new functional materials based on the polymerization of the lyotropic inverted hexagonal phase will be presented as one example of our general approach. Issues in the design and photopolymerization of functional amphiphilic monomers that adopt this LC architecture will be discussed. More importantly, the use of the resulting nanostructured polymer networks in three areas of application will be presented: (1) as templates for the synthesis of functional nanocomposites; (2) as tunable heterogeneous catalysts, and (3) as nanoporous membrane and separation media. In particular, issues pertaining to the contribution of nanoscale architecture to the performance of these systems will be highlighted. Opportunities for

Readiness of the ATLAS liquid argon calorimeter for LHC collisions

DOE PAGES

Aad, G.; Abbott, B.; Abdallah, J.; ...

2010-08-20

The ATLAS liquid argon calorimeter has been operating continuously since August 2006. At this time, only part of the calorimeter was readout, but since the beginning of 2008, all calorimeter cells have been connected to the ATLAS readout system in preparation for LHC collisions. This paper gives an overview of the liquid argon calorimeter performance measured in situ with random triggers, calibration data, cosmic muons, and LHC beam splash events. Results on the detector operation, timing performance, electronics noise, and gain stability are presented. High energy deposits from radiative cosmic muons and beam splash events allow to check the intrinsicmore » constant term of the energy resolution. The uniformity of the electromagnetic barrel calorimeter response along η (averaged over Φ) is measured at the percent level using minimum ionizing cosmic muons. Finally, studies of electromagnetic showers from radiative muons have been used to cross-check the Monte Carlo simulation. The performance results obtained using the ATLAS readout, data acquisition, and reconstruction software indicate that the liquid argon calorimeter is well-prepared for collisions at the dawn of the LHC era.« less

Quantum-state-resolved CO2 scattering dynamics at the gas-liquid interface: dependence on incident angle.

PubMed

Perkins, Bradford G; Nesbitt, David J

2007-08-09

Energy transfer dynamics at the gas-liquid interface have been probed with a supersonic molecular beam of CO2 and a clean perfluorinated-liquid surface in vacuum. High-resolution infrared spectroscopy measures both the rovibrational state populations and the translational distributions for the scattered CO2 flux. The present study investigates collision dynamics as a function of incident angle (thetainc = 0 degrees, 30 degrees, 45 degrees, and 60 degrees), where column-integrated quantum state populations are detected along the specular-scattering direction (i.e., thetascat approximately thetainc). Internal state rovibrational and Doppler translational distributions in the scattered CO2 yield clear evidence for nonstatistical behavior, providing quantum-state-resolved support for microscopic branching of the gas-liquid collision dynamics into multiple channels. Specifically, the data are remarkably well described by a two-temperature model, which can be associated with both a trapping desorption (TD) component emerging at the surface temperature (Trot approximately TS) and an impulsive scattering (IS) component appearing at hyperthermal energies (Trot > TS). The branching ratio between the TD and IS channels is found to depend strongly on thetainc, with the IS component growing dramatically with increasingly steeper angle of incidence.

Polymeric Beads for Organic Coatings

DTIC Science & Technology

1982-10-31

Clear Solid Polymeric Beads A solid polymeric bead is comprised of a sol id mass of polymerized unsaturated polyester/styrene resin mixture . 2. lear...than the current unsaturated polyester resin . For example, a bead male from acrylic resin could be more trans- - parent, more durable and provide more...0.44 Isopropyl Alcohol I 11.26 I 1 .73 60% Wt. Alkyd Resin - Volume I 251.26 i 30.52 " Sol ids 51% 1 I Anti.-Skinning Agent I 0.90 I 0.12 Mineral

Ejector/liquid ring pump provides <0. 30 mm Hg vacuum for polymerization vessel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lockwood, A.; Gaines, A.

1982-03-01

Firestone Fibers and Textiles Company, a division of Firestone Tire and Rubber Company, manufactures tire and industrial yarns of polyester and nylon-6. Nylon-6 molding and extrusion resins are also produced at the plant in Hopewell, Virginia. The process for making polyester requires an extremely low vacuum on the polymerization reactor. A consistent polymerization vessel vacuum of 0.3 mm Hg is needed, but the existing vacuum source, a five-stage steam jet ejector, could only provide a 0.5 mm Hg level. Two options were considered when the company decided to replace the original system with a system designed for 0.15 mm Hgmore » with a non-condensible gas load of 10.8 lb/hr. A new five-stage jet ejector system to meet these requirements would use 1395 lb/hr of 100 psig steam. The other option was a hybrid vacuum source composed of a three-stage steam ejector system and a liquid ring vacuum pump that is more energy efficient than ejectors for low vacuum applications. The hybrid system was selected because the three-stage jet ejector would use only 1240 lb/hr of 100 psig steam. The liquid ring vacuum pump would increase the material and installation cost of the system by about $4000, but the savings in steam consumption would pay back the added cost in less than two years. The jet ejector/liquid ring vacuum pump system has provided both the capacity and the extremely low vacuum needed for the polyester polymerization vessel, after making a small modification. The hybrid vacuum source is reliable, requires only routine maintenance, and will contiue to save substantial amounts of steam each year compared to the five-stage steam jet ejector.« less

High-pressure phase diagrams of liquid CO2 and N2

NASA Astrophysics Data System (ADS)

Boates, Brian; Bonev, Stanimir

2011-06-01

The phase diagrams of liquid CO2 and N2 have been investigated using first-principles theory. Both materials exhibit transitions to conducting liquids at high temperatures (T) and relatively modest pressures (P). Furthermore, both liquids undergo polymerization phase transitions at pressures comparable to their solid counterparts. The liquid phase diagrams have been divided into several regimes through a detailed analysis of changes in bonding, as well as structural and electronic properties for pressures and temperatures up to 200 GPa and 10 000 K, respectively. Similarities and differences between the high- P and T behavior of these fluids will be discussed. Calculations of the Hugoniot are in excellent agreement with available experimental data. Work supported by NSERC, LLNL, and the Killam Trusts. Prepared by LLNL under Contract DE-AC52-07NA27344.

Polymerization of perfluorobutadiene

NASA Technical Reports Server (NTRS)

Newman, J.; Toy, M. S.

1970-01-01

Diisopropyl peroxydicarbonate dissolved in liquid perfluorobutadiene is conducted in a sealed vessel at the autogenous pressure of polymerization. Reaction temperature, ratio of catalyst to monomer, and amount of agitation determine degree of polymerization and product yield.

The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes

PubMed Central

Akhmetshina, Alsu A.; Davletbaeva, Ilsiya M.; Grebenschikova, Ekaterina S.; Sazanova, Tatyana S.; Petukhov, Anton N.; Atlaskin, Artem A.; Razov, Evgeny N.; Zaripov, Ilnaz I.; Martins, Carla F.; Neves, Luísa A.; Vorotyntsev, Ilya V.

2015-01-01

Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested for He, N2, NH3, H2S, and CO2 gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF6] and [emim][Tf2N]. The modification of SILMs by nanosize silica particles leads to an increase of NH3 separation relatively to CO2 or H2S. PMID:26729177

Comparison between polymerized ionic liquids synthesized using chain-growth and step-growth mechanisms used as stationary phase in gas chromatography.

PubMed

Roeleveld, Kevin; David, Frank; Lynen, Frédéric

2016-06-17

In this study the merits of polymerized imidazolium based ionic liquid (PIL) stationary phases obtained via condensation and free radical polymerizations are compared as stationary phases in gas chromatography (GC). Poly(1-vinyl-3-butyl-imidazolium - bis(trifluoromethane)sulfonamide) (poly(ViC4Im(+) NTf2(-))) was obtained via a chain-growth mechanism while poly(propylimidazolium-NTf2) (poly(C3Im(+) NTf2(-))) was synthesized via a step-growth polymerization. The thermal stability of both polymers was assessed using thermal gravimetric analysis and compared with bleeding profiles obtained from the statically coated GC columns (30m×0.25mm×0.25μm). The performance was compared to what could be obtained on commercially available 1,5-di(2,3-dimethylimidazolium)pentane(2+) 2NTf2(-) (SLB-IL111) ionic liquid based columns. It was observed that the step-growth polymer was more thermally stable, up to 325°C, while the chain-growth polymer showed initial degradation at 250°C. Both polymers allowed reaching minimal plate heights of 0.400-0.500mm for retained solutes such as benzaldehyde, acetophenone, 1-methylnaphthalene and aniline. Assessment of the McReynolds constants illustrated that the polarity of the step-growth polymer was similar to the SLB-IL111 column, while displaying improved column stability. The PIL phases and particularly the so far little studied condensation based polymer shows particular retention and satisfactory column performance for polar moieties such as esters, amine and carbonyl functionalities. Copyright © 2016 Elsevier B.V. All rights reserved.

Kinetic and Mechanistic Study of Vapor-Phase Free Radical Polymerization onto Liquid Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, Malancha

The primary objective of this proposal was to study vapor deposition of polymers onto liquid surfaces. Deposition onto liquid surfaces is a relatively new area of research because the past few decades have focused on deposition onto solid materials. We used initiated chemical vapor deposition to deposit polymers onto the liquid surfaces. The process is a one-step, solventless, free-radical polymerization process in which monomer and initiator molecules are flowed into a vacuum chamber. We found that the surface tension interaction between the polymer and the liquid determines whether a film or nanoparticles are formed. We also found that we couldmore » form gels by using soluble monomers. We found that we could tune the size of the nanoparticles by varying the viscosity of the liquid and the process parameters including pressure and time. These insights allow scalable synthesis of polymer materials for a variety of separation and catalysis applications.« less

GMC COLLISIONS AS TRIGGERS OF STAR FORMATION. I. PARAMETER SPACE EXPLORATION WITH 2D SIMULATIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Benjamin; Loo, Sven Van; Tan, Jonathan C.

We utilize magnetohydrodynamic (MHD) simulations to develop a numerical model for giant molecular cloud (GMC)–GMC collisions between nearly magnetically critical clouds. The goal is to determine if, and under what circumstances, cloud collisions can cause pre-existing magnetically subcritical clumps to become supercritical and undergo gravitational collapse. We first develop and implement new photodissociation region based heating and cooling functions that span the atomic to molecular transition, creating a multiphase ISM and allowing modeling of non-equilibrium temperature structures. Then in 2D and with ideal MHD, we explore a wide parameter space of magnetic field strength, magnetic field geometry, collision velocity, andmore » impact parameter and compare isolated versus colliding clouds. We find factors of ∼2–3 increase in mean clump density from typical collisions, with strong dependence on collision velocity and magnetic field strength, but ultimately limited by flux-freezing in 2D geometries. For geometries enabling flow along magnetic field lines, greater degrees of collapse are seen. We discuss observational diagnostics of cloud collisions, focussing on {sup 13}CO(J = 2–1), {sup 13}CO(J = 3–2), and {sup 12}CO(J = 8–7) integrated intensity maps and spectra, which we synthesize from our simulation outputs. We find that the ratio of J = 8–7 to lower-J emission is a powerful diagnostic probe of GMC collisions.« less

Production of fungal antibiotics using polymeric solid supports in solid-state and liquid fermentation.

PubMed

Bigelis, Ramunas; He, Haiyin; Yang, Hui Y; Chang, Li-Ping; Greenstein, Michael

2006-10-01

The use of inert absorbent polymeric supports for cellular attachment in solid-state fungal fermentation influenced growth, morphology, and production of bioactive secondary metabolites. Two filamentous fungi exemplified the utility of this approach to facilitate the discovery of new antimicrobial compounds. Cylindrocarpon sp. LL-Cyan426 produced pyrrocidines A and B and Acremonium sp. LL-Cyan416 produced acremonidins A-E when grown on agar bearing moist polyester-cellulose paper and generated distinctly different metabolite profiles than the conventional shaken or stationary liquid fermentations. Differences were also apparent when tenfold concentrated methanol extracts from these fermentations were tested against antibiotic-susceptible and antibiotic-resistant Gram-positive bacteria, and zones of inhibition were compared. Shaken broth cultures of Acremonium sp. or Cylindrocarpon sp. showed complex HPLC patterns, lower levels of target compounds, and high levels of unwanted compounds and medium components, while agar/solid support cultures showed significantly increased yields of pyrrocidines A and B and acremonidins A-E, respectively. This method, mixed-phase fermentation (fermentation with an inert solid support bearing liquid medium), exploited the increase in surface area available for fungal growth on the supports and the tendency of some microorganisms to adhere to solid surfaces, possibly mimicking their natural growth habits. The production of dimeric anthraquinones by Penicillium sp. LL-WF159 was investigated in liquid fermentation using various inert polymeric immobilization supports composed of polypropylene, polypropylene cellulose, polyester-cellulose, or polyurethane. This culture produced rugulosin, skyrin, flavomannin, and a new bisanthracene, WF159-A, after fermentation in the presence and absence of polymeric supports for mycelial attachment. The physical nature of the different support systems influenced culture morphology and relative

Mutations to the Formin Homology 2 Domain of INF2 Protein Have Unexpected Effects on Actin Polymerization and Severing*

PubMed Central

Ramabhadran, Vinay; Gurel, Pinar S.; Higgs, Henry N.

2012-01-01

INF2 (inverted formin 2) is a formin protein with unusual biochemical characteristics. As with other formins, the formin homology 2 (FH2) domain of INF2 accelerates actin filament assembly and remains at the barbed end, modulating elongation. The unique feature of INF2 is its ability to sever filaments and enhance depolymerization, which requires the C-terminal region. Physiologically, INF2 acts in the secretory pathway and is mutated in two human diseases, focal and segmental glomerulosclerosis and Charcot-Marie-Tooth disease. In this study, we investigate the effects of mutating two FH2 residues found to be key in other formins: Ile-643 and Lys-792. Surprisingly, neither mutation abolishes barbed end binding, as judged by pyrene-actin and total internal reflection (TIRF) microscopy elongation assays. The I643A mutation causes tight capping of a subset of filaments, whereas K792A causes slow elongation of all filaments. The I643A mutation has a minor inhibitory effect on polymerization activity but causes almost complete abolition of severing and depolymerization activity. The K792A mutation has relatively small effects on polymerization, severing, and depolymerization. In cells, the K792A mutant causes actin accumulation around the endoplasmic reticulum to a similar extent as wild type, whereas the I643A mutant causes no measurable polymerization. The inability of I643A to induce actin polymerization in cells is explained by its inability to promote robust actin polymerization in the presence of capping protein. These results highlight an important point: it is dangerous to assume that mutation of conserved FH2 residues will have equivalent effects in all formins. The work also suggests that both mutations have effects on the mechanism of processive elongation. PMID:22879592

The effect of varying linker length on ion-transport properties in polymeric ionic liquids

NASA Astrophysics Data System (ADS)

Keith, Jordan; Mogurampelly, Santosh; Wheatle, Bill; Ganesan, Venkat

We report results of atomistic molecular dynamics simulations on polymerized 1-butyl-3-(n-alkyl)imidazolium ionic liquids with PF6- counterions. Consistent with experimental observations, we observe that the mobility of the PF6- ions increases with increasing n-alkyl linker length. Analysis of our results suggests that the motion of PF6- ions is driven by intermolecular ion hopping between chains, which in turn is influenced by ion-pair coordination numbers and intermolecular ionic separation distances. With increasing linker length, we observe 1) the anions coordinating less closely with cations and 2) intermolecular hopping distances decreasing.

Correlating morphology to dc conductivity in polymerized ionic liquids

NASA Astrophysics Data System (ADS)

Iacob, Ciprian; Matusmoto, Atsushi; Inoue, Tadashi; Runt, James

Polymerized ionic liquids (PILs) combine the attractive mechanical characteristics of polymers and unique physico-chemical properties of low molecular weight ionic liquids in the same material. PILs have shown remarkable advantages when employed in electrochemical devices such as dye-sensitized solar cells and lithium batteries, among others. Understanding their ionic transport mechanism is the key for designing highly conductive PILs. In the current study, the correlation between morphology and charge transport in two homologous series of PILs with systematic variation of the alkyl chain length and anions is investigated using broadband dielectric spectroscopy, rheology, differential scanning calorimetry and X-ray scattering. As the alkyl chain length increases, the backbone-to-backbone separation increases, and dc-conductivity consequently decreases. The cations dominate structural dynamics since they are attached to the polymer chains, while the anions are smaller and more mobile ionic species thereby controlling the ionic conductivity. Further interpretation of decoupling of dc conductivity from the segmental relaxation enabled the correlation between polymer morphology and dc conductivity. Supported by the National Science Foundation, Polymers Program.

Photo-triggered solvent-free metamorphosis of polymeric materials.

PubMed

Honda, Satoshi; Toyota, Taro

2017-09-11

Liquefaction and solidification of materials are the most fundamental changes observed during thermal phase transitions, yet the design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion remains challenging. Here, we demonstrate that solvent-free repeatable molecular architectural transformation between liquid-star and nonliquid-network polymers that relies on cleavage and reformation of a covalent bond in hexaarylbiimidazole. Liquid four-armed star-shaped poly(n-butyl acrylate) and poly(dimethyl siloxane) with 2,4,5-triphenylimidazole end groups were first synthesized. Subsequent oxidation of the 2,4,5-triphenylimidazoles into 2,4,5-triphenylimidazoryl radicals and their coupling with these liquid star polymers to form hexaarylbiimidazoles afforded the corresponding nonliquid network polymers. The resulting nonliquid network polymers liquefied upon UV irradiation and produced liquid star-shaped polymers with 2,4,5-triphenylimidazoryl radical end groups that reverted to nonliquid network polymers again by recoupling of the generated 2,4,5-triphenylimidazoryl radicals immediately after terminating UV irradiation.The design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion is challenging. Here, the authors show solvent-free repeatable molecular architectural transformation between liquid-star and non-liquid-network polymers by the cleavage and reformation of covalent bonds in the polymer chain.

21 CFR 177.2250 - Filters, microporous polymeric.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Filters, microporous polymeric. 177.2250 Section... Repeated Use § 177.2250 Filters, microporous polymeric. Microporous polymeric filters identified in... liquid food. (a) Microporous polymeric filters consist of a suitably permeable, continuous, polymeric...

Identifying the dynamics of actin and tubulin polymerization in iPSCs and in iPSC-derived neurons

PubMed Central

Magliocca, Valentina; Petrini, Stefania; Franchin, Tiziana; Borghi, Rossella; Niceforo, Alessia; Abbaszadeh, Zeinab; Bertini, Enrico; Compagnucci, Claudia

2017-01-01

The development of the nervous system requires cytoskeleton-mediated processes coordinating self-renewal, migration, and differentiation of neurons. It is not surprising that many neurodevelopmental problems and neurodegenerative disorders are caused by deficiencies in cytoskeleton-related genes. For this reason, we focus on the cytoskeletal dynamics in proliferating iPSCs and in iPSC-derived neurons to better characterize the underpinnings of cytoskeletal organization looking at actin and tubulin repolymerization studies using the cell permeable probes SiR-Actin and SiR-Tubulin. During neurogenesis, each neuron extends an axon in a complex and changing environment to reach its final target. The dynamic behavior of the growth cone and its capacity to respond to multiple spatial information allows it to find its correct target. We decided to characterize various parameters of the actin filaments and microtubules. Our results suggest that a rapid re-organization of the cytoskeleton occurs 45 minutes after treatments with de-polymerizing agents in iPSCs and 60 minutes in iPSC-derived neurons in both actin filaments and microtubules. The quantitative data confirm that the actin filaments have a primary role in the re-organization of the cytoskeleton soon after de-polymerization, while microtubules have a major function following cytoskeletal stabilization. In conclusion, we investigate the possibility that de-polymerization of the actin filaments may have an impact on microtubules organization and that de-polymerization of the microtubules may affect the stability of the actin filaments. Our results suggest that a reciprocal influence of the actin filaments occurs over the microtubules and vice versa in both in iPSCs and iPSC-derived neurons. PMID:29340040

Modelling droplet collision outcomes for different substances and viscosities

NASA Astrophysics Data System (ADS)

Sommerfeld, Martin; Kuschel, Matthias

2016-12-01

The main objective of the present study is the derivation of models describing the outcome of binary droplet collisions for a wide range of dynamic viscosities in the well-known collision maps (i.e. normalised lateral droplet displacement at collision, called impact parameter, versus collision Weber number). Previous studies by Kuschel and Sommerfeld (Exp Fluids 54:1440, 2013) for different solution droplets having a range of solids contents and hence dynamic viscosities (here between 1 and 60 mPa s) revealed that the locations of the triple point (i.e. coincidence of bouncing, stretching separation and coalescence) and the critical Weber number (i.e. condition for the transition from coalescence to separation for head-on collisions) show a clear dependence on dynamic viscosity. In order to extend these findings also to pure liquids and to provide a broader data basis for modelling the viscosity effect, additional binary collision experiments were conducted for different alcohols (viscosity range 1.2-15.9 mPa s) and the FVA1 reference oil at different temperatures (viscosity range 3.0-28.2 mPa s). The droplet size for the series of alcohols was around 365 and 385 µm for the FVA1 reference oil, in each case with fixed diameter ratio at Δ= 1. The relative velocity between the droplets was varied in the range 0.5-3.5 m/s, yielding maximum Weber numbers of around 180. Individual binary droplet collisions with defined conditions were generated by two droplet chains each produced by vibrating orifice droplet generators. For recording droplet motion and the binary collision process with good spatial and temporal resolution high-speed shadow imaging was employed. The results for varied relative velocity and impact angle were assembled in impact parameter-Weber number maps. With increasing dynamic viscosity a characteristic displacement of the regimes for the different collision scenarios was also observed for pure liquids similar to that observed for solutions. This

New Accurate Oscillator Strengths and Electron Excitation Collision Strengths for N I

NASA Astrophysics Data System (ADS)

Tayal, S. S.

2006-03-01

The nonorthogonal orbitals technique in a multiconfiguration Hartree-Fock approach is used to calculate oscillator strengths and transition probabilities of N I lines. The relativistic effects are allowed by means of Breit-Pauli operators. The length and velocity forms of oscillator strengths show good agreement for most transitions. The B-spline R-matrix with pseudostates approach has been used to calculate electron excitation collision strengths and rates. The nonorthogonal orbitals are used for an accurate description of both target wave functions and the R-matrix basis functions. The 24 spectroscopic bound and autoionizing states together with 15 pseudostates are included in the close-coupling expansion. The collision strengths for transitions between fine-structure levels are calculated by transforming the LS-coupled K-matrices to K-matrices in an intermediate coupling scheme. Thermally averaged collision strengths have been determined by integrating collision strengths over a Maxwellian distribution of electron energies over a temperature range suitable for the modeling of astrophysical plasmas. The oscillator strengths and thermally averaged collision strengths are presented for transitions between the fine-structure levels of the 2s22p3 4So, 2Do, 2Po, 2s2p4 4P, 2s22p23s 4P, and 2P terms and from these levels to the levels of the 2s22p23p 2So, 4Do, 4Po, 4So, 2Do, 2Po, 2s22p23s 2D, 2s22p24s 4P, 2P, 2s22p23d 2P, 4F, 2F, 4P, 4D, and 2D terms. Thermally averaged collision strengths are tabulated over a temperature range from 500 to 50,000 K.

Polymeric Materials With Additives for Durability and Radiation Shielding in Space

NASA Technical Reports Server (NTRS)

Kiefer, Richard

2011-01-01

Polymeric materials are attractive for use in space structures because of their light weight and high strength In addition, polymers are made of elements with low atomic numbers (Z), primarily carbon (C), hydrogen (H), oxygen (0), and nitrogen (N) which provide the best shielding from galactic cosmic rays (GCR) (ref. 1). Galactic cosmic rays are composed primarily of nuclei (i.e., fully ionized atoms) plus a contribution of about 2% from electrons and positrons. There is a small but significant component of GCR particles with high charge (Z > 10) and high energy (E >100 GeV) (ref. 2). These so-called HZE particles comprise only 1 to 2% of the cosmic ray fluence but they interact with very high specific ionization and contribute 50% of the long- term dose to humans. The best shield for this radiation would be liquid hydrogen, which is not feasible. For this reason, hydrogen-containing polymers make the most effective practical shields. Moreover, neutrons are formed in the interactions of GCR particles with materials. Neutrons can only lose energy by collisions or reactions with a nucleus since they are uncharged. This is a process that is much less probable than the Coulombic interactions of charged particles. Thus, neutrons migrate far from the site of the reaction in which they were formed. This increases the probability of neutrons reaching humans or electronic equipment. Fast neutrons (> 1 MeV) can interact with silicon chips in electronic equipment resulting in the production of recoil ions which can cause single event upsets (SEU) in sensitive components (ref. 3). Neutrons lose energy most effectively by elastic collisions with light atoms, particularly hydrogen atoms. Therefore, hydrogen-containing polymers are not only effective in interacting with GCR particles; they are also effective in reducing the energy of the neutrons formed in the interactions.

Surface NH2-rich nanoparticles: Solidifying ionic-liquid electrolytes and improving the performance of dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Fang, Yanyan; Ma, Pin; Fu, Nianqing; Zhou, Xiaowen; Fang, Shibi; Lin, Yuan

2017-12-01

The surface properties of nanoparticles have a significant influence on the properties of the gel electrolytes. Herein, the surface NH2-rich nanoparticle (A-SiO2), with a tightening network, is synthesized by silanizing SiO2 nanoparticles with pre-polymerized aminopropyltriethoxysilane, which is further employed to prepare ionic-liquid gel electrolytes for dye-sensitized solar cells. The addition of a small amount of A-SiO2 can effectively solidify the ionic-liquid, whereas a large number of NH2 groups on the SiO2 surface leads to a large negative shift of the TiO2 conduction band edge, and can react with I3- in the form of a Lewis complex, resulting in an increase in the concentration of I- and a decrease in the concentration of I3- in the electrolyte. In addition, the ionic-liquid gel electrolyte possesses thixotropic behavior, which allows it to easily penetrate into the inner part of the TiO2 mesoporous film. As a result, large improvements of the photovoltage from 695 mV to 785 mV and of the photocurrent from 13.3 mA cm-2 to 14.9 mA cm-2 are achieved. This leads to significant enhancement of the power conversion efficiency, from 6.2% to 8.1%, for the cell with A-SiO2 compared to that of the pristine ionic-liquid electrolyte.

Production of monodisperse, polymeric microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Rhim, Won-Kyu (Inventor); Hyson, Michael T. (Inventor); Chang, Manchium (Inventor)

1990-01-01

Very small, individual polymeric microspheres with very precise size and a wide variation in monomer type and properties are produced by deploying a precisely formed liquid monomer droplet, suitably an acrylic compound such as hydroxyethyl methacrylate into a containerless environment. The droplet which assumes a spheroid shape is subjected to polymerizing radiation such as ultraviolet or gamma radiation as it travels through the environment. Polymeric microspheres having precise diameters varying no more than plus or minus 5 percent from an average size are recovered. Many types of fillers including magnetic fillers may be dispersed in the liquid droplet.

Poly(1-Vinyl-1,2,4-triazolium) Poly(Ionic Liquid)s: Synthesis and the Unique Behavior in Loading Metal Ions.

PubMed

Zhang, Weiyi; Yuan, Jiayin

2016-07-01

Herein, the synthesis of a series of poly(4-alkyl-1-vinyl-1,2,4-triazolium) poly(ionic liquid)s is reported either via straightforward free radical polymerization of their corresponding ionic liquid monomers or via anion metathesis of the polymer precursors bearing halide as counter anion. The ionic liquid monomers are first prepared via N-alkylation reaction of commercially available 1-vinyl-1,2,4-triazole with alkyl iodides, followed by anion metathesis with targeted fluorinated anions. The thermal properties and solubilities of these poly(ionic liquid)s have been systematically investigated. Interestingly, it is found that the poly(4-ethyl-1-vinyl-1,2,4-triazolium) poly(ionic liquid) exhibited an improved loading capacity of transition metal ions in comparison with its imidazolium counterpart. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymeric ionic liquid based on magnetic materials fabricated through layer-by-layer assembly as adsorbents for extraction of pesticides.

PubMed

He, Lijun; Cui, Wenhang; Wang, Yali; Zhao, Wenjie; Xiang, Guoqiang; Jiang, Xiuming; Mao, Pu; He, Juan; Zhang, Shusheng

2017-11-03

In this study, layer-by-layer assembly of polyelectrolyte multilayer films on magnetic silica provided a convenient and controllable way to prepare polymeric ionic liquid-based magnetic adsorbents. The resulting particles were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, and magnetic measurements. The data showed that the magnetic particles had more homogeneous spherical shapes with higher saturation magnetization when compared to those obtained by free radical polymerization method. This facilitated the convenient collection of magnetic particles, with higher extraction repeatability. The extraction performance of the multilayer polymeric ionic liquid-based adsorbents was evaluated by magnetic solid-phase extraction of four pesticides including quinalphos, fenthion, phoxim, and chlorpropham. The data suggested that the extraction efficiency depended on the number of layers in the film. The parameters affecting the extraction efficiency were optimized, and good linearity ranging from 2 to 250μgL -1 was obtained with correlation coefficients of 0.9994-0.9998. Moreover, the proposed method presented low limit of detection (0.5μgL -1 , S/N=3) and limit of quantification (1.5μgL -1 , S/N=10), and good repeatability expressed by the relative standard deviation (2.0%-4.6%, n=5). The extraction recoveries of four pesticides were found to range from 58.9% to 85.8%. The reliability of the proposed method was demonstrated by analyzing environmental water samples, and the results revealed satisfactory spiked recovery, relative standard deviation, and selectivity. Copyright © 2017 Elsevier B.V. All rights reserved.

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation.

PubMed

Chopade, Sujay A; Anderson, Evan L; Schmidt, Peter W; Lodge, Timothy P; Hillmyer, Marc A; Bühlmann, Philippe

2017-10-27

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.

The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes.

PubMed

Akhmetshina, Alsu A; Davletbaeva, Ilsiya M; Grebenschikova, Ekaterina S; Sazanova, Tatyana S; Petukhov, Anton N; Atlaskin, Artem A; Razov, Evgeny N; Zaripov, Ilnaz I; Martins, Carla F; Neves, Luísa A; Vorotyntsev, Ilya V

2015-12-30

Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf₂N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested for He, N₂, NH₃, H₂S, and CO₂ gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF₆] and [emim][Tf₂N]. The modification of SILMs by nanosize silica particles leads to an increase of NH₃ separation relatively to CO₂ or H₂S.

LC-MS/MS analysis of uncommon paracetamol metabolites derived through in vitro polymerization and nitration reactions in liquid nitrogen.

PubMed

Trettin, Arne; Jordan, Jens; Tsikas, Dimitrios

2014-09-01

Paracetamol (acetaminophen, APAP) is a commonly used analgesic drug. Known paracetamol metabolites include the glucuronide, sulfate and mercapturate. N-Acetyl-benzoquinonimine (NAPQI) is considered the toxic intermediate metabolite of paracetamol. In vitro and in vivo studies indicate that paracetamol is also metabolized to additional poorly characterized metabolites. For example, metabolomic studies in urine samples of APAP-treated mice revealed metabolites such as APAP-sulfate-APAP and APAP-S-S-APAP in addition to the classical phase II metabolites. Here, we report on the development and application of LC-MS and LC-MS/MS approaches to study reactions of unlabelled and (2)H-labelled APAP with unlabelled and (15)N-labelled nitrite in aqueous phosphate buffers (pH 7.4) upon their immersion into liquid nitrogen (-196°C). In mechanistic studies, these reactions were also studied in aqueous buffer prepared in (18)O-labelled water. LC-MS and LC-MS/MS analyses were performed on a reverse-phase material (C18) using gradient elution (2mM ammonium acetate/acetonitrile), in positive and negative electrospray mode. We identified a series of APAP metabolites including di-, tri- and tetra-APAP, mono- and di-nitro-APAP and nitric ester of di-APAP. Our study indicates that nitrite induces oxidation, i.e., polymerization and nitration of APAP, when buffered APAP/nitrite solutions are immersed into liquid nitrogen. These reactions are specific for nitrite with respect to nitrate and do not proceed via intermediate formation of NAPQI. Potassium ions and physiological saline but not thiols inhibit nitrite- and shock-freeze-induced reactions of paracetamol. The underlying mechanism likely involves in situ formation of NO2 radicals from nitrite secondary to profound pH reduction (down to pH 1) and disproportionation. Polymeric paracetamol species can be analyzed as pentafluorobenzyl derivatives by LC-MS but not by GC-MS. Copyright © 2013 Elsevier B.V. All rights reserved.

Ultrafast preparation of a polyhedral oligomeric silsesquioxane-based ionic liquid hybrid monolith via photoinitiated polymerization, and its application to capillary electrochromatography of aromatic compounds.

PubMed

Zhang, Bingyu; Lei, Xiaoyun; Deng, Lijun; Li, Minsheng; Yao, Sicong; Wu, Xiaoping

2018-06-06

An ionic liquid hybrid monolithic capillary column was prepared within 7 min via photoinitiated free-radical polymerization of an ionic liquid monomer (1-butyl-3-vinylimidazolium-bis[(trifluoromethyl)sulfonyl]imide); VBIMNTF 2 ) and a methacryl substituted polyhedral oligomeric silsesquioxane (POSS-MA) acting as a cross-linker. The effects of composition of prepolymerization solution and initiation time on the porous structure and electroosmotic flow (EOF) of monolithic column were investigated. The hybrid monolith was characterized by scanning electron microscopy and FTIR. Owing to the introduction of a rigid nanosized POSS silica core and ionic liquids with multiple interaction sites, the monolithic column has a well-defined 3D skeleton morphology, good mechanical stability, and a stable anodic electroosmotic flow. The hybrid monolithic stationary phase was applied to the capillary electrochromatographic separation of various alkylbenzenes, phenols, anilines and polycyclic aromatic hydrocarbons (PAHs). The column efficiency is highest (98,000 plates/m) in case of alkylbenzenes. Mixed-mode retention mechanisms including hydrophobic interactions, π-π stacking, electrostatic interaction and electrophoretic mobility can be observed. This indicates the potential of this material in terms of efficient separation of analytes of different structural type. Graphical Abstract Preparation of a mixed-mode ionic liquid hybrid monolithic column via photoinitiated polymerization of methacryl substituted polyhedral oligomeric silsesquioxane (POSS-MA) and 1-butyl-3-vinylimidazolium-bis[(trifluoromethyl)sulfonyl]imide (VBIMNTF 2 ) ionic liquid for use in capillary electrochromatography.

Graphene oxide reinforced polymeric ionic liquid monolith solid-phase microextraction sorbent for high-performance liquid chromatography analysis of phenolic compounds in aqueous environmental samples.

PubMed

Sun, Min; Bu, Yanan; Feng, Juanjuan; Luo, Chuannan

2016-01-01

A graphene oxide reinforced polymeric ionic liquids monolith was obtained by copolymerization of graphene oxide doped 1-(3-aminopropyl)-3-(4-vinylbenzyl)imidazolium 4-styrenesulfonate monomer and 1,6-di-(3-vinylimidazolium) hexane bihexafluorophosphate cross-linking agent. Coupled to high-performance liquid chromatography, the monolith was used as a solid-phase microextraction sorbent to analyze several phenolic compounds in aqueous samples. Under the optimized extraction and desorption conditions, linear ranges were 5-400 μg/L for 3-nitrophenol, 2-nitrophenol, and 2,5-dichlorophenol and 2-400 μg/L for 4-chlorophenol, 2-methylphenol, and 2,4,6-trichlorophenol (R(2) = 0.9973-0.9988). The limits of detection were 0.5 μg/L for 3-nitrophenol and 2-nitrophenol and 0.2 μg/L for the rest of the analytes. The proposed method was used to determine target analytes in groundwater from an industrial park and river water. None of the analytes was detected. Relative recoveries were in the range of 75.5-113%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A recyclable and reusable supported Cu(I) catalyzed azide-alkyne click polymerization

NASA Astrophysics Data System (ADS)

Wu, Haiqiang; Li, Hongkun; Kwok, Ryan T. K.; Zhao, Engui; Sun, Jing Zhi; Qin, Anjun; Tang, Ben Zhong

2014-05-01

The azide-alkyne click polymerization (AACP) has emerged as a powerful tool for the synthesis of functional polytriazoles. While, for the Cu(I)-catalyzed AACP, the removal of the catalytic Cu(I) species from the resulting polytriazoles is difficult, and the research on the recyclability and reusability of the catalyst remains intact. Herein, we reported the first example of using recyclable and reusable supported Cu(I) catalyst of CuI@A-21 for the AACP. CuI@A-21 could not only efficiently catalyze the AACP but also be reused for at least 4 cycles. Moreover, pronounced reduction of copper residues in the products was achieved. Apart from being a green and cost-effective polymer synthesis strategy, this method will also broaden the application of AACP in material and biological sciences and provide guidelines for other polymerizations with metal catalysts.

Quantum state-resolved energy transfer dynamics at gas-liquid interfaces: IR laser studies of CO2 scattering from perfluorinated liquids.

PubMed

Perkins, Bradford G; Häber, Thomas; Nesbitt, David J

2005-09-01

An apparatus for detailed study of quantum state-resolved inelastic energy transfer dynamics at the gas-liquid interface is described. The approach relies on supersonic jet-cooled molecular beams impinging on a continuously renewable liquid surface in a vacuum and exploits sub-Doppler high-resolution laser absorption methods to probe rotational, vibrational, and translational distributions in the scattered flux. First results are presented for skimmed beams of jet-cooled CO(2) (T(beam) approximately 15 K) colliding at normal incidence with a liquid perfluoropolyether (PFPE) surface at E(inc) = 10.6(8) kcal/mol. The experiment uses a tunable Pb-salt diode laser for direct absorption on the CO(2) nu(3) asymmetric stretch. Measured rotational distributions in both 00(0)0 and 01(1)0 vibrational manifolds indicate CO(2) inelastically scatters from the liquid surface into a clearly non-Boltzmann distribution, revealing nonequilibrium dynamics with average rotational energies in excess of the liquid (T(s) = 300 K). Furthermore, high-resolution analysis of the absorption profiles reveals that Doppler widths correspond to temperatures significantly warmer than T(s) and increase systematically with the J rotational state. These rotational and translational distributions are consistent with two distinct gas-liquid collision pathways: (i) a T approximately 300 K component due to trapping-desorption (TD) and (ii) a much hotter distribution (T approximately 750 K) due to "prompt" impulsive scattering (IS) from the gas-liquid interface. By way of contrast, vibrational populations in the CO(2) bending mode are inefficiently excited by scattering from the liquid, presumably reflecting much slower T-V collisional energy transfer rates.

Preparation of stir cake sorptive extraction based on polymeric ionic liquid for the enrichment of benzimidazole anthelmintics in water, honey and milk samples.

PubMed

Wang, Yulei; Zhang, Jie; Huang, Xiaojia; Yuan, Dongxing

2014-08-20

In this work, a new stir cake sorptive extraction (SCSE) using polymeric ionic liquid monolith as sorbent was prepared. The sorbent was obtained by in situ copolymerization of an ionic liquid, 1-allyl-3-methylimidazolium bis[(trifluoro methyl)sulfonyl]imide (AMII) and divinylbenzene (DB) in the presence of N,N-dimethylformamide. The influence of the content of ionic liquid and the porogen in the polymerization mixture on extraction performance was studied thoroughly. The physicochemical properties of the polymeric ionic liquid were characterized by infrared spectroscopy, elemental analysis, scanning electron microscopy and mercury intrusion porosimetry. The usefulness of SCSE-AMIIDB was demonstrated by the enrichment of trace benzimidazole anthelmintics. Several parameters affecting the extraction efficiency were investigated, and under the optimized conditions, a simple and effective method for the determination of trace benzimidazoles residues in water, milk and honey samples was established by coupling SCSE-AMIIDB with high performance liquid chromatography/diode array detection (SCSE-AMIIDB-HPLC/DAD). Results indicated that the limits of detection (S/N=3) for target compounds were 0.020-0.072 μg L(-1), 0.035-0.10 μg L(-1) and 0.026-0.076 μg L(-1) in water, milk and honey samples, respectively. In addition, an acceptable reproducibility was achieved by evaluating the repeatability and intermediate precision with relative standard deviations (RSD) of less than 9% and 11%, respectively. Finally, the established AMII-SCSE-HPLC/DAD method was successfully applied for the determination of benzimidazoles residues in milk, honey and environmental water samples. Recoveries obtained for the determination of benzimidazole anthelmintics in spiking samples ranged from 70.2% to 117.6%, with RSD below 12% in all cases. Copyright © 2014 Elsevier B.V. All rights reserved.

An Experimental Examination of Combustion of Isolated Liquid Fuel Droplets with Polymeric and Nanoparticle Additives

NASA Astrophysics Data System (ADS)

Ghamari, Mohsen

In spite of recent attention to renewable sources of energy, liquid hydrocarbon fuels are still the main source of energy for industrial and transportation systems. Manufactures and consumers are consistently looking for ways to optimize the efficiency of fuel combustion in terms of cost, emissions and consumer safety. In this regard, increasing burning rate of liquid fuels has been of special interest in both industrial and transportation systems. Recent studies have shown that adding combustible nano-particles could have promising effects on improving combustion performance of liquid fuels. Combustible nano-particles could enhance radiative and conductive heat transfer and also mixing within the droplet. Polymeric additive have also shown promising effect on improving fire safety by suppressing spreading behavior and splatter formation in case of crash scenario. Polymers are also known to have higher burning rate than regular hydrocarbon fuels. Therefore adding polymeric additive could have the potential to increase the burning rate. In this work, combustion dynamics of liquid fuel droplets with both polymeric and nanoparticle additives is studied in normal gravity. High speed photography is employed and the effect of additive concentration on droplet burning rate, burning time, extinction and soot morphology is investigated. Polymer added fuel was found to have a volatility controlled combustion with four distinct regimes. The first three zones are associated with combustion of base fuel while the polymer burns last and after a heating zone because of its higher boiling point. Polymer addition reduces the burning rate of the base fuel in the first zone by means of increasing viscosity and results in nucleate boiling and increased burning rates in the second and third stages. Overall, polymer addition resulted in a higher burning rate and shorter burning time in most of the scenarios. Colloidal suspensions of carbon-based nanomaterials in liquid fuels were also

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chopade, Sujay A.; Anderson, Evan L.; Schmidt, Peter W.

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethylmore » sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.« less

Kinetics of bulk photo-initiated copper(i)-catalyzed azide-alkyne cycloaddition (CuAAC) polymerizations.

PubMed

Song, Han Byul; Baranek, Austin; Bowman, Christopher N

2016-01-21

Photoinitiation of polymerizations based on the copper(i)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction enables spatio-temporal control and the formation of mechanically robust, highly glassy photopolymers. Here, we investigated several critical factors influencing photo-CuAAC polymerization kinetics via systematic variation of reaction conditions such as the physicochemical nature of the monomers; the copper salt and photoinitiator types and concentrations; light intensity; exposure time and solvent content. Real time Fourier transform infrared spectroscopy (FTIR) was used to monitor the polymerization kinetics in situ . Six different di-functional azide monomers and four different tri-functional alkyne monomers containing either aliphatic, aromatic, ether and/or carbamate substituents were synthesized and polymerized. Replacing carbamate structures with ether moieties in the monomers enabled an increase in conversion from 65% to 90% under similar irradiation conditions. The carbamate results in stiffer monomers and higher viscosity mixtures indicating that chain mobility and diffusion are key factors that determine the CuAAC network formation kinetics. Photoinitiation rates were manipulated by altering various aspects of the photo-reduction step; ultimately, a loading above 3 mol% per functional group for both the copper catalyst and the photoinitiator showed little or no rate dependence on concentration while a loading below 3 mol% exhibited 1 st order rate dependence. Furthermore, a photoinitiating system consisting of camphorquinone resulted in 60% conversion in the dark after only 1 minute of 75 mW cm -2 light exposure at 400-500 nm, highlighting a unique characteristic of the CuAAC photopolymerization enabled by the combination of the copper(i)'s catalytic lifetime and the nature of the step-growth polymerization.

Phosphines bearing alkyne substituents: synthesis and hydrophosphination polymerization.

PubMed

Greenberg, Sharonna; Stephan, Douglas W

2009-09-07

A synthetic route is described for a series of phosphines bearing pendant alkyne substituents, from the conversion of BrC(6)H(2)R(2)C[triple bond]CR' (R = Me, i-Pr; R' = Ph, SiMe(3)) to [(mu-Br)Cu(Et(2)N)(2)PC(6)H(2)R(2)C[triple bond]CR'](2) and subsequently to Cl(2)PC(6)H(2)R(2)C[triple bond]CR' and H(2)PC(6)H(2)R(2)C[triple bond]CR'. Lithiation and subsequent alkylation yield the secondary phosphines R(H)PC(6)H(2)(i-Pr)(2)C[triple bond]CPh (R = CH(2)i-Pr, CH(2)Ph). Intermolecular hydrophosphination-polymerization is used to prepare the polymeric species [RPC(6)H(2)(i-Pr)(2)CH=CPh](n), which can then be sulfurized to give [RP(S)C(6)H(2)(i-Pr)(2)CH=CPh](n). The polymeric products were characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and gel permeation chromatography. These data indicate a degree of polymerization (DP(n)) of up to 60. Discussion of the mechanism is augmented with gas-phase density functional theory calculations.

Comparison of Plasma Polymerization under Collisional and Collision-Less Pressure Regimes.

PubMed

Saboohi, Solmaz; Jasieniak, Marek; Coad, Bryan R; Griesser, Hans J; Short, Robert D; Michelmore, Andrew

2015-12-10

While plasma polymerization is used extensively to fabricate functionalized surfaces, the processes leading to plasma polymer growth are not yet completely understood. Thus, reproducing processes in different reactors has remained problematic, which hinders industrial uptake and research progress. Here we examine the crucial role pressure plays in the physical and chemical processes in the plasma phase, in interactions at surfaces in contact with the plasma phase, and how this affects the chemistry of the resulting plasma polymer films using ethanol as the gas precursor. Visual inspection of the plasma reveals a change from intense homogeneous plasma at low pressure to lower intensity bulk plasma at high pressure, but with increased intensity near the walls of the chamber. It is demonstrated that this occurs at the transition from a collision-less to a collisional plasma sheath, which in turn increases ion and energy flux to surfaces at constant RF power. Surface analysis of the resulting plasma polymer films show that increasing the pressure results in increased incorporation of oxygen and lower cross-linking, parameters which are critical to film performance. These results and insights help to explain the considerable differences in plasma polymer properties observed by different research groups using nominally similar processes.

Intelligent Local Avoided Collision (iLAC) MAC Protocol for Very High Speed Wireless Network

NASA Astrophysics Data System (ADS)

Hieu, Dinh Chi; Masuda, Akeo; Rabarijaona, Verotiana Hanitriniala; Shimamoto, Shigeru

Future wireless communication systems aim at very high data rates. As the medium access control (MAC) protocol plays the central role in determining the overall performance of the wireless system, designing a suitable MAC protocol is critical to fully exploit the benefit of high speed transmission that the physical layer (PHY) offers. In the latest 802.11n standard [2], the problem of long overhead has been addressed adequately but the issue of excessive colliding transmissions, especially in congested situation, remains untouched. The procedure of setting the backoff value is the heart of the 802.11 distributed coordination function (DCF) to avoid collision in which each station makes its own decision on how to avoid collision in the next transmission. However, collision avoidance is a problem that can not be solved by a single station. In this paper, we introduce a new MAC protocol called Intelligent Local Avoided Collision (iLAC) that redefines individual rationality in choosing the backoff counter value to avoid a colliding transmission. The distinguishing feature of iLAC is that it fundamentally changes this decision making process from collision avoidance to collaborative collision prevention. As a result, stations can avoid colliding transmissions with much greater precision. Analytical solution confirms the validity of this proposal and simulation results show that the proposed algorithm outperforms the conventional algorithms by a large margin.

Self-Assembled Polymeric Ionic Liquid-Functionalized Cellulose Nano-crystals: Constructing 3D Ion-conducting Channels Within Ionic Liquid-based Composite Polymer Electrolytes.

PubMed

Shi, Qing Xuan; Xia, Qing; Xiang, Xiao; Ye, Yun Sheng; Peng, Hai Yan; Xue, Zhi Gang; Xie, Xiao Lin; Mai, Yiu-Wing

2017-09-04

Composite polymeric and ionic liquid (IL) electrolytes are some of the most promising electrolyte systems for safer battery technology. Although much effort has been directed towards enhancing the transport properties of polymer electrolytes (PEs) through nanoscopic modification by incorporating nano-fillers, it is still difficult to construct ideal ion conducting networks. Here, a novel class of three-dimensional self-assembled polymeric ionic liquid (PIL)-functionalized cellulose nano-crystals (CNC) confining ILs in surface-grafted PIL polymer chains, able to form colloidal crystal polymer electrolytes (CCPE), is reported. The high-strength CNC nano-fibers, decorated with PIL polymer chains, can spontaneously form three-dimensional interpenetrating nano-network scaffolds capable of supporting electrolytes with continuously connected ion conducting networks with IL being concentrated in conducting domains. These new CCPE have exceptional ionic conductivities, low activation energies (close to bulk IL electrolyte with dissolved Li salt), high Li + transport numbers, low interface resistances and improved interface compatibilities. Furthermore, the CCPE displays good electrochemical properties and a good battery performance. This approach offers a route to leak-free, non-flammable and high ionic conductivity solid-state PE in energy conversion devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A New Route for High-Purity Organic Materials: High-Pressure-Ramp-Induced Ultrafast Polymerization of 2-(Hydroxyethyl)Methacrylate

NASA Astrophysics Data System (ADS)

Evlyukhin, E.; Museur, L.; Traore, M.; Perruchot, C.; Zerr, A.; Kanaev, A.

2015-12-01

The synthesis of highly biocompatible polymers is important for modern biotechnologies and medicine. Here, we report a unique process based on a two-step high-pressure ramp (HPR) for the ultrafast and efficient bulk polymerization of 2-(hydroxyethyl)methacrylate (HEMA) at room temperature without photo- and thermal activation or addition of initiator. The HEMA monomers are first activated during the compression step but their reactivity is hindered by the dense glass-like environment. The rapid polymerization occurs in only the second step upon decompression to the liquid state. The conversion yield was found to exceed 90% in the recovered samples. The gel permeation chromatography evidences the overriding role of HEMA2•• biradicals in the polymerization mechanism. The HPR process extends the application field of HP-induced polymerization, beyond the family of crystallized monomers considered up today. It is also an appealing alternative to typical photo- or thermal activation, allowing the efficient synthesis of highly pure organic materials.

Effects of Monomer Structure on Their Organization and Polymerization in a Smectic Liquid Crystal

PubMed

Guymon; Hoggan; Clark; Rieker; Walba; Bowman

1997-01-03

Photopolymerizable diacrylate monomers dissolved in fluid-layer smectic A and smectic C liquid crystal (LC) hosts exhibited significant spatial segregation and orientation that depend strongly on monomer structure. Small, flexible monomers such as 1,6-hexanediol diacrylate (HDDA) oriented parallel to the smectic layers and intercalated, whereas rod-shaped mesogen-like monomers such as 1,4-di-(4-(6-acryloyloxyhexyloxy)benzoyloxy)-2-methylbenzene (C6M) oriented normal to the smectic layers and collected within them. Such spatial segregation caused by the smectic layering dramatically enhanced photopolymerization rates; for HDDA, termination rates were reduced, whereas for C6M, both the termination and propagation rates were increased. These polymerization precursor structures suggest novel materials-design paradigms for gel LCs and nanophase-separated polymer systems.

Synthesis of thermo-responsive bovine hemoglobin imprinted nanoparticles by combining ionic liquid immobilization with aqueous precipitation polymerization.

PubMed

Wang, Yongmei; Yang, Chongchong; Sun, Yan; Qiu, Fengtao; Xiang, Yang; Fu, Guoqi

2018-02-01

Surface molecular imprinting over functionalized nanoparticles has proved to be an effective approach for construction of artificial nanomaterials for protein recognition. Herein, we report a strategy for synthesis of core-shell protein-imprinted nanoparticles by the functionalization of nano-cores with ionic liquids followed by aqueous precipitation polymerization to build thermo-responsive imprinted polymer nano-shells. The immobilized ionic liquids can form multiple interactions with the protein template. The polymerization process can produce thermo-reversible physical crosslinks, which are advantageous to enhancing imprinting and facilitating template removal. With bovine hemoglobin as a model template, the imprinted nanoparticles showed temperature-sensitivity in both dispersion behaviors and rebinding capacities. Compared with the ionic-liquid-modified core nanoparticles, the imprinted particles exhibited greatly increased selectivity and two orders of magnitude higher binding affinity for the template protein. The imprinted nanoparticles achieved relatively high imprinting factor up to 5.0 and specific rebinding capacity of 67.7 mg/g, respectively. These nanoparticles also demonstrated rapid rebinding kinetics and good reproducibility after five cycles of adsorption-regeneration. Therefore, the presented approach may be viable for the fabrication of high-performance protein-imprinted nanoparticles with temperature sensitivity. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dopamine Polymerization in Liquid Marbles: A General Route to Janus Particle Synthesis.

PubMed

Sheng, Yifeng; Sun, Guanqing; Ngai, To

2016-04-05

Coating a liquid with a particle shell not only renders a droplet superhydrophobic but also isolates a well-confined microenvironment for miniaturized chemical processes. Previously, we have demonstrated that particles at the liquid marble interface provide an ideal platform for the site-selective modification of superhydrophobic particles. However, the need for a special chemical reaction limits their potential use for the fabrication of Janus particles with various properties. Herein, we combine the employment of liquid marbles as microreactors with the remarkable adhesive ability of polydopamine to develop a general route for the synthesis of Janus particles from micrometer-sized superhydrophobic particles. We demonstrate that dopamine polymerization and deposition inside liquid marbles could be used for the selective surface modification of microsized silica particles, resulting in the formation of Janus particles. Moreover, it is possible to manipulate the Janus balance of the particles via the addition of surfactants and/or organic solvents to tune the interfacial energy. More importantly, owing to the many functional groups in polydopamine, we show that versatile strategies could be introduced to use these partially polydopamine-coated silica particles as platforms for further modification, including nanoparticle immobilization, metal ion chelation and reduction, as well as for chemical reactions. Given the flexibility in the choice of cores and the modification strategies, this developed method is distinctive in its high universality, good controllability, and great practicability.

30 CFR 250.1162 - When may I burn produced liquid hydrocarbons?

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 2 2012-07-01 2012-07-01 false When may I burn produced liquid hydrocarbons... Gas Production Requirements Flaring, Venting, and Burning Hydrocarbons § 250.1162 When may I burn... burn any produced liquid hydrocarbons. The Regional Supervisor may allow you to burn liquid...

30 CFR 250.1162 - When may I burn produced liquid hydrocarbons?

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 2 2014-07-01 2014-07-01 false When may I burn produced liquid hydrocarbons... Gas Production Requirements Flaring, Venting, and Burning Hydrocarbons § 250.1162 When may I burn... burn any produced liquid hydrocarbons. The Regional Supervisor may allow you to burn liquid...

30 CFR 250.1162 - When may I burn produced liquid hydrocarbons?

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 2 2013-07-01 2013-07-01 false When may I burn produced liquid hydrocarbons... Gas Production Requirements Flaring, Venting, and Burning Hydrocarbons § 250.1162 When may I burn... burn any produced liquid hydrocarbons. The Regional Supervisor may allow you to burn liquid...

Polymeric ionic liquid coatings versus commercial solid-phase microextraction coatings for the determination of volatile compounds in cheeses.

PubMed

Trujillo-Rodríguez, María J; Yu, Honglian; Cole, William T S; Ho, Tien D; Pino, Verónica; Anderson, Jared L; Afonso, Ana M

2014-04-01

The extraction performance of four polymeric ionic liquid (PIL)-based solid-phase microextraction (SPME) coatings has been studied and compared to that of commercial SPME coatings for the extraction of 16 volatile compounds in cheeses. The analytes include 2 free fatty acids, 2 aldehydes, 2 ketones and 10 phenols and were determined by headspace (HS)-SPME coupled to gas chromatography (GC) with flame-ionization detection (FID). The PIL-based coatings produced by UV co-polymerization were more efficient than PIL-based coatings produced by thermal AIBN polymerization. Partition coefficients of analytes between the sample and the coating (Kfs) were estimated for all PIL-based coatings and the commercial SPME fiber showing the best performance among the commercial fibers tested: carboxen-polydimethylsyloxane (CAR-PDMS). For the PIL-based fibers, the highest K(fs) value (1.96 ± 0.03) was obtained for eugenol. The normalized calibration slope, which takes into account the SPME coating thickness, was also used as a simpler approximate tool to compare the nature of the coating within the determinations, with results entirely comparable to those obtained with estimated K(fs) values. The PIL-based materials obtained by UV co-polymerization containing the 1-vinyl-3-hexylimidazolium chloride IL monomer and 1,12-di(3-vinylimiazolium)dodecane dibromide IL crosslinker exhibited the best performance in the extraction of the select analytes from cheeses. Despite a coating thickness of only 7 µm, this copolymeric sorbent coating was capable of quantitating analytes in HS-SPME in a 30 to 2000 µg L(-1) concentration range, with correlation coefficient (R) values higher than 0.9938, inter-day precision values (as relative standard deviation in %) varying from 6.1 to 20%, and detection limits down to 1.6 µg L(-1). Copyright © 2013 Elsevier B.V. All rights reserved.

30 CFR 250.1162 - When may I burn produced liquid hydrocarbons?

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 2 2010-07-01 2010-07-01 false When may I burn produced liquid hydrocarbons... Requirements Flaring, Venting, and Burning Hydrocarbons § 250.1162 When may I burn produced liquid hydrocarbons... hydrocarbons. The Regional Supervisor may allow you to burn liquid hydrocarbons if you demonstrate that...

Quaternized polymeric microgels as metal free catalyst for H2 production from the methanolysis of sodium borohydride

NASA Astrophysics Data System (ADS)

Sahiner, Nurettin; Sengel, Sultan Butun

2016-12-01

Polymeric microgels derived from tris(2-amino ethyl)amine (TAEA) and glycerol diglycidyl ether as p(TAEA-co-GDE) via microemulsion polymerization techniques are protonated by 0.5 M HCl treatment as p(TAEA-co-GDE)-HCl). These microgels are then exposed to anion exchange reactions with differ ionic liquid forming salts, such as potassium thiocyanate (PTC), sodium dicyanamide (SDCA), ammonium hexafluorophosphate (AHFP), and sodium tetrafluoroborate (STFB) in aqueous medium for the preparation of p(TAEA-co-GDE) based ionic liquid colloidal microgels. These anions exchanged p(TAEA-co-GDE) ionic liquid colloids (ILCs) are directly used as catalyst for hydrogen (H2) generation from the methanol solution of sodium borohydride (NaBH4). Various parameters affecting the H2 production rate such as the catalyst types, NaBH4 amount, and the temperature are investigated. It is found that the methanolysis of NaBH4 catalyzed by p(TAEA-co-GDE)-HCl obeys the first order reaction kinetic. The activation energy, enthalpy and entropy of the protonated p(TAEA-co-GDE) microgels are calculated and found as the 30.37 kJ mol-1, 27.96 kJ mol-1, and -148.08 J mol-1 K-1, respectively. Furthermore, the hydrogen generation rate of 3018 mL min-1 g-1 catalyzed by p(TAEA-co-GDE)-HCl catalyst is attained.

I. Direct observation of zirconocene-catalyzed alkene polymerization via NMR and the role of an aluminum alkyl during polymerization. II. Design and evaluation of an online nanoscience course for teachers

NASA Astrophysics Data System (ADS)

Tomasik, Janice Hall

The plastics industry has been revolutionalized by development of group 4 metallocene polymerization catalysts. These catalysts have higher activities and stereoselectivities than traditional heterogeneous Ziegler-Natta polymerization catalysts, and produce polymers with narrower molecular weight distributions and with better control of the polymer stereochemistry. The reaction kinetics of catalytic alkene polymerizations are complicated and difficult to resolve macroscopically. To overcome these difficulties, research has used NMR spectroscopy to directly observe catalytic reaction intermediates; many advances in our understanding of the complex mechanisms behind these polymerization reactions have resulted. In this work, the direct observation of alkene insertion into zirconocene-polymeryls via NMR spectroscopy is presented. Alkenes studied are 3-methylpentene, styrene, and 1,4-pentadiene. Kinetic measurements are reported for the polymerization of 3-methylpentene by rac-(EBI)Zr(Me)(MeB(C6F 5)3) (EBI = C2H4(1-indenyl)2) and rac-(EBI)Zr(polyhexenyl)(MeB(C6F5) 3). Also presented are NMR spectroscopic characterizations of rac-(EBI)Zr(styrenyl)(MeB(C6F5)3) and rac-(EBI)Zr(1,4-pentadienyl)(MeB(C6F 5)3). In addition, NMR spectroscopy is used to directly monitor the behavior of an aluminum alkyl during the polymerization of 1-hexene by rac -(EBI)2Zr(Me)(MeB(C6F5)3). The rates of polymerization are not inhibited by Al(iBu) 2(BHT), Al(Me)(BHT)2, or Al(iBu)3 (BHT = 2,6-di- tert-butyl-4-methylphenyl). Detailed measurement of polymerization rate and catalyst speciation demonstrate that BHT modified aluminum alkyls protect active sites from decomposition in the presence of protic impurities such as methanol. Also presented in this work is the design and evaluation of an online course for teachers about nanoscience. Nanotechnology is an important emerging field that is estimated to need about 2 million workers worldwide by 2015. Therefore the educational system is being

Multifunctional Iodide-Free Polymeric Ionic Liquid for Quasi-Solid-State Dye-Sensitized Solar Cells with a High Open-Circuit Voltage.

PubMed

Lin, Yi-Feng; Li, Chun-Ting; Lee, Chuan-Pei; Leu, Yow-An; Ezhumalai, Yamuna; Vittal, R; Chen, Ming-Chou; Lin, Jiang-Jen; Ho, Kuo-Chuan

2016-06-22

A polymeric ionic liquid, poly(oxyethylene)-imide-imidazolium selenocyanate (POEI-IS), was newly synthesized and used for a multifunctional gel electrolyte in a quasi-solid-state dye-sensitized solar cell (QSS-DSSC). POEI-IS has several functions: (a) acts as a gelling agent for the electrolyte of the DSSC, (b) possesses a redox mediator of SeCN(-), which is aimed to form a SeCN(-)/(SeCN)3(-) redox couple with a more positive redox potential than that of traditional I(-)/I3(-), (c) chelates the potassium cations through the lone pair electrons of the oxygen atoms of its poly(oxyethylene)-imide-imidazolium (POEI-I) segments, and (d) obstructs the recombination of photoinjected electrons with (SeCN)3(-) ions in the electrolyte through its POEI-I segments. Thus, the POEI-IS renders a high open-circuit voltage (VOC) to the QSS-DSSC due to its functions of b-d and prolongs the stability of the cell due to its function of a. The QSS-DSSC with the gel electrolyte containing 30 wt % of the POEI-IS in liquid selenocyanate electrolyte exhibited a high VOC of 825.50 ± 3.51 mV and a high power conversion efficiency (η) of 8.18 ± 0.02%. The QSS-DSSC with 30 wt % POEI-IS retained up to 95% of its initial η after an at-rest stability test with the period of more than 1,000 h.

Coherent X-ray diffraction imaging of nanoengineered polymeric capsules

NASA Astrophysics Data System (ADS)

Erokhina, S.; Pastorino, L.; Di Lisa, D.; Kiiamov, A. G.; Faizullina, A. R.; Tayurskii, D. A.; Iannotta, S.; Erokhin, V.

2017-10-01

For the first time, nanoengineered polymeric capsules and their architecture have been studied with coherent X-ray diffraction imaging technique. The use of coherent X-ray diffraction imaging technique allowed us to analyze the samples immersed in a liquid. We report about the significant difference between polymeric capsule architectures under dry and liquid conditions.

Preparation a new sorbent based on polymeric ionic liquid for stir cake sorptive extraction of organic compounds and inorganic anions.

PubMed

Huang, Xiaojia; Wang, Yulei; Hong, Qiuyun; Liu, Yi; Yuan, Dongxing

2013-11-01

A new multi-interaction sorbent (MIS) based on polymeric ionic liquid was prepared and used as extractive medium of stir cake sorptive extraction (SCSE). In the presence of dimethyl sulfoxide, an ionic liquid, 1-vinylbenzyl-3-methylimidazolium chloride was used as monomer to copolymerize in situ with divinylbenzene to form the MIS. The influences of the content of monomer and the porogen solvent in the polymerization mixture on the extraction performance were investigated thoroughly. The MIS was characterized by infrared spectroscopy, elemental analysis, scanning electron microscopy and mercury intrusion porosimetry. Parabens and aromatic amines were used to investigate the extraction performance of MIS-SCSE for apolar and strongly polar analytes, respectively. The extraction parameters for parabens and aromatic amines were optimized. At the same time, simple and sensitive analytical methods for parabens and aromatic amines in real samples were developed by the combination of MIS-SCSE and HPLC/DAD. Some inorganic anions, such as F(-), Br(-), NO3(-), PO4(3-) and SO4(2-), were used to test the extraction performance of MIS-SCSE for anions. Results indicated that mechanism involved in the extraction of MIS is the multi-interaction modes including π-π, hydrophobic, hydrogen-bonding, dipole-dipole and anion-exchange interactions. Copyright © 2013 Elsevier B.V. All rights reserved.

Removal of radioactive contaminants by polymeric microspheres.

PubMed

Osmanlioglu, Ahmet Erdal

2016-11-01

Radionuclide removal from radioactive liquid waste by adsorption on polymeric microspheres is the latest application of polymers in waste management. Polymeric microspheres have significant immobilization capacity for ionic substances. A laboratory study was carried out by using poly(N-isopropylacrylamide) for encapsulation of radionuclide in the liquid radioactive waste. There are numbers of advantages to use an encapsulation technology in radioactive waste management. Results show that polymerization step of radionuclide increases integrity of solidified waste form. Test results showed that adding the appropriate polymer into the liquid waste at an appropriate pH and temperature level, radionuclide was encapsulated into polymer. This technology may provide barriers between hazardous radioactive ions and the environment. By this method, solidification techniques became easier and safer in nuclear waste management. By using polymer microspheres as dust form, contamination risks were decreased in the nuclear industry and radioactive waste operations.

Pressure-induced structural change in liquid GeI4.

PubMed

Fuchizaki, Kazuhiro; Nishimura, Hironori; Hase, Takaki; Saitoh, Hiroyuki

2017-12-27

The similarity in the shape of the melting curve of GeI 4 to that of SnI 4 suggests that a liquid-liquid transition as observed in liquid SnI 4 is also expected to occur in liquid GeI 4 . Because the slope of the melting curve of GeI 4 abruptly changes at around 3 GPa, in situ synchrotron diffraction measurements were conducted to examine closely the structural changes upon compression at around 3 GPa. The reduced radial distribution functions of the high- and low-pressure liquid states of GeI 4 share the same feature inherent in the high-pressure (high-density) and low-pressure (low-density) radial distribution functions of liquid SnI 4 . This feature allows us to introduce local order parameters that we may use to observe the transition. Unlike the transition in liquid SnI 4 , the transition from the low-pressure to the high-pressure structure seems sluggish. We speculate that the liquid-liquid critical point of GeI 4 is no longer a thermodynamically stable state and is slightly located below the melting curve. As a result, the structural change is said to be a crossover rather than a transition. The behavior of the local-order parameters implies a metastable extension of the liquid-liquid phase boundary with a negative slope.

Determination of volatile polycyclic aromatic hydrocarbons in waters using headspace solid-phase microextraction with a benzyl-functionalized crosslinked polymeric ionic liquid coating.

PubMed

Merdivan, Melek; Pino, Verónica; Anderson, Jared L

2017-08-01

A benzyl-functionalized crosslinked polymeric ionic liquid (PIL), produced through the co-polymerization of the 1-vinylbenzyl-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide (VBHDIM-NTf 2 ) ionic liquid (IL) monomer and 1,12-di(3-vinylbenzylimidazolium)dodecane bis[(trifluoromethyl)sulfonyl]imide ((DVBIM) 2 C 12- 2NTf 2 ) IL crosslinker, was successfully used as a sorbent coating in headspace solid-phase microextraction (SPME) coupled to gas chromatography (GC) with flame-ionization detection (FID) to determine seven volatile polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. Optimum extraction conditions for the PAHs when using the novel sorbent include an extraction temperature of 50°C, an ionic strength content adjusted with 30% (w/v) NaCl in the aqueous sample, and an extraction time of 60 min. The extraction performance of the crosslinked PIL fiber was compared to the SPME commercial coating polydimethylsiloxane fiber. The calibration ranges of the studied PAHs were linear in the range of 0.02-20 µg L -1 for the crosslinked PIL fiber. The accuracy of the proposed method was demonstrated by examining the spiked recoveries of seven PAHs which produced values ranging from 67.2% to 130% (for river- and seawater samples), and precision values lower than 9.4% for a spiked level of 1 µg L -1 , and detection limits between 0.01 and 0.04 µg L -1 , which supports the sensitivity of the method using GC-FID.

A polymeric liquid membrane electrode responsive to 3,3',5,5'-tetramethylbenzidine oxidation for sensitive peroxidase/peroxidase mimetic-based potentiometric biosensing.

PubMed

Wang, Xuewei; Yang, Yangang; Li, Long; Sun, Mingshuang; Yin, Haogen; Qin, Wei

2014-05-06

The oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) has great utility in bioanalysis such as peroxidase/peroxidase mimetic-based biosensing. In this paper, the behaviors of TMB oxidation intermediates/products in liquid/liquid biphasic systems have been investigated for the first time. The free radical, charge transfer complex, and diimine species generated by TMB oxidation are all positively charged under acidic and near-neutral conditions. Electron paramagnetic resonance and visible absorbance spectroscopy data demonstrate that these cationic species can be effectively transferred from an aqueous phase into a water-immiscible liquid phase functionalized by an appropriate cation exchanger. Accordingly, sensitive potential responses of TMB oxidation have been obtained on a cation exchanger-doped polymeric liquid membrane electrode under mildly acidic and near-neutral conditions. By using the membrane electrode responsive to TMB oxidations, two sensitive potentiometric biosensing schemes including the peroxidase-labeled sandwich immunoassay and G-quadruplex DNAzyme-based DNA hybridization assay have been developed. The obtained detection limits for the target antigen and DNA are 0.02 ng/mL and 0.1 nM, respectively. Coupled with other advantages such as low cost, high reliability, and ease of miniaturization and integration, the proposed polymeric liquid membrane electrode holds great promise as a facile and efficient transducer for TMB oxidation and related biosensing applications.

Carprofen-imprinted monolith prepared by reversible addition-fragmentation chain transfer polymerization in room temperature ionic liquids.

PubMed

Ban, Lu; Han, Xu; Wang, Xian-Hua; Huang, Yan-Ping; Liu, Zhao-Sheng

2013-10-01

To obtain fast separation, ionic liquids were used as porogens first in combination with reversible addition-fragmentation chain transfer (RAFT) polymerization to prepare a new type of molecularly imprinted polymer (MIP) monolith. The imprinted monolithic column was synthesized using a mixture of carprofen (template), 4-vinylpyridine, ethylene glycol dimethacrylate, [BMIM]BF4, and chain transfer agent (CTA). Some polymerization factors, such as template-monomer molar ratio, the degree of crosslinking, the composition of the porogen, and the content of CTA, on the column efficiency and imprinting effect of the resulting MIP monolith were systematically investigated. Affinity screening of structurally similar compounds with the template can be achieved in 200 s on the MIP monolith due to high column efficiency (up to 12,070 plates/m) and good column permeability. Recognition mechanism of the imprinted monolith was also investigated.

Melting line of polymeric nitrogen

NASA Astrophysics Data System (ADS)

Yakub, L. N.

2013-05-01

We made an attempt to predict location of the melting line of polymeric nitrogen using two equations for Helmholtz free energy: proposed earlier for cubic gauche-structure and developed recently for liquid polymerized nitrogen. The P-T relation, orthobaric densities and latent heat of melting were determined using a standard double tangent construction. The estimated melting temperature decreases with increasing pressure, alike the temperature of molecular-nonmolecular transition in solid. We discuss the possibility of a triple point (solid-molecular fluid-polymeric fluid) at ˜80 GPa and observed maximum of melting temperature of nitrogen.

Sensitive determination of estrogens in environmental waters treated with polymeric ionic liquid-based stir cake sorptive extraction and liquid chromatographic analysis.

PubMed

Chen, Lei; Mei, Meng; Huang, Xiaojia; Yuan, Dongxing

2016-05-15

A simple, sensitive and environmentally friendly method using polymeric ionic liquid-based stir cake sorptive extraction followed by high performance liquid chromatography with diode array detection (HPLC/DAD) has been developed for efficient quantification of six selected estrogens in environmental waters. To extract trace estrogens effectively, a poly (1-ally-3-vinylimidazolium chloride-co-ethylene dimethacrylate) monolithic cake was prepared and used as the sorbent of stir cake sorptive extraction (SCSE). The effects of preparation conditions of sorbent and extraction parameters of SCSE for estrogens were investigated and optimized. Under optimal conditions, the developed method showed satisfactory analytical performance for targeted analytes. Low limits of detection (S/N=3) and quantification limits (S/N=10) were achieved within the range of 0.024-0.057 µg/L and 0.08-0.19 µg/L, respectively. Good linearity of method was obtained for analytes with the correlation coefficients (R(2)) above 0.99. At the same time, satisfactory method repeatability and reproducibility was achieved in terms of intra- and inter-day precisions, respectively. Finally, the established SCSE-HPLC/DAD method was successfully applied for the determination of estrogens in different environmental water samples. Recoveries obtained for the determination of estrogens in spiked samples ranged from 71.2% to 108%, with RSDs below 10% in all cases. Copyright © 2016 Elsevier B.V. All rights reserved.

Anionic polymerization of p-(2,2'-diphenylethyl)styrene and applications to graft copolymers.

PubMed

Huang, Minglu; Han, Bingyong; Lu, Jianmin; Yang, Wantai; Fu, Zhifeng

2017-01-01

Well-controlled anionic polymerization of an initiator-functionalized monomer, p -(2,2'-diphenylethyl)styrene (DPES), was achieved for the first time. The polymerization was performed in a mixed solvent of cyclohexane and tetrahydrofuran (THF) at 40 °C with n -BuLi as initiator. When the volume ratio of cyclohexane to THF was 20, the anionic polymerization of DPES showed living polymerization characteristics, and well-defined block copolymer PDPES- b -PS was successfully synthesized. Furthermore, radical polymerization of methyl methacrylate in the presence of PDPES effectively afforded a graft copolymer composed of a polystyrene backbone and poly(methyl methacrylate) branches. The designation of analogous monomers and polymers was of great significance to synthesize a variety of sophisticated copolymer and functionalize polymer materials.

AsS melt under pressure: one substance, three liquids.

PubMed

Brazhkin, V V; Katayama, Y; Kondrin, M V; Hattori, T; Lyapin, A G; Saitoh, H

2008-04-11

An in situ high-temperature--high-pressure study of liquid chalcogenide AsS by x-ray diffraction, resistivity measurements, and quenching from melt is presented. The obtained data provide direct evidence for the existence in the melt under compression of two transformations: one is from a moderate-viscosity molecular liquid to a high-viscosity nonmetallic polymerized liquid at P approximately 1.6-2.2 GPa; the other is from the latter to a low-viscosity metallic liquid at P approximately 4.6-4.8 GPa. Upon rapid cooling, molecular and metallic liquids crystallize to normal and high-pressure phases, respectively, while a polymerized liquid is easily quenched to a new AsS glass. General aspects of multiple phase transitions in liquid AsS, including relations to the phase diagram of the respective crystalline, are discussed.

Free Radical Polymerization of Styrene: A Radiotracer Experiment

ERIC Educational Resources Information Center

Mazza, R. J.

1975-01-01

Describes an experiment designed to acquaint the chemistry student with polymerization reactions, vacuum techniques, liquid scintillation counting, gas-liquid chromatography, and the handling of radioactive materials. (MLH)

Obtention of injectable platelets rich-fibrin (i-PRF) and its polymerization with bone graft: technical note.

PubMed

Mourão, Carlos Fernando de Almeida Barros; Valiense, Helder; Melo, Elias Rodrigues; Mourão, Natália Belmock Mascarenhas Freitas; Maia, Mônica Diuana-Calasans

2015-01-01

The use of autologous platelet concentrates, represent a promising and innovator tools in the medicine and dentistry today. The goal is to accelerate hard and soft tissue healing. Among them, the platelet-rich plasma (PRP) is the main alternative for use in liquid form (injectable). These injectable form of platelet concentrates are often used in regenerative procedures and demonstrate good results. The aim of this study is to present an alternative to these platelet concentrates using the platelet-rich fibrin in liquid form (injectable) and its use with particulated bone graft materials in the polymerized form.

30 CFR 250.1162 - When may I burn produced liquid hydrocarbons?

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 2 2011-07-01 2011-07-01 false When may I burn produced liquid hydrocarbons... SHELF Oil and Gas Production Requirements Flaring, Venting, and Burning Hydrocarbons § 250.1162 When may I burn produced liquid hydrocarbons? (a) You must request and receive approval from the Regional...

Radical Polymerization of Diene Hydrocarbons in a Presence of Peroxide of Hydrogen and Solvent. 1. Effectiveness of Initiation and Rate of Expansion H2O2 during Oligomerization in Metallic Equipment

DTIC Science & Technology

1990-04-10

the hydroxyl groups. These are liquid oligobutadienes of brand R-15M and R-45M (firm "Sinclair Retgochemical Suc."/OSA) [5, 6, 10] and hydroxyl... ionic mechanism. Most promising, in view of simplicity and cheapness, is considered the I DOC - 90010000 PAGE - method of the radical polymerization of...Initiators of polimerization in this method are the hydroxyl radicals, which are generated during the homolytic decomposition of peroxide of hydrogen PDO

Development, optimisation and application of polyurethane foams as new polymeric phases for stir bar sorptive extraction.

PubMed

Neng, N R; Pinto, M L; Pires, J; Marcos, P M; Nogueira, J M F

2007-11-09

In this contribution, polyurethane foams are proposed as new polymeric phases for stir bar sorptive extraction (SBSE). Assays performed for polyurethane synthesis demonstrated that four series of formulations (P(1), P(2), P(3) and P(4)) present remarkable stability and excellent mechanical resistance to organic solvents. For polymer clean-up treatment, acetonitrile proved to be the best solvent under sonification, ensuring the reduction of the contamination and interferences. SBSE assays performed on these polyurethane polymers followed by liquid desorption and high-performance liquid chromatography-diode array detection (LD-HPLC-DAD) or large volume injection-capillary gas chromatography-mass spectrometry (LD-LVI-GC-MS), showed that P(2) presents the best recovery yields for atrazine, 2,3,4,5-tetrachlorophenol and fluorene, used as model compounds in water samples at a trace level. SBSE(P(2)) assays performed on this polymer mixed up with several adsorbent materials, i.e. activated carbon, a mesoporous material and a calixarene, did not bring any advantages in relation with the polymeric matrix alone. The comparison between assays performed by SBSE(P(2)) and by the conventional SBSE(PDMS) showed much better performance for the former phase on aqueous samples spiked with atrazine, 2,3,4,5-tetrachlorophenol and fluorene, in which the foremost two analytes present recovery values 3- and 10-fold higher, respectively. The polyurethanes proposed as new polymeric phases for SBSE provided powerful capabilities for the enrichment of organic compounds from aqueous matrices, showing to be indicated mainly in the case of the more polar analytes.

Equilibrium polymerization models of re-entrant self-assembly

NASA Astrophysics Data System (ADS)

Dudowicz, Jacek; Douglas, Jack F.; Freed, Karl F.

2009-04-01

As is well known, liquid-liquid phase separation can occur either upon heating or cooling, corresponding to lower and upper critical solution phase boundaries, respectively. Likewise, self-assembly transitions from a monomeric state to an organized polymeric state can proceed either upon increasing or decreasing temperature, and the concentration dependent ordering temperature is correspondingly called the "floor" or "ceiling" temperature. Motivated by the fact that some phase separating systems exhibit closed loop phase boundaries with two critical points, the present paper analyzes self-assembly analogs of re-entrant phase separation, i.e., re-entrant self-assembly. In particular, re-entrant self-assembly transitions are demonstrated to arise in thermally activated equilibrium self-assembling systems, when thermal activation is more favorable than chain propagation, and in equilibrium self-assembly near an adsorbing boundary where strong competition exists between adsorption and self-assembly. Apparently, the competition between interactions or equilibria generally underlies re-entrant behavior in both liquid-liquid phase separation and self-assembly transitions.

Nanocomposites Based on Luminescent Colloidal Nanocrystals and Polymeric Ionic Liquids towards Optoelectronic Applications

PubMed Central

Panniello, Annamaria; Ingrosso, Chiara; Coupillaud, Paul; Tamborra, Michela; Binetti, Enrico; Curri, Maria Lucia; Agostiano, Angela; Taton, Daniel; Striccoli, Marinella

2014-01-01

Polymeric ionic liquids (PILs) are an interesting class of polyelectrolytes, merging peculiar physical-chemical features of ionic liquids with the flexibility, mechanical stability and processability typical of polymers. The combination of PILs with colloidal semiconducting nanocrystals leads to novel nanocomposite materials with high potential for batteries and solar cells. We report the synthesis and properties of a hybrid nanocomposite made of colloidal luminescent CdSe nanocrystals incorporated in a novel ex situ synthesized imidazolium-based PIL, namely, either a poly(N-vinyl-3-butylimidazolium hexafluorophosphate) or a homologous PIL functionalized with a thiol end-group exhibiting a chemical affinity with the nanocrystal surface. A capping exchange procedure has been implemented for replacing the pristine organic capping molecules of the colloidal CdSe nanocrystals with inorganic chalcogenide ions, aiming to disperse the nano-objects in the PILs, by using a common polar solvent. The as-prepared nanocomposites have been studied by TEM investigation, UV-Vis, steady-state and time resolved photoluminescence spectroscopy for elucidating the effects of the PIL functionalization on the morphological and optical properties of the nanocomposites. PMID:28788477

Angle-resolved molecular beam scattering of NO at the gas-liquid interface

NASA Astrophysics Data System (ADS)

Zutz, Amelia; Nesbitt, David J.

2017-08-01

This study presents first results on angle-resolved, inelastic collision dynamics of thermal and hyperthermal molecular beams of NO at gas-liquid interfaces. Specifically, a collimated incident beam of supersonically cooled NO (2 Π 1/2, J = 0.5) is directed toward a series of low vapor pressure liquid surfaces ([bmim][Tf2N], squalane, and PFPE) at θinc = 45(1)°, with the scattered molecules detected with quantum state resolution over a series of final angles (θs = -60°, -30°, 0°, 30°, 45°, and 60°) via spatially filtered laser induced fluorescence. At low collision energies [Einc = 2.7(9) kcal/mol], the angle-resolved quantum state distributions reveal (i) cos(θs) probabilities for the scattered NO and (ii) electronic/rotational temperatures independent of final angle (θs), in support of a simple physical picture of angle independent sticking coefficients and all incident NO thermally accommodating on the surface. However, the observed electronic/rotational temperatures for NO scattering reveal cooling below the surface temperature (Telec < Trot < TS) for all three liquids, indicating a significant dependence of the sticking coefficient on NO internal quantum state. Angle-resolved scattering at high collision energies [Einc = 20(2) kcal/mol] has also been explored, for which the NO scattering populations reveal angle-dependent dynamical branching between thermal desorption and impulsive scattering (IS) pathways that depend strongly on θs. Characterization of the data in terms of the final angle, rotational state, spin-orbit electronic state, collision energy, and liquid permit new correlations to be revealed and investigated in detail. For example, the IS rotational distributions reveal an enhanced propensity for higher J/spin-orbit excited states scattered into near specular angles and thus hotter rotational/electronic distributions measured in the forward scattering direction. Even more surprisingly, the average NO scattering angle (�

Binary collision approximations for the memory function for density fluctuations in equilibrium atomic liquids

NASA Astrophysics Data System (ADS)

Noah, Joyce E.

Time correlation functions of density fluctuations of liquids at equilibrium can be used to relate the microscopic dynamics of a liquid to its macroscopic transport properties. Time correlation functions are especially useful since they can be generated in a variety of ways, from scattering experiments to computer simulation to analytic theory. The kinetic theory of fluctuations in equilibrium liquids is an analytic theory for calculating correlation functions using memory functions. In this work, we use a diagrammatic formulation of the kinetic theory to develop a series of binary collision approximations for the collisional part of the memory function. We define binary collisions as collisions between two distinct density fluctuations whose identities are fixed during the duration of a collsion. R approximations are for the short time part of the memory function, and build upon the work of Ranganathan and Andersen. These approximations have purely repulsive interactions between the fluctuations. The second type of approximation, RA approximations, is for the longer time part of the memory function, where the density fluctuations now interact via repulsive and attractive forces. Although RA approximations are a natural extension of R approximations, they permit two density fluctuations to become trapped in the wells of the interaction potential, leading to long-lived oscillatory behavior, which is unphysical. Therefore we consider S approximations which describe binary particles which experience the random effect of the surroundings while interacting via repulsive or repulsive and attractive interactions. For each of these approximations for the memory function we numerically solve the kinetic equation to generate correlation functions. These results are compared to molecular dynamics results for the correlation functions. Comparing the successes and failures of the different approximations, we conclude that R approximations give more accurate intermediate and

Heterodinuclear titanium/zinc catalysis: synthesis, characterization and activity for CO2/epoxide copolymerization and cyclic ester polymerization.

PubMed

Garden, Jennifer A; White, Andrew J P; Williams, Charlotte K

2017-02-21

The preparation of heterodinuclear complexes, especially those comprising early-late transition metals coordinated by a simple or symmetrical ancillary ligand, represents a fundamental challenge and an opportunity to prepare catalysts benefitting from synergic properties. Here, two new mixed titanium(iv)-zinc(ii) complexes, [LTi(O i Pr) 2 ZnEt] and [LTi(O i Pr) 2 ZnPh], both coordinated by a diphenolate tetra(amine) macrocyclic ligand (L), are prepared. The synthesis benefits from the discovery that reaction of the ligand with a single equivalent of titanium tetrakis(iso-propoxide) allows the efficient formation of a mono-Ti(iv) complex, [LTi(O i Pr) 2 ]. All new complexes are characterized by a combination of single crystal X-ray diffraction, multinuclear NMR spectroscopy and mass spectrometry techniques. The two heterobimetallic complexes, [LTi(O i Pr) 2 ZnEt] and [LTi(O i Pr) 2 ZnPh], feature trianionic coordination by the macrocyclic ligand and bridging alkoxide groups coordinate to both the different metal centres. The heterodinuclear catalysts are compared to the mono-titanium analogue, [LTi(O i Pr) 2 ], in various polymerization reactions. In the alternating copolymerizations of carbon dioxide and cyclohexene oxide, the mono-titanium complex is totally inactive whilst the heterodinuclear complexes show moderate activity (TOF = 3 h -1 ); it should be noted the activity is measured using just 1 bar pressure of carbon dioxide. In the ring opening polymerization of lactide and ε-caprolactone, the mono-Ti(iv) complex is totally inactive whilst the heterodinuclear complexes show moderate-high activities, qualified by comparison to other known titanium polymerization catalysts (l-lactide, k obs = 11 × 10 -4 s -1 at 70 °C, 1 M in [lactide]) and ε-caprolactone (k obs = 5 × 10 -4 s -1 at 70 °C, 0.9 M in [ε-caprolactone]).

Ionic Liquids as a Medium for Ionic Chain Polymerizations: An Environmentally Responsible Approach to Macromolecular Synthesis with Controlled Architecture

DTIC Science & Technology

2004-09-16

published in non peer-reviewed journals: 1. Gross, SM, Hamilton JL. "Polymer Gels for Use in Lithium Polymer Batteries", Nebraska Academy of Science...a process for the anionic polymerization of styrene and methyl methacrylate in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ...Current polymer electrolyte composites used for these applications typically comprise polyethers with ethylene carbonate solvents containing lithium

Liquid Crystals in Chromatography

NASA Astrophysics Data System (ADS)

Witkiewicz, Zygfryd

The following sections are included: * INTRODUCTION * LIQUID CRYSTALS SUITABLE FOR GAS CHROMATOGRAPHY * Monomeric Liquid Crystal Stationary Phases * Polymeric Liquid Crystal Stationary Phases * Polymeric Liquid Crystal Stationary Phases * Conventional Analytical Columns * Capillary Columns * FACTORS AFFECTING THE CHROMATOGRAPHIC SEPARATIONS ON LIQUID CRYSTAL STATIONARY PHASES * Kind of Mesophase of the Liquid Crystal * Molecular Structure of the Liquid Crystals and of the Chromatographed Substances * Substrate on which the Liquid Crystal is Deposited * ANALYTICAL APPLICATIONS OF LIQUID CRYSTAL STATIONARY PHASES IN GAS CHROMATOGRAPHY * Separation of Isomers of Benzene and Naphthalene Derivatives * Separation of Alkane and Alkene Isomers * Separation of Mixtures of Benzene and Aliphatic Hydrocarbon Derivatives Containing Heteroatoms * Separation of Polynuclear Hydrocarbons * INVESTIGATION OF THE PROPERTIES OF LIQUID CRYSTALS BY GAS CHROMATOGRAPHY * APPLICATION OF LIQUID CRYSTALS IN LIQUID CHROMATOGRAPHY * Column Chromatography * Thin-Layer Chromatography * APPLICATION OF LIQUID CRYSTAL STATIONARY PHASES IN SUPERCRITICAL FLUID CHROMATOGRAPHY * FINAL REMARKS * References

Molecularly imprinted electrochemical sensing interface based on in-situ-polymerization of amino-functionalized ionic liquid for specific recognition of bovine serum albumin.

PubMed

Wang, Yanying; Han, Miao; Liu, Guishen; Hou, Xiaodong; Huang, Yina; Wu, Kangbing; Li, Chunya

2015-12-15

A molecularly imprinted polymer film was in situ polymerized on a carboxyl functionalized multi-walled carbon nanotubes modified glassy carbon electrode surface under room temperature. This technique provides a promising imprinting approach for protein in an aqueous solution using 3-(3-aminopropyl)-1-vinylimidazolium tetrafluoroborate ionic liquid as functional monomer, N, N'-methylenebisacrylamide as crossing linker, ammonium persulfate and N,N,N',N'-tetramethylethylenediamine as initiator, and bovine serum albumin (BSA) as template. The molecularly imprinted polymerized ionic liquid film shows enhanced accessibility, high specificity and sensitivity towards BSA. Electrochemical sensing performance of the imprinted sensor was thoroughly investigated using K3Fe[CN]6/K4Fe[CN]6 as electroactive probes. Under optimal conditions, the current difference before and after specific recognition of BSA was found linearly related to its concentration in the range from 1.50×10(-9) to 1.50×10(-6) mol L(-1). The detection limit was calculated to be 3.91×10(-10) mol L(-1) (S/N=3). The practical application of the imprinted sensor was demonstrated by determining BSA in liquid milk samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Dual functions of imidazole-based polymeric ionic liquid (PIL) on the anticorrosive performance of graphene-based waterborne epoxy coatings

NASA Astrophysics Data System (ADS)

Liu, Chengbao; Du, Peng; Nan, Feng; Zhao, Haichao; Wang, Liping

2018-06-01

Dispersion of graphene nanosheets in a water and polymer matrix has been rarely achieved due to graphene’s hydrophobicity, which thus impedes its potential anticorrosive application. In this study, stable graphene aqueous dispersion was obtained by using imidazole-based polymeric ionic liquid (PIL) as the dispersant with ultrasonic vibration. Stacked graphene sheets were exfoliated to a few layers via cation-π interaction between PIL and graphene nanosheets. Electrochemical impedance measurements were taken to investigate the anticorrosion performance of epoxy coatings with or without polymeric ionic liquid–graphene (PIL–G) hybrids. Results indicated that the PIL–G hybrid significantly enhanced the long-term protective performance of epoxy coatings, which was attributed to the synergistic effects of the corrosion-inhibitive PIL and impermeable graphene nanosheets.

O2-O2 and O2-N2 collision-induced absorption mechanisms unravelled

NASA Astrophysics Data System (ADS)

Karman, Tijs; Koenis, Mark A. J.; Banerjee, Agniva; Parker, David H.; Gordon, Iouli E.; van der Avoird, Ad; van der Zande, Wim J.; Groenenboom, Gerrit C.

2018-05-01

Collision-induced absorption is the phenomenon in which interactions between colliding molecules lead to absorption of light, even for transitions that are forbidden for the isolated molecules. Collision-induced absorption contributes to the atmospheric heat balance and is important for the electronic excitations of O2 that are used for remote sensing. Here, we present a theoretical study of five vibronic transitions in O2-O2 and O2-N2, using analytical models and numerical quantum scattering calculations. We unambiguously identify the underlying absorption mechanism, which is shown to depend explicitly on the collision partner—contrary to textbook knowledge. This explains experimentally observed qualitative differences between O2-O2 and O2-N2 collisions in the overall intensity, line shape and vibrational dependence of the absorption spectrum. It is shown that these results can be used to discriminate between conflicting experimental data and even to identify unphysical results, thus impacting future experimental studies and atmospheric applications.

Electron collisions with the HCOOH···(H2O)n complexes (n = 1, 2) in liquid phase: the influence of microsolvation on the π* resonance of formic acid.

PubMed

Freitas, T C; Coutinho, K; Varella, M T do N; Lima, M A P; Canuto, S; Bettega, M H F

2013-05-07

We report momentum transfer cross sections for elastic collisions of low-energy electrons with the HCOOH···(H2O)n complexes, with n = 1, 2, in liquid phase. The scattering cross sections were computed using the Schwinger multichannel method with pseudopotentials in the static-exchange and static-exchange plus polarization approximations, for energies ranging from 0.5 eV to 6 eV. We considered ten different structures of HCOOH···H2O and six structures of HCOOH···(H2O)2 which were generated using classical Monte Carlo simulations of formic acid in aqueous solution at normal conditions of temperature and pressure. The aim of this work is to investigate the influence of microsolvation on the π* shape resonance of formic acid. Previous theoretical and experimental studies reported a π* shape resonance for HCOOH at around 1.9 eV. This resonance can be either more stable or less stable in comparison to the isolated molecule depending on the complex structure and the water role played in the hydrogen bond interaction. This behavior is explained in terms of (i) the polarization of the formic acid molecule due to the water molecules and (ii) the net charge of the solute. The proton donor or acceptor character of the water molecules in the hydrogen bond is important for understanding the stabilization versus destabilization of the π* resonances in the complexes. Our results indicate that the surrounding water molecules may affect the lifetime of the π* resonance and hence the processes driven by this anion state, such as the dissociative electron attachment.

Monodisperse, polymeric microspheres produced by irradiation of slowly thawing frozen drops

NASA Technical Reports Server (NTRS)

Rhim, Won-Kyu (Inventor); Hyson, Michael T. (Inventor); Chung, Sang-Kun (Inventor); Colvin, Michael S. (Inventor); Chang, Manchium (Inventor)

1991-01-01

Monodisperse, polymeric microspheres are formed by injecting uniformly shaped droplets of radiation polymerizable monomers, preferably a biocompatible monomer, having covalent binding sites such as hydroxyethylmethacrylate, into a zone, impressing a like charge on the droplet so that they mutually repel each other, spheroidizing the droplets within the zone and collecting the droplets in a pool of cryogenic liquid. As the droplets enter the liquid, they freeze into solid, glassy microspheres, which vaporizes a portion of the cryogenic liquid to form a layer. The like-charged microspheres, suspended within the layer, move to the edge of the vessel holding the pool, are discharged, fall and are collected. The collected microspheres are irradiated while frozen in the cryogenic liquid to form latent free radicals. The frozen microspheres are then slowly thawed to activate the free radicals which polymerize the monomer to form evenly-sized, evenly-shaped, monodisperse polymeric microspheres.

Tuning preparation conditions towards optimized separation performance of thermally polymerized organo-silica monolithic columns in capillary liquid chromatography.

PubMed

Gharbharan, Deepa; Britsch, Denae; Soto, Gabriela; Weed, Anna-Marie Karen; Svec, Frantisek; Zajickova, Zuzana

2015-08-21

Tuning of preparation conditions, such as variations in the amount of a porogen, concentration of an aqueous acid catalyst, and adjustment in polymerization temperature and time, towards optimized chromatographic performance of thermally polymerized monolithic capillaries prepared from 3-(methacryloyloxy)propyltrimethoxysilane has been carried out. Performance of capillary columns in reversed-phase liquid chromatography was assessed utilizing various sets of solutes. Results describing hydrophobicity, steric selectivity, and extent of hydrogen bonding enabled comparison of performance of hybrid monolithic columns prepared under thermal (TSG) and photopolymerized (PSG) conditions. Reduced amounts of porogen in the polymerization mixture, and prolonged reaction times were necessary for the preparation of monolithic columns with enhanced retention and column efficiency that reached to 111,000 plates/m for alkylbenzenes with shorter alkyl chains. Both increased concentration of catalyst and higher temperature resulted in faster polymerization but inevitably in insufficient time for pore formation. Thermally polymerized monoliths produced surfaces, which were slightly more hydrophobic (a methylene selectivity of 1.28±0.002 TSG vs 1.20±0.002 PSG), with reduced number of residual silanols (a caffeine/phenol selectivity of 0.13±0.001 TSG vs 0.17±0.003 PSG). However, steric selectivity of 1.70±0.01 was the same for both types of columns. The batch-to-batch repeatability was better using thermal initiation compared to monolithic columns prepared under photopolymerized conditions. RSD for retention factor of benzene was 3.7% for TSG capillaries (n=42) vs. 6.6% for PSG capillaries (n=18). A similar trend was observed for columns prepared within the same batch. Copyright © 2015 Elsevier B.V. All rights reserved.

Molecular and mesoscopic study of ionic liquids and their use as solvents of active agents released by polymeric vehicles

NASA Astrophysics Data System (ADS)

Ramos-Rodríguez, Daniel-Apolinar; Rodríguez-Hidalgo, María-del-Rosario; Soto-Figueroa, César; Vicente, Luis

2010-03-01

This work explores the diffusivity of the drug albendazole contained in a polymeric vehicle, Styrene-Divinylbenzene (ST-DVD), when it is subject to different environments. The environments consist of water and three different ionic liquids. First, the solubility parameters of these ionic liquids, [BMIM][PF6], [HMIM][Br] and [BMIM][BF4], and albendazole were evaluated by means of molecular dynamics employing COMPASS force-field and a NPT ensemble at 298 K. Then a mesoscopic simulation using Dissipative Particle Dynamics (DPD) was used. In the presence of ionic liquids the albendazole exhibits a diffusivity in [BMIM][PF6] around ten times that shown in [BMIM][BF4] or [HMIM][Br]. This is connected with the corresponding solvent power. The results obtained from these molecular and mesoscopic simulations are consistent with reported experimental results and are useful to predict and evaluate the solvent power of ionic liquids applied to drugs of pharmaceutical use.

Lasing properties of polymerized chiral nematic Bragg onion microlasers.

PubMed

Humar, Matjaž; Araoka, Fumito; Takezoe, Hideo; Muševič, Igor

2016-08-22

Dye doped photocurable cholesteric liquid crystal was used to produce solid Bragg onion omnidirectional lasers. The lasers were produced by dispersing and polymerizing chiral nematic LC with parallel surface anchoring of LC molecules at the interface, extracted and transferred into another medium. Lasing characteristics were studied in carrier medium with different refractive index. The lasing in spherical cholesteric liquid crystal was attributed to two mechanisms, photonic bandedge lasing and lasing of whispering-gallery modes. The latter can be suppressed by using a higher index carrier fluid to prevent total internal reflection on the interface of the spheres. Pulse-to-pulse stability and threshold characteristics were also studied and compared to non-polymerized lasers. The polymerization process greatly increases the lasing stability.

Enhanced production of ψ (2 S ) mesons in heavy ion collisions

NASA Astrophysics Data System (ADS)

Cho, Sungtae

2015-05-01

I study the production of a ψ (2 S ) meson in heavy ion collisions. I evaluate Wigner functions for the ψ (2 S ) meson using both Gaussian and Coulomb wave functions, and investigate the wave function dependence in the ψ (2 S ) meson production by recombination of charm and anticharm quarks. The enhanced transverse momentum distribution of ψ (2 S ) mesons compared to that of J /ψ mesons, originated from wave function distributions of the ψ (2 S ) and J /ψ meson in momentum space, provides a plausible explanation for the recent measurement of the nuclear modification factor ratio between the ψ (2 S ) and J /ψ meson.

Beer Law Constants and Vapor Pressures of HgI2 over HgI2(s,l)

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Zhu, Shen; Ramachandran, N.; Burger, A.

2002-01-01

Optical absorption spectra of the vapor phase over HgI2(s,l) were measured at sample temperatures between 349 and 610 K for wavelengths between 200 and 600 nm. The spectra show the samples sublimed congruently into HGI2 without any observed Hg or I2 absorption spectra. The Beer's Law constants for 15 wavelengths between 200 and 440 nm were derived. From these constants the vapor pressure of HgI2, P, was found to be a function of temperature for the liquid and the solid beta-phases: ln P(atm) = -7700/T(K) + 12.462 (liquid phase) and ln P(atm) = -10150/T(K) + 17.026 (beta-phase). The expressions match the enthalpies of vaporization and sublimation of 15.30 and 20.17 kcal/mole respectively, for the liquid and the beta-phase HgI2. The difference in the enthalpies gives an enthalpy of fusion of 4.87 kcal/mole, and the intersection of the two expressions gives a melting point of 537 K.

Integration of CuAAC Polymerization and Controlled Radical Polymerization into Electron Transfer Mediated "Click-Radical" Concurrent Polymerization.

PubMed

Xue, Wentao; Wang, Jie; Wen, Ming; Chen, Gaojian; Zhang, Weidong

2017-03-01

The successful chain-growth copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization employing Cu(0)/pentamethyldiethylenetriamine (PMDETA) and alkyl halide as catalyst is first investigated by a combination of nuclear magnetic resonance, gel-permeation chromatography, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. In addition, the electron transfer mediated "click-radical" concurrent polymerization utilizing Cu(0)/PMDETA as catalyst is successfully employed to generate well-defined copolymers, where controlled CuAAC polymerization of clickable ester monomer is progressed in the main chain acting as the polymer backbone, the controlled radical polymerization (CRP) of acrylic monomer is carried out in the side chain. Furthermore, it is found that there is strong collaborative effect and compatibility between CRP and CuAAC polymerization to improve the controllability. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Soft x ray window encapsulant for HgI2 detectors

NASA Technical Reports Server (NTRS)

Entine, G.; Shah, K.; Squillante, M.

1987-01-01

HgI2 is an excellent semiconductor material for a low energy, room temperature x-ray spectrometer. The high values of the atomic numbers for its constituent elements gives high x-ray and gamma ray stopping power. The band gap of HgI2 is significantly higher than other commonly used semiconductors. Owing to the large value band gap, the leakage current for HgI2 devices is smaller, thus allowing low noise performance. Devices fabricated from HgI2 crystals have demonstrated energy resolution sufficient to distinguish the x-ray emission from the neighboring elements on the periodic table. Also the power requirements of HgI2 are very low. These characteristics make a HgI2 spectrometer an ideal component in a satellite based detection system. Unfortunately, HgI2 crystals tend to deteriorate with time, even if protected by standard semiconductor encapsulants. This degradation ruins the performance of the device in terms of its energy resolution and pulse amplitude. The degrading mechanism is believed to be material loss occurring from below the electrodes, due to high vapor pressure of HgI2 at room temperature. To address this major obstacle to rapid expansion of HgI2 technology, a research program aimed at improving device stability by encapsulation with inert polymeric materials was carried out. The program focused specifically on optimizing the encapsulant materials and their deposition techniques. The principal objectives for this program were device encapsulation, device testing, and accelerated testing to ensure very long term stability of these high resolution sensors. A variety of encapsulants were investigated with the selection criteria based on their chemical diffusion barrier properties, mechanical stability, reactivity, and morphology of encapsulant films. The investigation covered different classes of encapsulants including solvent based encapsulants, vapor deposited encapsulants, and plasma polymerized encapsulants. A variety of characterization techniques

Polymerization in the gas phase, in clusters, and on nanoparticle surfaces.

PubMed

El-Shall, M Samy

2008-07-01

Gas phase and cluster experiments provide unique opportunities to quantitatively study the effects of initiators, solvents, chain transfer agents, and inhibitors on the mechanisms of polymerization. Furthermore, a number of important phenomena, unique structures, and novel properties may exist during gas-phase and cluster polymerization. In this regime, the structure of the growing polymer may change dramatically and the rate coefficient may vary significantly upon the addition of a single molecule of the monomer. These changes would be reflected in the properties of the oligomers deposited from the gas phase. At low pressures, cationic and radical cationic polymerizations may proceed in the gas phase through elimination reactions. In the same systems at high pressure, however, the ionic intermediates may be stabilized, and addition without elimination may occur. In isolated van der Waals clusters of monomer molecules, sequential polymerization with several condensation steps can occur on a time scale of a few microseconds following the ionization of the gas-phase cluster. The cluster reactions, which bridge gas-phase and condensed-phase chemistry, allow examination of the effects of controlled states of aggregation. This Account describes several examples of gas-phase and cluster polymerization studies where the most significant results can be summarized as follows: (1) The carbocation polymerization of isobutene shows slower rates with increasing polymerization steps resulting from entropy barriers, which could explain the need for low temperatures for the efficient propagation of high molecular weight polymers. (2) Radical cation polymerization of propene can be initiated by partial charge transfer from an ionized aromatic molecule such as benzene coupled with covalent condensation of the associated propene molecules. This novel mechanism leads exclusively to the formation of propene oligomer ions and avoids other competitive products. (3) Structural information

Angle-resolved molecular beam scattering of NO at the gas-liquid interface.

PubMed

Zutz, Amelia; Nesbitt, David J

2017-08-07

This study presents first results on angle-resolved, inelastic collision dynamics of thermal and hyperthermal molecular beams of NO at gas-liquid interfaces. Specifically, a collimated incident beam of supersonically cooled NO ( 2 Π 1/2 , J = 0.5) is directed toward a series of low vapor pressure liquid surfaces ([bmim][Tf 2 N], squalane, and PFPE) at θ inc = 45(1)°, with the scattered molecules detected with quantum state resolution over a series of final angles (θ s = -60°, -30°, 0°, 30°, 45°, and 60°) via spatially filtered laser induced fluorescence. At low collision energies [E inc = 2.7(9) kcal/mol], the angle-resolved quantum state distributions reveal (i) cos(θ s ) probabilities for the scattered NO and (ii) electronic/rotational temperatures independent of final angle (θ s ), in support of a simple physical picture of angle independent sticking coefficients and all incident NO thermally accommodating on the surface. However, the observed electronic/rotational temperatures for NO scattering reveal cooling below the surface temperature (T elec < T rot < T S ) for all three liquids, indicating a significant dependence of the sticking coefficient on NO internal quantum state. Angle-resolved scattering at high collision energies [E inc = 20(2) kcal/mol] has also been explored, for which the NO scattering populations reveal angle-dependent dynamical branching between thermal desorption and impulsive scattering (IS) pathways that depend strongly on θ s . Characterization of the data in terms of the final angle, rotational state, spin-orbit electronic state, collision energy, and liquid permit new correlations to be revealed and investigated in detail. For example, the IS rotational distributions reveal an enhanced propensity for higher J/spin-orbit excited states scattered into near specular angles and thus hotter rotational/electronic distributions measured in the forward scattering direction. Even more surprisingly, the average NO scattering angle

Polymerization of Conducting Polymers Confined to Free Surfaces: A comparison of the Langmuir-Blodgett Polymerization of 3-Alkyl Pyrroles and 2- Alkyl Anilines

DTIC Science & Technology

1992-05-19

Confined to Free Surfaces: A Comparison of the Langmuir-Blodgett Polymerization of 3- Alkyl Pyrroles and 2- Alkyl Anilines Submitted for Publication in...Surfaces: A Comparison of the Langmuir Blodgett Polymerizations of 3- alkyl pyrroles and 2- alkyl anilines R. S. Duran and H.C. Zhou Dept. of Chemistry...polymerization reactions in more detail and compare them. To do this, the polymerization reactions were run under two conditions. In the first case

Effect of degree of crosslinking and polymerization of 3D printable polymer/ionic liquid composites on performance of stretchable piezoresistive sensors

NASA Astrophysics Data System (ADS)

Lee, Jeongwoo; Faruk Emon, Md Omar; Vatani, Morteza; Choi, Jae-Won

2017-03-01

Ionic liquid (IL)/polymer composites (1-ethyl-3-methyl-imidazolium tetrafluoroborate (EMIMBF4)/2-[[(butylamino)carbonyl]oxy]ethyl acrylate (BACOEA)) were fabricated to use as sensing materials for stretchable piezoresistive tactile sensors. The detectability of the IL/polymer composites was enhanced because the ionic transport properties of EMIMBF4 in the composites were improved by the synergic actions between the coordinate sites generated by the local motion of BACOEA chain segments under enough activation energy. The performance of the piezoresistive sensors was investigated with the degree of crosslinking and polymerization of the IL/polymer composites. As the compressive strain was increased, the distance between two electrodes decreased, and the motion of polymer chains and IL occurred, resulting in a decrease in the electrical resistance of the sensors. We have confirmed that the sensitivity of the sensors are affected by the degree of crosslink and polymerization of the IL/polymer composites. In addition, all of the materials (skins, sensing material, and electrode) used in this study are photo-curable, and thus the stretchable piezoresistive tactile sensors can be successfully fabricated by 3D printing.

Frontal Polymerization in Microgravity: Bubble Behavior and Convection on the KC-135 Aircraft

NASA Technical Reports Server (NTRS)

Pojman, John A.; Ainsworth, William; Chekanov, Yuri; Masere, Jonathan; Volpert, Vitaly; Dumont, Thierry; Wilke, Hermann

2001-01-01

Frontal polymerization is a mode of converting monomer into polymer via a localized exothermic reaction zone that propagates through the coupling of thermal diffusion and Arrhenius reaction kinetics. Frontal polymerization was discovered in Russia by Chechilo and Enikolopyan in 1972. The macrokinetics and dynamics of frontal polymerization have been examined in detail and applications for materials synthesis considered. Large temperature and concentration gradients that occur in the front lead to large density gradients. A schematic is presented for a liquid monomer, usually a monoacrylate, being converted to a liquid (thermoplastic) polymer. The velocity can be controlled by the initiator concentration but is on the order of a cm/min. If the liquid monomer is multifunctional, then a solid (thermoset) polymer is formed. Convection can occur with all types of monomers if the front propagates up a tube. Bowden et al. studied liquid/solid systems. McCaughey et al. studied liquid polymer systems. Descending fronts in thermoplastic systems are also susceptible to the Rayleigh-Taylor instability.

Pressure-Induced Polymerization of LiN(CN) 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keefer, Derek W.; Gou, Huiyang; Purdy, Andrew P.

The high-pressure behavior of lithium dicyanamide (LiN(CN) 2) was studied with in situ Raman and infrared (IR) spectroscopies, and synchrotron angle-dispersive powder X-ray diffraction (PXRD) in a diamond anvil cell (DAC) to 22 GPa. The fundamental vibrational modes associated with molecular units were assigned using a combination of experimental data and density functional perturbation theory. Some low-frequency modes were observed for the first time. On the basis of spectroscopic and diffraction data, we suggest a polymorphic phase transformation at ~8 GPa, wherein dicyanamide ions remain as discrete molecular species. Above ca. 18 GPa, dicyanamide units polymerize, forming a largely disorderedmore » network, and the extent of polymerization may be increased by annealing at elevated temperature. The polymerized product consists of tricyanomelaminate-like groups containing sp 2-hybidized carbon–nitrogen bonds and exhibits a visible absorption edge near 540 nm. The product is recoverable to ambient conditions but is not stable in air/moisture.« less

The role of disclinations on the organization and conductivity in liquid crystal nanocomposites

NASA Astrophysics Data System (ADS)

Martinez-Miranda, Luz J.; Romero-Hasler, P.; Meneses-Franco, A.; Soto-Bustamante, E. A.

The structure of TiO2 nanoparticles in a liquid crystal nanocomposite was found to be an oblique structure due to the alignment of the TiO2 with respect to the liquid crystals. This order is anisotropic due to the ordering of the liquid crystals. The particles are highly localized in the nanocomposite, which has consequences in the electrical percolation. We want to obtain an understanding of how the nanoparticles organize in this highly localized fashion. The nanoparticles and the liquid crystals phase separate, with the nanoparticles accumulating in the defects exhibited by the liquid crystal even after being sonicated initially. The liquid crystal is polymerized by the process of electropolymerization that takes place in the isotropic phase of the monomers. The nanoparticles are free to move away from the defects where they phase separate since the defects disappear in the isotropic. We believe the polymerization imposes a limitation in the movement of the nanoparticles. The combination of the accumulation in the disclinations, the polymerization in the isotropic and the formation of the liquid crystal unit side chains can affect the conductivity of the nanocomposite. NSF-OISE-1157589; Fondecyt Project 1130187; CONICYT scholarships 21130413 and 21090713.

Liquid-liquid two phase systems for the production of porous hydrogels and hydrogel microspheres for biomedical applications: A tutorial review

PubMed Central

Elbert, Donald L.

2010-01-01

Macroporous hydrogels may have direct applications in regenerative medicine as scaffolds to support tissue formation. Hydrogel microspheres may be used as drug delivery vehicles or as building blocks to assemble modular scaffolds. A variety of techniques exist to produce macroporous hydrogels and hydrogel microspheres. A subset of these relies on liquid-liquid two phase systems. Within this subset, vastly different types of polymerization processes are found. In this review, the history, terminology and classification of liquid-liquid two phase polymerization and crosslinking are described. Instructive examples of hydrogel microsphere and macroporous scaffold formation by precipitation/dispersion, emulsion and suspension polymerizations are used to illustrate the nature of these processes. The role of the kinetics of phase separation in determining the morphology of scaffolds and microspheres is also delineated. Brief descriptions of miniemulsion, microemulsion polymerization and ionotropic gelation are also included. PMID:20659596

Microcapsules fabricated from liquid marbles stabilized with latex particles.

PubMed

Ueno, Kazuyuki; Hamasaki, Sho; Wanless, Erica J; Nakamura, Yoshinobu; Fujii, Syuji

2014-03-25

Millimeter- and centimeter-sized "liquid marbles" were readily prepared by rolling water droplets on a powder bed of dried submicrometer-sized polystyrene latex particles carrying poly[2-(diethylamino)ethyl methacrylate] hairs (PDEA-PS). Scanning electron microscopy studies indicated that flocs of the PDEA-PS particles were adsorbed at the surface of these water droplets, leading to stable spherical liquid marbles. The liquid marbles were deformed as a result of water evaporation to adopt a deflated spherical geometry, and the rate of water evaporation decreased with increasing atmospheric relative humidity. Conversely, liquid marbles formed using saturated aqueous LiCl solution led to atmospheric water absorption by the liquid marbles and a consequent mass increase. The liquid marbles can be transformed into polymeric capsules containing water by exposure to solvent vapor: the PDEA-PS particles were plasticized with the solvent vapor to form a polymer film at the air-water interface of the liquid marbles. The polymeric capsules with aqueous volumes of 250 μL or less kept their oblate ellipsoid/near spherical shape even after complete water evaporation, which confirmed that a rigid polymeric capsule was successfully formed. Both the rate of water evaporation from the pure water liquid marbles and the rate of water adsorption into the aqueous LiCl liquid marbles were reduced with an increase of solvent vapor treatment time. This suggests that the number and size of pores within the polymer particles/flocs on the liquid marble surface decreased due to film formation during exposure to organic solvent vapor. In addition, organic-inorganic composite capsules and colloidal crystal capsules were fabricated from liquid marbles containing aqueous SiO2 dispersions.

Poly(ionic liquid)/Ionic Liquid Ion-Gels with High "Free" Ionic Liquid Content: Platform Membrane Materials for CO2/Light Gas Separations.

PubMed

Cowan, Matthew G; Gin, Douglas L; Noble, Richard D

2016-04-19

-films (ca. 100-nm-thick active layer). Traditional polymeric membrane materials are limited by a trade-off between permeability and selectivity empirically described by the "Robeson upper bound"-placing the desired membrane properties beyond reach. Therefore, the investigation of advanced and composite materials that can overcome the limitations of traditional polymeric materials is the focus of significant academic and industrial research. In particular, there has been substantial work on ionic-liquid (IL)-based materials due to their gas transport properties. This review provides an overview of our collaborative work on developing poly(ionic liquid)/ionic liquid (PIL/IL) ion-gel membrane technology. We detail developmental work on the preparation of PIL/IL composites and describe how this chemical technology was adapted to allow the roll-to-roll processing and preparation of membranes with defect-free active layers ca. 100 nm thick, CO2 permeances of over 6000 GPU, and CO2/N2 selectivity of ≥20-properties with the potential to reduce the cost of CO2 removal from coal-fired power plant flue gas to ca. $15 per ton of CO2 captured. Additionally, we examine the materials developments that have produced advanced PIL/IL composite membranes. These advancements include cross-linked PIL/IL blends, step-growth PIL/IL networks with facilitated transport groups, and PIL/IL composites with microporous additives for CO2/CH4 separations.

Determination of erythromycin in human plasma, using column liquid chromatography with a polymeric packing material, alkaline mobile phase and amperometric detection.

PubMed

Nilsson, L G; Walldorf, B; Paulsen, O

1987-12-25

A method based on column liquid chromatography was developed for determination of plasma concentrations of erythromycin. PRP-1, a polymeric type of packing material suitable for chromatography and amperometric detection at high pH, was used. The effect of pH on the column performance and on the electrochemical response was studied. A pH of ca. 10 was found to be optimal. After extraction with tert.-butyl methyl ether, plasma concentrations down to 0.2 mumol/l could be measured, using automated sample injection. Oleandomycin was used as internal standard. The method was used for determination of plasma concentrations in a pharmacokinetic study under steady-state conditions.

Electrical and structural characterization of plasma polymerized polyaniline/TiO2 heterostructure diode: a comparative study of single and bilayer TiO2 thin film electrode.

PubMed

Ameen, Sadia; Akhtar, M Shaheer; Kimi, Young Soon; Yang, O-Bong; Shin, Hyung-Shik

2011-04-01

A heterostructure was fabricated using p-type plasma polymerized polyaniline (PANI) and n-type (single and bilayer) titanium dioxide (TiO2) thin film on FTO glass. The deposition of single and bilayer TiO2 thin film on FTO substrate was achieved through doctor blade followed by dip coating technique before subjected to plasma enhanced polymerization. To fabricate p-n heterostructure, a plasma polymerization of aniline was conducted using RF plasma at 13.5 MHz and at the power of 120 W on the single and bilayer TiO2 thin film electrodes. The morphological, optical and the structural characterizations revealed the formation of p-n heterostructures between PANI and TiO2 thin film. The PANI/bilayer TiO2 heterostructure showed the improved current-voltage (I-V) characteristics due to the substantial deposition of PANI molecules into the bilayer TiO2 thin film which provided good conducting pathway and reduced the degree of excitons recombination. The change of linear I-V behavior of PANI/TiO2 heterostructure to non linear behavior with top Pt contact layer confirmed the formation of Schottky contact at the interfaces of Pt layer and PANI/TiO2 thin film layers.

Pressure-induced structural change in liquid GeI₄.

PubMed

Fuchizaki, Kazuhiro; Nishimura, Hironori; Hase, Takaki; Saitoh, Hiroyuki

2017-12-13

The similarity in the shape of the melting curve of GeI₄ to that of SnI₄ suggests that a liquid-liquid transition as observed in liquid SnI₄ is also expected to occur in liquid GeI₄. Because the slope of the melting curve of GeI₄ abruptly changes at around 3 GPa, in situ synchrotron diffraction measurements were conducted to examine closely the structural changes upon compression at around 3 GPa. The reduced radial distribution functions of the high- and low-pressure liquid states of GeI₄ share the same feature inherent in the high-pressure (high-density) and low-pressure (low-density) radial distribution functions of liquid SnI₄. This feature allows us to introduce local order parameters that we may use to observe the transition. Unlike the transition in liquid SnI₄, the transition from the low-pressure to the high-pressure structure seems sluggish. We speculate that the liquid-liquid critical point of GeI₄ is no longer a thermodynamically stable state and is slightly located below the melting curve. As a result, the structural change is said to be a crossover rather than a transition. The behavior of the local-order parameters implies a metastable extension of the liquid-liquid phase boundary with a negative slope. . © 2017 IOP Publishing Ltd.

Block copolymers from ionic liquids for the preparation of thin carbonaceous shells

PubMed Central

Hanif, Sadaf; Oschmann, Bernd; Spetter, Dmitri; Tahir, Muhammad Nawaz; Tremel, Wolfgang

2017-01-01

This paper describes the controlled radical polymerization of an ionic-liquid monomer by RAFT polymerization. This allows the control over the molecular weight of ionic liquid blocks in the range of 8000 and 22000 and of the block-copolymer synthesis. In this work we focus on block copolymers with an anchor block. They can be used to control the formation of TiO2 nanoparticles, which are functionalized thereafter with a block of ionic-liquid polymer. Pyrolysis of these polymer functionalized inorganic nanoparticles leads to TiO2 nanoparticles coated with a thin carbonaceous shell. Such materials may, e.g., be interesting as battery materials. PMID:28904612

Block copolymers from ionic liquids for the preparation of thin carbonaceous shells.

PubMed

Hanif, Sadaf; Oschmann, Bernd; Spetter, Dmitri; Tahir, Muhammad Nawaz; Tremel, Wolfgang; Zentel, Rudolf

2017-01-01

This paper describes the controlled radical polymerization of an ionic-liquid monomer by RAFT polymerization. This allows the control over the molecular weight of ionic liquid blocks in the range of 8000 and 22000 and of the block-copolymer synthesis. In this work we focus on block copolymers with an anchor block. They can be used to control the formation of TiO 2 nanoparticles, which are functionalized thereafter with a block of ionic-liquid polymer. Pyrolysis of these polymer functionalized inorganic nanoparticles leads to TiO 2 nanoparticles coated with a thin carbonaceous shell. Such materials may, e.g., be interesting as battery materials.

COLLISIONS BETWEEN GRAVITY-DOMINATED BODIES. I. OUTCOME REGIMES AND SCALING LAWS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leinhardt, Zoee M.; Stewart, Sarah T., E-mail: Zoe.Leinhardt@bristol.ac.uk, E-mail: sstewart@eps.harvard.edu

2012-01-20

Collisions are the core agent of planet formation. In this work, we derive an analytic description of the dynamical outcome for any collision between gravity-dominated bodies. We conduct high-resolution simulations of collisions between planetesimals; the results are used to isolate the effects of different impact parameters on collision outcome. During growth from planetesimals to planets, collision outcomes span multiple regimes: cratering, merging, disruption, super-catastrophic disruption, and hit-and-run events. We derive equations (scaling laws) to demarcate the transition between collision regimes and to describe the size and velocity distributions of the post-collision bodies. The scaling laws are used to calculate mapsmore » of collision outcomes as a function of mass ratio, impact angle, and impact velocity, and we discuss the implications of the probability of each collision regime during planet formation. Collision outcomes are described in terms of the impact conditions and the catastrophic disruption criteria, Q*{sub RD}-the specific energy required to disperse half the total colliding mass. All planet formation and collisional evolution studies have assumed that catastrophic disruption follows pure energy scaling; however, we find that catastrophic disruption follows nearly pure momentum scaling. As a result, Q*{sub RD} is strongly dependent on the impact velocity and projectile-to-target mass ratio in addition to the total mass and impact angle. To account for the impact angle, we derive the interacting mass fraction of the projectile; the outcome of a collision is dependent on the kinetic energy of the interacting mass rather than the kinetic energy of the total mass. We also introduce a new material parameter, c*, that defines the catastrophic disruption criteria between equal-mass bodies in units of the specific gravitational binding energy. For a diverse range of planetesimal compositions and internal structures, c* has a value of 5 {+-} 2

Ion transport and softening in a polymerized ionic liquid

DOE PAGES

Kumar, Rajeev; Bocharova, Vera; Strelcov, Evgheni; ...

2014-11-13

Polymerized ionic liquids (PolyILs) are promising materials for various solid state electronic applications such as dye-sensitized solar cells, lithium batteries, actuators, field-effect transistors, light emitting electrochemical cells, and electrochromic devices. However, fundamental understanding of interconnection between ionic transport and mechanical properties in PolyILs is far from complete. In this paper, local charge transport and structural changes in films of a PolyIL are studied using an integrated experiment-theory based approach. Experimental data for the kinetics of charging and steady state current–voltage relations can be explained by taking into account the dissociation of ions under an applied electric field (known as themore » Wien effect). Onsager's theory of the Wien effect coupled with the Poisson–Nernst–Planck formalism for the charge transport is found to be in excellent agreement with the experimental results. The agreement between the theory and experiments allows us to predict structural properties of the PolyIL films. We have observed significant softening of the PolyIL films beyond certain threshold voltages and formation of holes under a scanning probe microscopy (SPM) tip, through which an electric field was applied. Finally, the observed softening is explained by the theory of depression in glass transition temperature resulting from enhanced dissociation of ions with an increase in applied electric field.« less

Beer Law Constants and Vapor Pressures of HgI2 over HgI2(s,l)

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Zhu, Shen; Ramachandran, N.; Burger, A.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

The optical absorption spectra of the vapor phase over HgI2(s,l) were measured for wavelengths between 200 and 600 nm. The spectra show that the sample sublimed congruently into HgI2 with no Hg or I2 absorption spectrum observed. The Beer's Law constants for 15 wavelengths between 200 and 440 nm were determined. From these constants the vapor pressure of H912, P, was established as a function of temperatures for the liquid and the solid Beta-phases. The expressions correspond to the enthalpies of vaporization and sublimation of 15.30 and 20.17 Kcal/mole, respectively, for the liquid and the Beta-phase HgI2. The difference in the enthalpies gives an enthalpy of fusion of 4.87 Kcal/mole and the intersection of the two expressions gives a melting point of 537 K.

Radical routes to interstellar glycolaldehyde. The possibility of stereoselectivity in gas-phase polymerization reactions involving CH(2)O and ˙CH(2)OH.

PubMed

Wang, Tianfang; Bowie, John H

2010-10-21

A previous report that the interstellar molecule glycolaldehyde (HOCH(2)CHO) can be made from hydroxymethylene (HOCH:) and formaldehyde has been revisited at the CCSD(T)/6-311++G(3df,2p)//MP2/6-311++G(3df,2p) level of theory. This reaction competes with the formation of acetic acid and methylformate, molecules which have also been detected in interstellar clouds. Other possible modes of formation of glycolaldehyde by radical/radical reactions have been shown to be viable theoretically as follows: HO˙+˙CH2CHO -->HOCH2CHO [ΔG(Γ)(298K)=-303kJ mol⁻¹] HOCH2˙+˙CHO-->HOCH2CHO (-259kJ mol⁻¹). The species in these two processes are known interstellar molecules. Key radicals ˙CH(2)CHO and ˙CH(2)OH in these sequences have been shown to be stable for the microsecond duration of neutralization/reionization experiments in the dual collision cells of a VG ZAB 2HF mass spectrometer. The polymerization reaction HOCH(2)CH˙OH + nCH(2)O → HOCH(2)[CH(OH)](n)˙CHOH (n = 1 to 3) has been studied theoretically and shown to be energetically feasible, as is the cyclization reaction of HOCH(2)[(CH(2)OH)(4)]˙CHOH (in the presence of one molecule of water at the reacting centre) to form glucose. The probability of such a reaction sequence is small even if polymerization were to occur in interstellar ice containing a significant concentration of CH(2)O. The large number of stereoisomers produced by such a reaction sequence makes the formation of a particular sugar, again for example glucose, an inefficient synthesis. The possibility of stereoselectivity occurring during the polymerization was investigated for two diastereoisomers of HOCH(2)[(CHOH)](2)˙CHOH. No significant difference was found in the transition state energies for addition of CH(2)O to these two diastereoisomers, but a barrier difference of 12 kJ mol(-1) was found for the H transfer reactions ˙OCH(2)[(CHOH)](2)CH(2)OH → HOCH(2)[(CHOH)(2)˙CHOH of the two diastereoisomers.

Pentacene-based organic thin film transistors, integrated circuits, and active matrix displays on polymeric substrates

NASA Astrophysics Data System (ADS)

Sheraw, Christopher Duncan

2003-10-01

Organic thin film transistors are attractive candidates for a variety of low cost, large area commercial electronics including smart cards, RF identification tags, and flat panel displays. Of particular interest are high performance organic thin film transistors (TFTs) that can be fabricated on flexible polymeric substrates allowing low-cost, lightweight, rugged electronics such as flexible active matrix displays. This thesis reports pentacene organic thin film transistors fabricated on flexible polymeric substrates with record performance, the fastest photolithographically patterned organic TFT integrated circuits on polymeric substrates reported to date, and the fabrication of the organic TFT backplanes used to build the first organic TFT-driven active matrix liquid crystal display (AMLCD), also the first AMLCD on a flexible substrate, ever reported. In addition, the first investigation of functionalized pentacene derivatives used as the active layer in organic thin film transistors is reported. A low temperature (<110°C) process technology was developed allowing the fabrication of high performance organic TFTs, integrated circuits, and large TFT arrays on flexible polymeric substrates. This process includes the development of a novel water-based photolithographic active layer patterning process using polyvinyl alcohol that allows the patterning of organic semiconductor materials for elimination of active layer leakage current without causing device degradation. The small molecule aromatic hydrocarbon pentacene was used as the active layer material to fabricate organic TFTs on the polymeric material polyethylene naphthalate with field-effect mobility as large as 2.1 cm2/V-s and on/off current ratio of 108. These are the best values reported for organic TFTs on polymeric substrates and comparable to organic TFTs on rigid substrates. Analog and digital integrated circuits were also fabricated on polymeric substrates using pentacene TFTs with propagation delay as

Reduction of in-source collision-induced dissociation and thermolysis of sulopenem prodrugs for quantitative liquid chromatography/electrospray ionization mass spectrometric analysis by promoting sodium adduct formation.

PubMed

Wujcik, Chad E; Kadar, Eugene P

2008-10-01

Six chromatographically resolved sulopenem prodrugs were monitored for their potential to undergo both in-source collision-induced dissociation (CID) and thermolysis. Initial Q1 scans for each prodrug revealed the formation of intense [Prodrug2 + H]+, [Prodrug2 + Na]+, [Prodrug + Na]+, and [Sulopenem + Na]+ ions. Non-adduct-associated sulopenem ([Sulopenem + H]+) along with several additional lower mass ions were also observed. Product ion scans of [Prodrug3 + Na]+ showed the retention of the sodium adduct in the collision cell continuing down to opening of the beta-lactam ring. In-source CID and temperature experiments were conducted under chromatographic conditions while monitoring several of the latter ion transitions (i.e., adducts, dimers and degradants/fragments) for a given prodrug. The resulting ion profiles indicated the regions of greatest stability for temperature and declustering potential (DP) that provided the highest signal intensity for each prodrug and minimized in-source degradation. The heightened stability of adduct ions, relative to their appropriate counterpart (i.e., dimer to dimer adduct and prodrug to prodrug adduct ions), was observed under elevated temperature and DP conditions. The addition of 100 microM sodium to the mobile phase further enhanced the formation of these more stable adduct ions, yielding an optimal [Prodrug + Na]+ ion signal at temperatures from 400 to 600 degrees C. A clinical liquid chromatography/tandem mass spectrometry (LC/MS/MS) assay for sulopenem prodrug PF-04064900 in buffered whole blood was successfully validated using sodium-fortified mobile phase and the [PF-04064900 + Na]+ ion for quantitation. A conservative five-fold increase in sensitivity from previously validated preclinical assays using the [PF-04064900 + H]+ precursor ion was achieved.

Polymerization of euphorbia oil with Lewis acid in carbon dioxide media

USDA-ARS?s Scientific Manuscript database

Boron trifluoride diethyl etherate (BF3-OEt2) Lewis acid catalyzed ring-opening polymerization of euphorbia oil (EO), a natural epoxy oil, in liquid carbon dioxide was conducted in an effort to develop useful vegetable oil based polymers. The resulting polymers (RPEO) were characterized by FTIR, 1H-...

Understanding glass formation and ion transport in polymeric ionic liquids using computer simulations

NASA Astrophysics Data System (ADS)

Patra, Tarak; Yang, Junhong; Cheng, Yiz; Simmons, David

Polymeric ionic liquids (PILs) are very promising materials to enable more environmentally stable high density energy storage devices. Realization of PILs providing high environmental and mechanical stability while maximizing ion conductivity would be accelerated by an improved molecular level understanding of their structure and dynamics. Extensive evidence suggests that both mechanical properties and ion conductivity in anhydrous PILs are intimately related to the PIL's glass formation behavior. This represents a major challenge to the rational design of these materials, given that the basic nature of glass formation and its connection to molecular properties remains a substantial open question in polymer and condensed matter physics. Here we describe coarse-grained and atomistic molecular dynamics simulations probing the relationship between PIL architecture and interactions, glass formation behavior, and ion transport characteristics. These studies provide guidance towards the design of PILs with improved stability and ion conductivity for future energy applications.

Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fan, Fei; Wang, Yangyang; Hong, Tao

2015-07-17

Polymerized ionic liquids (PolyILs) are promising candidates for energy storage and electrochemical devices applications. Understanding their ionic transport mechanism is the key for designing highly conductive PolyILs. By using broadband dielectric spectroscopy (BDS), rheology, and differential scanning calorimetry (DSC), a systematic study has been carried out to provide a better understanding of the ionic transport mechanism in PolyILs with different pendant groups. The variation of pendant groups results in different dielectric, mechanical, and thermal properties of these PolyILs. The Walden plot analysis shows that the data points for all these PolyILs fall above the ideal Walden line, and the deviationmore » from the ideal line increases upon approaching the glass transition temperature (T g). Moreover, the conductivity for these PolyILs at their Tgs are much higher than the usually reported value 10 15 S/cm for polymer electrolytes, in which the ionic transport is closely coupled to the segmental dynamics. These results indicate a decoupling of ionic conductivity from the segmental relaxation in these materials. The degree of decoupling increases with the increase of the fragility of polymer segmental relaxation. Finally, we relate this observation to a decrease in polymer packing efficiency with an increase in fragility.« less

Construction of Au@Pt core—satellite nanoparticles based on in-situ reduction of polymeric ionic liquid protected gold nanoparticles

NASA Astrophysics Data System (ADS)

Wu, Wenlan; Li, Junbo; Zou, Sheng; Guo, Jinwu; Zhou, Huiyun

2017-03-01

A method of in-situ reduction to prepare Au@Pt core-satellite nanoparticles (NPs) is described by using Au NPs coating poly[1-methyl 3-(2-methacryloyloxy propylimidazolium bromine)] (PMMPImB-@-Au NPs) as the template. After electrostatic complex chloroplatinic acid with PMMPImB shell, the composite NP was directly reduced with N2H4 to produce Au@Pt core-satellite NPs. The characterization of composite and core-satellite NPs under different amounts of chloroplatinic acid were studied by DLS, UV-vis absorption spectrum and TEM. The satellite Pt NPs with a small size ( 2 nm) dotted around Au core, and the resulting Au@Pt core-satellite NPs showed a red-shift surface plasmon resonance (SPR) and a good dispersion due to effectively electrostatic repulsion providing by the polymeric ionic liquid (PIL) shell. Finally, Au@Pt core-satellite NPs exhibit an enhanced catalytic activity and cycled catalytic capability for the reduction of p-nitrophenol with NaBH4.

Utilization of highly robust and selective crosslinked polymeric ionic liquid-based sorbent coatings in direct-immersion solid-phase microextraction and high-performance liquid chromatography for determining polar organic pollutants in waters.

PubMed

Pacheco-Fernández, Idaira; Najafi, Ali; Pino, Verónica; Anderson, Jared L; Ayala, Juan H; Afonso, Ana M

2016-09-01

Several crosslinked polymeric ionic liquid (PIL)-based sorbent coatings of different nature were prepared by UV polymerization onto nitinol wires. They were evaluated in a direct-immersion solid-phase microextraction (DI-SPME) method in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD). The studied PIL coatings contained either vinyl alkyl or vinylbenzyl imidazolium-based (ViCnIm- or ViBCnIm-) IL monomers with different anions, as well as different dicationic IL crosslinkers. The analytical performance of these PIL-based SPME coatings was firstly evaluated for the extraction of a group of 10 different model analytes, including hydrocarbons and phenols, while exhaustively comparing the performance with commercial SPME fibers such as polydimethylsyloxane (PDMS), polyacrylate (PA) and polydimethylsiloxane/divinylbenzene (PDMS/DVB), and using all fibers under optimized conditions. Those fibers exhibiting a high selectivity for polar compounds were selected to carry out an analytical method for a group of 5 alkylphenols, including bisphenol-A (BPA) and nonylphenol (n-NP). Under optimum conditions, average relative recoveries of 108% and inter-day precision values (3 non-consecutive days) lower than 19% were obtained for a spiked level of 10µgL(-1). Correlations coefficients for the overall method ranged between 0.990 and 0.999, and limits of detection were down to 1µgL(-1). Tap water, river water, and bottled water were analyzed to evaluate matrix effects. Comparison with the PA fiber was also performed in terms of analytical performance. Partition coefficients (logKfs) of the alkylphenols to the SPME coating varied from 1.69 to 2.45 for the most efficient PIL-based fiber, and from 1.58 to 2.30 for the PA fiber. These results agree with those obtained by the normalized calibration slopes, pointing out the affinity of these PILs-based coatings. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis of Size-Tunable CO2-Philic Imprinted Polymeric Particles (MIPs) for Low-Pressure CO2 Capture Using Oil-in-Oil Suspension Polymerization.

PubMed

Nabavi, Seyed Ali; Vladisavljević, Goran T; Zhu, Yidi; Manović, Vasilije

2017-10-03

Highly selective molecularly imprinted poly[acrylamide-co-(ethylene glycol dimethacrylate)] polymer particles (MIPs) for CO 2 capture were synthesized by suspension polymerization via oil-in-oil emulsion. Creation of CO 2 -philic, amide-decorated cavities in the polymer matrix led to a high affinity to CO 2 . At 0.15 bar CO 2 partial pressure, the CO 2 /N 2 selectivity was 49 (corresponding to 91% purity of the gas stream after regeneration), and reached 97 at ultralow CO 2 partial pressures. The imprinted polymers showed considerably higher CO 2 uptakes compared to their nonimprinted counterparts, and the maximum equilibrium CO 2 capture capacity of 1.1 mmol g -1 was achieved at 273 K. The heat of adsorption was below 32 kJ mol -1 and the temperature of onset of intense thermal degradation was 351-376 °C. An increase in monomer-to-cross-linker molar ratio in the dispersed phase up to 1:2.5 led to a higher affinity toward CO 2 due to higher density of selective amide groups in the polymer network. MIPs are a promising option for industrial packed and fluidized bed CO 2 capture systems due to large particles with a diameter up to 1200 μm and irregular oblong shapes formed due to arrested coalescence during polymerization, occurring as a result of internal elasticity of the partially polymerized semisolid drops.

In-situ polymerization PLOT columns I: divinylbenzene

NASA Technical Reports Server (NTRS)

Shen, T. C.

1992-01-01

A novel method for preparation of porous-layer open-tubular (PLOT) columns is described. The method involves a simple and reproducible, straight-forward in-situ polymerization of monomer directly on the metal tube.

Synthesis and structural studies of heterobimetallic alkoxide complexes supported by bis(phenolate) ligands: efficient catalysts for ring-opening polymerization of L-lactide.

PubMed

Chen, Hsuan-Ying; Liu, Mei-Yu; Sutar, Alekha Kumar; Lin, Chu-Chieh

2010-01-18

A series of heterobimetallic titanium(IV) complexes [LTi(O(i)Pr)(mu-O(i)Pr)(2)Li(THF)(2)], [LTi(O(i)Pr)(mu-O(i)Pr)(2)Na(THF)(2)], [LTi(mu-O(i)Pr)(2)Zn(O(i)Pr)(2)], and [LTi(mu-O(i)Pr)(2)Mg(O(i)Pr)(2)] (where L = bidentate bisphenol ligands) have been synthesized and characterized including a structural determination of [L(1)Ti(mu(2)-O(i)Pr)(2)(O(i)Pr)Li(THF)(2)] (1a). These complexes were investigated for their utility in the ring-opening polymerization (ROP) of l-lactide (LA). Polymerization activities have been shown to correlate with the electronic properties of the substituent within the bisphenol ligand. In contrast to monometallic titanium initiator 1e, all the heterobimetallic titanium initiators (Ti-Li, Ti-Na, Ti-Zn, and Ti-Mg) show enhanced catalytic activity toward ring-opening polymerization (ROP) of l-LA. In addition, the use of electron-donating methoxy or methylphenylsulfonyl functional ligands reveals the highest activity. The bisphenol bimetallic complexes give rise to controlled ring-opening polymerization, as shown by the linear relationship between the percentage conversion and the number-average molecular weight. The polymerization kinetics using 2c as an initiator were also studied, and the experimental results indicate that the reaction rate is first-order with respect to both monomer and catalyst concentration with a polymerization rate constant, k = 81.64 M(-1) min(-1).

The Viscosity of Polymeric Fluids.

ERIC Educational Resources Information Center

Perrin, J. E.; Martin, G. C.

1983-01-01

To illustrate the behavior of polymeric fluids and in what respects they differ from Newtonian liquids, an experiment was developed to account for the shear-rate dependence of non-Newtonian fluids. Background information, procedures, and results are provided for the experiment. Useful in transport processes, fluid mechanics, or physical chemistry…

Membrane separation of ionic liquid solutions

DOEpatents

Campos, Daniel; Feiring, Andrew Edward; Majumdar, Sudipto; Nemser, Stuart

2015-09-01

A membrane separation process using a highly fluorinated polymer membrane that selectively permeates water of an aqueous ionic liquid solution to provide dry ionic liquid. Preferably the polymer is a polymer that includes polymerized perfluoro-2,2-dimethyl-1,3-dioxole (PDD). The process is also capable of removing small molecular compounds such as organic solvents that can be present in the solution. This membrane separation process is suitable for drying the aqueous ionic liquid byproduct from precipitating solutions of biomass dissolved in ionic liquid, and is thus instrumental to providing usable lignocellulosic products for energy consumption and other industrial uses in an environmentally benign manner.

Cofilin, But Not Profilin, Is Required for Myosin-I-Induced Actin Polymerization and the Endocytic Uptake in Yeast

PubMed Central

Idrissi, Fatima-Zahra; Wolf, Bianka L.; Geli, M. Isabel

2002-01-01

Mutations in the budding yeast myosins-I (MYO3 and MYO5) cause defects in the actin cytoskeleton and in the endocytic uptake. Robust evidence also indicates that these proteins induce Arp2/3-dependent actin polymerization. Consistently, we have recently demonstrated, using fluorescence microscopy, that Myo5p is able to induce cytosol-dependent actin polymerization on the surface of Sepharose beads. Strikingly, we now observed that, at short incubation times, Myo5p induced the formation of actin foci that resembled the yeast cortical actin patches, a plasma membrane-associated structure that might be involved in the endocytic uptake. Analysis of the machinery required for the formation of the Myo5p-induced actin patches in vitro demonstrated that the Arp2/3 complex was necessary but not sufficient in the assay. In addition, we found that cofilin was directly involved in the process. Strikingly though, the cofilin requirement seemed to be independent of its ability to disassemble actin filaments and profilin, a protein that closely cooperates with cofilin to maintain a rapid actin filament turnover, was not needed in the assay. In agreement with these observations, we found that like the Arp2/3 complex and the myosins-I, cofilin was essential for the endocytic uptake in vivo, whereas profilin was dispensable. PMID:12429847

Identifying Ca2+-Binding Sites in Proteins by Liquid Chromatography-Mass Spectrometry Using Ca2+-Directed Dissociations

PubMed Central

Jamalian, Azadeh; Sneekes, Evert-Jan; Wienk, Hans; Dekker, Lennard J. M.; Ruttink, Paul J. A.; Ursem, Mario; Luider, Theo M.; Burgers, Peter C.

2014-01-01

Here we describe a new method to identify calcium-binding sites in proteins using high-resolution liquid chromatography-mass spectrometry in concert with calcium-directed collision-induced dissociations. Our method does not require any modifications to the liquid chromatography-mass spectrometry apparatus, uses standard digestion protocols, and can be applied to existing high-resolution MS data files. In contrast to NMR, our method is applicable to very small amounts of complex protein mixtures (femtomole level). Calcium-bound peptides can be identified using three criteria: (1) the calculated exact mass of the calcium containing peptide; (2) specific dissociations of the calcium-containing peptide from threonine and serine residues; and (3) the very similar retention times of the calcium-containing peptide and the free peptide. PMID:25023127

Hydrocarbon polymeric binder for advanced solid propellant

NASA Technical Reports Server (NTRS)

Potts, J. E. (Editor)

1972-01-01

A series of DEAB initiated isoprene polymerizations were run in the 5-gallon stirred autoclave reactor. Polymerization run parameters such as initiator concentration and feed rate were correlated with the molecular weight to provide a basis for molecular weight control in future runs. Synthetic methods were developed for the preparation of n-1,3-alkadienes. By these methods, 1,3-nonadiene was polymerized using DEAB initiator to give an ester-telechelic polynonadiene. This was subsequently hydrogenated with copper chromite catalyst to give a hydroxyl terminated saturated liquid hydrocarbon prepolymer having greatly improved viscosity characteristics and a Tg 18 degrees lower than that of the hydrogenated polyisoprenes. The hydroxyl-telechelic saturated polymers prepared by the hydrogenolysis of ester-telechelic polyisoprene were reached with diisocyanates under conditions favoring linear chain extension gel permeation chromatography was used to monitor this condensation polymerization. Fractions having molecular weights above one million were produced.

Experimental and ab initio studies of the reactive processes in gas phase i-C{sub 3}H{sub 7}Br and i-C{sub 3}H{sub 7}OH collisions with potassium ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

López, E.; Lucas, J. M.; Andrés, J. de

2014-10-28

Collisions between potassium ions and neutral i-C{sub 3}H{sub 7}Br and i-C{sub 3}H{sub 7}OH, all in their electronic ground state, have been studied in the 0.10–10.00 eV center of mass (CM) collision energy range, using the radiofrequency-guided ion beam technique. In K{sup +} + i-C{sub 3}H{sub 7}Br collisions KHBr{sup +} formation was observed and quantified, while the analogous KH{sub 2}O{sup +} formation in K{sup +} + i-C{sub 3}H{sub 7}OH was hardly detected. Moreover, formation of the ion-molecule adducts and their decomposition leading to C{sub 3}H{sub 7}{sup +} and either KBr or KOH, respectively, have been observed. For all these processes, absolutemore » cross-sections were measured as a function of the CM collision energy. Ab initio structure calculations at the MP2 level have given information about the potential energy surfaces (PESs) involved. In these, different stationary points have been characterized using the reaction coordinate method, their connectivity being ensured by using the intrinsic-reaction-coordinate method. From the measured excitation function for KHBr{sup +} formation the corresponding thermal rate constant at 303 K has been calculated. The topology of the calculated PESs allows an interpretation of the main features of the reaction dynamics of both systems, and in particular evidence the important role played by the potential energy wells in controlling the reactivity for the different reaction channels.« less

Hybrid Encapsulated Ionic Liquids for Post-Combustion Carbon Dioxide (CO 2) Capture

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brennecke, Joan; Degnan, Thomas; McCready, Mark

Ionic liquids (ILs) and Phase Change Ionic Liquids (PCILs) are excellent materials for selective removal of carbon dioxide from dilute post-combustion streams. However, they are typically characterized as having high viscosities, which impairs their effectiveness due to mass transfer limitations, caused by the high viscosities. In this project, we are examining the benefits of encapsulating ILs and PCILs in thin polymeric shells to produce particles of approximately 100 to 600 μm in diameter that can be used in a fluidized bed absorber. The particles are produced by microencapsulation of the ILs and PCILs in CO 2-permeable polymer shells. Here wemore » report on the synthesis of the IL and PCIL materials, measurements of thermophysical properties including CO 2 capacity and reprotonation equilibrium and kinetics, encapsulation of the ILs and PCILs, mechanical and thermodynamic testing of the encapsulated materials, development of a rate based model of the absorber, and the design of a laboratory scale unit to test the encapsulated particles for CO 2 capture ability and efficiency. We show that the IL/PCIL materials can be successfully encapsulated, that they retain CO 2 uptake capacity, and that the uptake rates are increased relative to a stagnant sample of IL liquid or PCIL powder.« less

Unexpectedly Facile Rh(I) Catalyzed Polymerization of Ethynylbenzaldehyde Type Monomers: Synthesis of Polyacetylenes Bearing Reactive and Easy Transformable Pendant Carbaldehyde Groups.

PubMed

Sedláček, Jan; Havelková, Lucie; Zedník, Jiří; Coufal, Radek; Faukner, Tomáš; Balcar, Hynek; Brus, Jiří

2017-04-01

The chain coordination polymerization of (ethynylarene)carbaldehydes with unprotected carbaldehyde groups, namely ethynylbenzaldehydes, 1-ethynylbenzene-3,5-dicarboxaldehyde, and 3-[(4-ethynylphenyl)ethynyl]benzaldehyde, is reported for the first time. Polymerization is catalyzed with various Rh(I) catalysts and yields poly(arylacetylene)s with one or two pendant carbaldehyde groups per monomeric unit. Surprisingly, the carbaldehyde groups of the monomers do not inhibit the polymerization unlike the carbaldehyde group of unsubstituted benzaldehyde that acts as a strong inhibitor of Rh(I) catalyzed polymerization of arylacetylenes. The inhibition ability of carbaldehyde groups in (ethynylarene)carbaldehydes seems to be eliminated owing to a simultaneous presence of unsaturated ethynyl groups in (ethynylarene)carbaldehydes. The reactive carbaldehyde groups make poly[(ethynylarene)carbaldehyde]s promising for functional appreciation via various postpolymerization modifications. The introduction of photoluminescence or chirality to poly(ethynylbenzaldehyde)s via quantitative modification of their carbaldehyde groups in reaction with either photoluminescent or chiral primary amines under formation of the polymers with Schiff-base-type pendant groups is given as an example. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of a Crack-Free, Hybrid Skin Layer with Tunable Surface Topography and Improved Gas Permeation Selectivity on Elastomers Using Gel–Liquid Infiltration Polymerization

DOE PAGES

Wang, Mengyuan; Gorham, Justin M.; Killgore, Jason P.; ...

2017-07-31

Surface modifications of elastomers and gels are crucial for emerging applications such as soft robotics and flexible electronics, in large part because they provide a platform to control wettability, adhesion, and permeability. Current surface modification methods via ultraviolet-ozone (UVO) and/or O2 plasma, atomic layer deposition (ALD), plasmas deposition, and chemical treatment impart a dense polymer or inorganic layer on the surface that is brittle and easy to fracture at low strain levels. This paper presents a new method, based on gel–liquid infiltration polymerization, to form hybrid skin layers atop elastomers. The method is unique in that it allows for controlmore » of the skin layer topography, with tunable feature sizes and aspect ratios as high as 1.8 without fracture. Unlike previous techniques, the skin layer formed here dramatically improves the barrier properties of the elastomer, while preserving skin layer flexibility. Furthermore, the method is versatile and likely applicable to most interfacial polymerization systems and network polymers on flat and patterned surfaces.« less

Formation of a Crack-Free, Hybrid Skin Layer with Tunable Surface Topography and Improved Gas Permeation Selectivity on Elastomers Using Gel–Liquid Infiltration Polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Mengyuan; Gorham, Justin M.; Killgore, Jason P.

Surface modifications of elastomers and gels are crucial for emerging applications such as soft robotics and flexible electronics, in large part because they provide a platform to control wettability, adhesion, and permeability. Current surface modification methods via ultraviolet-ozone (UVO) and/or O2 plasma, atomic layer deposition (ALD), plasmas deposition, and chemical treatment impart a dense polymer or inorganic layer on the surface that is brittle and easy to fracture at low strain levels. This paper presents a new method, based on gel–liquid infiltration polymerization, to form hybrid skin layers atop elastomers. The method is unique in that it allows for controlmore » of the skin layer topography, with tunable feature sizes and aspect ratios as high as 1.8 without fracture. Unlike previous techniques, the skin layer formed here dramatically improves the barrier properties of the elastomer, while preserving skin layer flexibility. Furthermore, the method is versatile and likely applicable to most interfacial polymerization systems and network polymers on flat and patterned surfaces.« less

Increased Rail Transit Vehicle Crashworthiness in Head-On Collisions. Volume I. Initial Impact.

DOT National Transportation Integrated Search

1980-06-01

A specific goal of safety is to reduce the number of injuries that may result from the collision of two trains. In Volume I, a two-dimensional analytic simulation model of the leading cars of two impacting transit car consists is formulated. This mod...

Comparing two tetraalkylammonium ionic liquids. I. Liquid phase structure.

PubMed

Lima, Thamires A; Paschoal, Vitor H; Faria, Luiz F O; Ribeiro, Mauro C C; Giles, Carlos

2016-06-14

X-ray scattering experiments at room temperature were performed for the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2]. The peak in the diffraction data characteristic of charge ordering in [N1444][NTf2] is shifted to longer distances in comparison to [N1114][NTf2], but the peak characteristic of short-range correlations is shifted in [N1444][NTf2] to shorter distances. Molecular dynamics (MD) simulations were performed for these ionic liquids using force fields available from the literature, although with new sets of partial charges for [N1114](+) and [N1444](+) proposed in this work. The shifting of charge and adjacency peaks to opposite directions in these ionic liquids was found in the static structure factor, S(k), calculated by MD simulations. Despite differences in cation sizes, the MD simulations unravel that anions are allowed as close to [N1444](+) as to [N1114](+) because anions are located in between the angle formed by the butyl chains. The more asymmetric molecular structure of the [N1114](+) cation implies differences in partial structure factors calculated for atoms belonging to polar or non-polar parts of [N1114][NTf2], whereas polar and non-polar structure factors are essentially the same in [N1444][NTf2]. Results of this work shed light on controversies in the literature on the liquid structure of tetraalkylammonium based ionic liquids.

Comparing two tetraalkylammonium ionic liquids. I. Liquid phase structure

NASA Astrophysics Data System (ADS)

Lima, Thamires A.; Paschoal, Vitor H.; Faria, Luiz F. O.; Ribeiro, Mauro C. C.; Giles, Carlos

2016-06-01

X-ray scattering experiments at room temperature were performed for the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2]. The peak in the diffraction data characteristic of charge ordering in [N1444][NTf2] is shifted to longer distances in comparison to [N1114][NTf2], but the peak characteristic of short-range correlations is shifted in [N1444][NTf2] to shorter distances. Molecular dynamics (MD) simulations were performed for these ionic liquids using force fields available from the literature, although with new sets of partial charges for [N1114]+ and [N1444]+ proposed in this work. The shifting of charge and adjacency peaks to opposite directions in these ionic liquids was found in the static structure factor, S(k), calculated by MD simulations. Despite differences in cation sizes, the MD simulations unravel that anions are allowed as close to [N1444]+ as to [N1114]+ because anions are located in between the angle formed by the butyl chains. The more asymmetric molecular structure of the [N1114]+ cation implies differences in partial structure factors calculated for atoms belonging to polar or non-polar parts of [N1114][NTf2], whereas polar and non-polar structure factors are essentially the same in [N1444][NTf2]. Results of this work shed light on controversies in the literature on the liquid structure of tetraalkylammonium based ionic liquids.

40 CFR 63.163 - Standards: Pumps in light liquid service.

Code of Federal Regulations, 2010 CFR

2010-07-01

... handling polymerizing monomers; (B) 2,000 parts per million or greater for pumps in food/medical service... visual inspection each calendar week for indications of liquids dripping from the pump seal. If there are... pump is checked by visual inspection each calendar week for indications of liquids dripping from the...

The kinetics of polyurethane structural foam formation: Foaming and polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rao, Rekha R.; Mondy, Lisa A.; Long, Kevin N.

We are developing kinetic models to understand the manufacturing of polymeric foams, which evolve from low viscosity Newtonian liquids, to bubbly liquids, finally producing solid foam. Closed-form kinetics are formulated and parameterized for PMDI-10, a fast curing polyurethane, including polymerization and foaming. PMDI- 10 is chemically blown, where water and isocyanate react to form carbon dioxide. The isocyanate reacts with polyol in a competing reaction, producing polymer. Our approach is unique, though it builds on our previous work and the polymerization literature. This kinetic model follows a simplified mathematical formalism that decouples foaming and curing, including an evolving glass transitionmore » temperature to represent vitrification. This approach is based on IR, DSC, and volume evolution data, where we observed that the isocyanate is always in excess and does not affect the kinetics. Finally, the kinetics are suitable for implementation into a computational fluid dynamics framework, which will be explored in subsequent papers.« less

The kinetics of polyurethane structural foam formation: Foaming and polymerization

DOE PAGES

Rao, Rekha R.; Mondy, Lisa A.; Long, Kevin N.; ...

2017-02-15

We are developing kinetic models to understand the manufacturing of polymeric foams, which evolve from low viscosity Newtonian liquids, to bubbly liquids, finally producing solid foam. Closed-form kinetics are formulated and parameterized for PMDI-10, a fast curing polyurethane, including polymerization and foaming. PMDI- 10 is chemically blown, where water and isocyanate react to form carbon dioxide. The isocyanate reacts with polyol in a competing reaction, producing polymer. Our approach is unique, though it builds on our previous work and the polymerization literature. This kinetic model follows a simplified mathematical formalism that decouples foaming and curing, including an evolving glass transitionmore » temperature to represent vitrification. This approach is based on IR, DSC, and volume evolution data, where we observed that the isocyanate is always in excess and does not affect the kinetics. Finally, the kinetics are suitable for implementation into a computational fluid dynamics framework, which will be explored in subsequent papers.« less

Conductivity Scaling Relationships of Nanostructured Membranes based on Hydrated Protic Polymerized Ionic Liquids: Effect of Domain Spacing

NASA Astrophysics Data System (ADS)

Sanoja, Gabriel; Popere, Bhooshan; Beckingham, Bryan; Evans, Christopher; Lynd, Nathaniel; Segalman, Rachel

Elucidating the relationship between chemical structure, morphology, and ionic conductivity is essential for designing novel materials for electrochemical applications. In this work, the effect of lamellar domain spacing (d) on ionic conductivity (σ) is investigated for a model system of hydrated block copolymer based on a protic polymerized ionic liquid. We present a strategy that allows for the synthesis of a well-defined series of narrowly dispersed PS- b - PIL with constant volume fraction of ionic liquid moieties (fIL ~ 0.39). These materials self-assemble into ordered lamellar morphologies with variable domain spacing (23-59 nm) as demonstrated by SAXS. PS- b - PIL membranes exhibit ionic conductivities above 10-4 S/cm at room temperature, which are independent of domain spacing. The conductivity scaling relationship demonstrated in this work suggests that a mechanically robust membrane can be designed without compromising its ability to transport ions. In addition, PIL-based membranes exhibit lower water uptake (λ = 10) in comparison with many proton-conducting systems reported elsewhere. The low water content of these materials makes them promising candidates for solar-fuels electrochemical devices.

Dissociation cross section for high energy O2-O2 collisions

NASA Astrophysics Data System (ADS)

Mankodi, T. K.; Bhandarkar, U. V.; Puranik, B. P.

2018-04-01

Collision-induced dissociation cross section database for high energy O2-O2 collisions (up to 30 eV) is generated and published using the quasiclassical trajectory method on the singlet, triplet, and quintet spin ground state O4 potential energy surfaces. At equilibrium conditions, these cross sections predict reaction rate coefficients that match those obtained experimentally. The main advantage of the cross section database based on ab initio computations is in the study of complex flows with high degree of non-equilibrium. Direct simulation Monte Carlo simulations using the reactive cross section databases are carried out for high enthalpy hypersonic oxygen flow over a cylinder at rarefied ambient conditions. A comparative study with the phenomenological total collision energy chemical model is also undertaken to point out the difference and advantage of the reported ab initio reaction model.

Method for inhibiting gum formation in liquid hydrocarbon mediums

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reid, D.K.

1990-07-17

This patent describes a method of inhibiting the formation of gum and sediment in a liquid hydrocarbonaceous medium. It comprises: adding to the medium an inhibiting amount of an alkyl 1,2-dihydroquinoline or polymerized alkyl 1,2-dihydroquinoline.

Modeling collisions in circumstellar debris disks

NASA Astrophysics Data System (ADS)

Nesvold, Erika

2015-10-01

Observations of resolved debris disks show a spectacular variety of features and asymmetries, including inner cavities and gaps, inclined secondary disks or warps, and eccentric, sharp-edged rings. Embedded exoplanets could create many of these features via gravitational perturbations, which sculpt the disk directly and by generating planetesimal collisions. In this thesis, I present the Superparticle Model/Algorithm for Collisions in Kuiper belts and debris disks (SMACK), a new method for simultaneously modeling, in 3-D, the collisional and dynamical evolution of planetesimals in a debris disk with planets. SMACK can simulate azimuthal asymmetries and how these asymmetries evolve over time. I show that SMACK is stable to numerical viscosity and numerical heating over 107 yr, and that it can reproduce analytic models of disk evolution. As an example of the algorithm's capabilities, I use SMACK to model the evolution of a debris ring containing a planet on an eccentric orbit and demonstrate that differential precession creates a spiral structure as the ring evolves, but collisions subsequently break up the spiral, leaving a narrower eccentric ring. To demonstrate SMACK's utility in studying debris disk physics, I apply SMACK to simulate a planet on a circular orbit near a ring of planetesimals that are experiencing destructive collisions. Previous simulations of a planet opening a gap in a collisionless debris disk have found that the width of the gap scales as the planet mass to the 2/7th power (alpha = 2/7). I find that gap sizes in a collisional disk still obey a power law scaling with planet mass, but that the index alpha of the power law depends on the age of the system t relative to the collisional timescale t coll of the disk by alpha = 0.32(t/ tcoll)-0.04, with inferred planet masses up to five times smaller than those predicted by the classical gap law. The increased gap sizes likely stem from the interaction between collisions and the mean motion

Polymerized-type I collagen downregulates inflammation and improves clinical outcomes in patients with symptomatic knee osteoarthritis following arthroscopic lavage: a randomized, double-blind, and placebo-controlled clinical trial.

PubMed

Furuzawa-Carballeda, Janette; Lima, Guadalupe; Llorente, Luis; Nuñez-Álvarez, Carlos; Ruiz-Ordaz, Blanca H; Echevarría-Zuno, Santiago; Hernández-Cuevas, Virgilio

2012-01-01

Polymerized-type I collagen (polymerized collagen) is a downmodulator of inflammation and cartilage regenerator biodrug. To evaluate the effect of intraarticular injections of polymerized collagen after arthroscopic lavage on inflammation and clinical improvement in patients with knee osteoarthritis (OA). Patients (n = 19) were treated with 6 intraarticular injections of 2 mL of polymerized collagen (n = 10) or 2 mL of placebo (n = 9) during 3 months. Followup was 3 months. The primary endpoints included Lequesne index, pain on a visual analogue scale (VAS), WOMAC, analgesic usage, the number of Tregs and proinflammatory/anti-inflammatory cytokine-expressing peripheral cells. Secondary outcomes were Likert score and drug evaluation. Clinical and immunological improvement was determined if the decrease in pain exceeds 20 mm on a VAS, 20% of clinical outcomes, and inflammatory parameters from baseline. Urinary levels of C-terminal crosslinking telopeptide of collagen type II (CTXII) and erythrocyte sedimentation rate (ESR) were determined. Polymerized collagen was safe and well tolerated. Patients had a statistically significant improvement (P < 0.05) from baseline versus polymerized collagen and versus placebo at 6 months on Lequesne index, VAS, ESR, Tregs IL-1β, and IL-10 peripheral-expressing cells. Urinary levels of CTXII were decreased 44% in polymerized collagen versus placebo. No differences were found on incidence of adverse events between groups. Polymerized collagen is safe and effective on downregulation of inflammation in patients with knee OA.

Polymerized-Type I Collagen Downregulates Inflammation and Improves Clinical Outcomes in Patients with Symptomatic Knee Osteoarthritis Following Arthroscopic Lavage: A Randomized, Double-Blind, and Placebo-Controlled Clinical Trial

PubMed Central

Furuzawa-Carballeda, Janette; Lima, Guadalupe; Llorente, Luis; Nuñez-Álvarez, Carlos; Ruiz-Ordaz, Blanca H.; Echevarría-Zuno, Santiago; Hernández-Cuevas, Virgilio

2012-01-01

Objectives. Polymerized-type I collagen (polymerized collagen) is a downmodulator of inflammation and cartilage regenerator biodrug. Aim. To evaluate the effect of intraarticular injections of polymerized collagen after arthroscopic lavage on inflammation and clinical improvement in patients with knee osteoarthritis (OA). Methods. Patients (n = 19) were treated with 6 intraarticular injections of 2 mL of polymerized collagen (n = 10) or 2 mL of placebo (n = 9) during 3 months. Followup was 3 months. The primary endpoints included Lequesne index, pain on a visual analogue scale (VAS), WOMAC, analgesic usage, the number of Tregs and proinflammatory/anti-inflammatory cytokine-expressing peripheral cells. Secondary outcomes were Likert score and drug evaluation. Clinical and immunological improvement was determined if the decrease in pain exceeds 20 mm on a VAS, 20% of clinical outcomes, and inflammatory parameters from baseline. Urinary levels of C-terminal crosslinking telopeptide of collagen type II (CTXII) and erythrocyte sedimentation rate (ESR) were determined. Results. Polymerized collagen was safe and well tolerated. Patients had a statistically significant improvement (P < 0.05) from baseline versus polymerized collagen and versus placebo at 6 months on Lequesne index, VAS, ESR, Tregs IL-1β, and IL-10 peripheral-expressing cells. Urinary levels of CTXII were decreased 44% in polymerized collagen versus placebo. No differences were found on incidence of adverse events between groups. Conclusion. Polymerized collagen is safe and effective on downregulation of inflammation in patients with knee OA. PMID:22545014

Comparing two tetraalkylammonium ionic liquids. I. Liquid phase structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lima, Thamires A.; Paschoal, Vitor H.; Faria, Luiz F. O.

2016-06-14

X-ray scattering experiments at room temperature were performed for the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N{sub 1114}][NTf{sub 2}], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N{sub 1444}][NTf{sub 2}]. The peak in the diffraction data characteristic of charge ordering in [N{sub 1444}][NTf{sub 2}] is shifted to longer distances in comparison to [N{sub 1114}][NTf{sub 2}], but the peak characteristic of short-range correlations is shifted in [N{sub 1444}][NTf{sub 2}] to shorter distances. Molecular dynamics (MD) simulations were performed for these ionic liquids using force fields available from the literature, although with new sets of partial charges for [N{sub 1114}]{sup +} and [N{sub 1444}]{sup +} proposed in this work.more » The shifting of charge and adjacency peaks to opposite directions in these ionic liquids was found in the static structure factor, S(k), calculated by MD simulations. Despite differences in cation sizes, the MD simulations unravel that anions are allowed as close to [N{sub 1444}]{sup +} as to [N{sub 1114}]{sup +} because anions are located in between the angle formed by the butyl chains. The more asymmetric molecular structure of the [N{sub 1114}]{sup +} cation implies differences in partial structure factors calculated for atoms belonging to polar or non-polar parts of [N{sub 1114}][NTf{sub 2}], whereas polar and non-polar structure factors are essentially the same in [N{sub 1444}][NTf{sub 2}]. Results of this work shed light on controversies in the literature on the liquid structure of tetraalkylammonium based ionic liquids.« less

Cationic Bulk Polymerization of Vinyl Ethers in the Liquid Crystalline Phase

DTIC Science & Technology

1991-10-30

mesophase, if any, cannot alone be responsible for the unusual results obtained in this study. Table 3 . Polymerization of’ 2 -[(4-cyano-4’-biphenvl)oxy...NCC 11-H-( /C20 \\ / z 0 h ab cd e f S(7.43-7.47) Li (1.27-1.73) d (6.88-6.93) ab(7.53-7.64) ( 3 8 - , 4 9 h ( 3 .4 4 ) 10 9 8 7 6 5 4 3 2 1 0 Figure...Macromol. Sci.-Rev. Makromol. Chem. 171, 137 (1979) 2 . C. M. Paleos, Chem. Soc. Rev. 14, 45 (1985) 3 . R. G. Weiss, Tetrahedron 44, 3413 (1988) 4. D. J

Polymerization of Building Blocks of Life on Europa and Other Icy Moons.

PubMed

Kimura, Jun; Kitadai, Norio

2015-06-01

The outer Solar System may provide a potential habitat for extraterrestrial life. Remote sensing data from the Galileo spacecraft suggest that the jovian icy moons--Europa, Ganymede, and possibly Callisto--may harbor liquid water oceans underneath their icy crusts. Although compositional information required for the discussion of habitability is limited because of significantly restricted observation data, organic molecules are ubiquitous in the Universe. Recently, in situ spacecraft measurements and experiments suggest that amino acids can be formed abiotically on interstellar ices and comets. These amino acids could be continuously delivered by meteorite or comet impacts to icy moons. Here, we show that polymerization of organic monomers, in particular amino acids and nucleotides, could proceed spontaneously in the cold environment of icy moons, in particular the jovian icy moon Europa as a typical example, based on thermodynamic calculations, though kinetics of formation are not addressed. Observed surface temperature on Europa is 120 and 80 K in the equatorial region and polar region, respectively. At such low temperatures, Gibbs energies of polymerization become negative, and the estimated thermal structure of the icy crust should contain a shallow region (i.e., at a depth of only a few kilometers) favorable for polymerization. Investigation of the possibility of organic monomer polymerization on icy moons could provide good constraints on the origin and early evolution of extraterrestrial life.

In situ AFM investigation of electrochemically induced surface-initiated atom-transfer radical polymerization.

PubMed

Li, Bin; Yu, Bo; Zhou, Feng

2013-02-12

Electrochemically induced surface-initiated atom-transfer radical polymerization is traced by in situ AFM technology for the first time, which allows visualization of the polymer growth process. It affords a fundamental insight into the surface morphology and growth mechanism simultaneously. Using this technique, the polymerization kinetics of two model monomers were studied, namely the anionic 3-sulfopropyl methacrylate potassium salt (SPMA) and the cationic 2-(metharyloyloxy)ethyltrimethylammonium chloride (METAC). The growth of METAC is significantly improved by screening the ammonium cations by the addition of ionic liquid electrolyte in aqueous solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of residual monomers resulting from the chemical polymerization process of dental materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boboia, S.; Moldovan, M.; Ardelean, I.

The residual monomer present in post-polymerized dental materials encourages premature degradation of the reconstructed tooth. That is why the residual monomer should be quantified in a simple, fast, accurate and reproducible manner. In our work we propose such an approach for accurate determination of the residual monomer in dental materials which is based on low-field nuclear magnetic resonance (NMR) relaxometry. The results of the NMR approach are compared with those of the high performance liquid chromatography (HPLC) technique. The samples under study contain the main monomers (2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane and triethylene glycol dimethacrylate) constituting the liquid phase of most dental materials andmore » an initiator. Two samples were analyzed with different ratios of chemical initiation systems: N,N-dimethyl-p-toluide: benzoyl peroxide (1:2 and 0.7:1.2). The results obtained by both techniques highlight that by reducing the initiator the polymerization process slows down and the amount of residual monomer reduces. This prevents the premature degradation of the dental fillings and consequently the reduction of the biomaterial resistance.« less

Photo-responsive polymeric micelles.

PubMed

Huang, Yu; Dong, Ruijiao; Zhu, Xinyuan; Yan, Deyue

2014-09-07

Photo-responsive polymeric micelles have received increasing attention in both academic and industrial fields due to their efficient photo-sensitive nature and unique nanostructure. In view of the photo-reaction mechanism, photo-responsive polymeric micelles can be divided into five major types: (1) photoisomerization polymeric micelles, (2) photo-induced rearrangement polymeric micelles, (3) photocleavage polymeric micelles, (4) photo-induced crosslinkable polymeric micelles, and (5) photo-induced energy conversion polymeric micelles. This review highlights the recent advances of photo-responsive polymeric micelles, including the design, synthesis and applications in various biomedical fields. Especially, the influence of different photo-reaction mechanisms on the morphology, structure and properties of the polymeric micelles is emphasized. Finally, the possible future directions and perspectives in this emerging area are briefly discussed.

Accessing siloxane functionalized polynorbornenes via vinyl-addition polymerization for CO 2 separation membranes

DOE PAGES

Mahurin, Shannon Mark; Sokolov, Alexei P.; Saito, Tomonori; ...

2016-07-06

Here, the vinyl addition polymerization of norbornylbased monomers bearing polar functional groups is often problematic, leading to low molecular weight polymers in poor yield. Herein, we provide proof-of-principle evidence that addition-type homopolymers of siloxane substituted norbornyl-based monomers may be readily synthesized using the catalyst trans-[Ni(C 6F 5) 2(SbPh 3) 2]. Polymerizations using this catalyst reached moderate to high conversion in just 5 min of polymerization and produced siloxanesubstituted polymers with molecular weights exceeding 100 kg/mol. These polymers showed excellent thermal stability (T d ≥ 362 °C) and were cast into membranes that displayed high CO 2 permeability and enhanced COmore » 2/N 2 selectivity as compared to related materials.« less

Synthesis of Highly Polymerized Water-soluble Cellulose Acetate by the Side Reaction in Carboxylate Ionic Liquid 1-ethyl-3-methylimidazolium Acetate

NASA Astrophysics Data System (ADS)

Pang, Jinhui; Liu, Xin; Yang, Jun; Lu, Fachuang; Wang, Bo; Xu, Feng; Ma, Mingguo; Zhang, Xueming

2016-09-01

In the present study, we describe a novel one-step method to prepare water-soluble cellulose acetate (WSCA) with higher degree of polymerization values (DP = 650-680) by in situ activation of carboxyl group in ionic liquid. First of all, cellulose was dissolved in 1-ethyl-3-methylimidazolium acetate (EmimAc) and reacted with dichloroacetyl chloride (Cl2AcCl) in order to make cellulose dichloroacetate. Under various conditions, a series of water soluble products were produced. Elemental analysis and NMR results confirmed that they were cellulose acetate with DS (degree of substitution) values in the range from 0.30 to 0.63. NMR studies demonstrated that Cl2AcCl reacted with acetate anion of EmimAc producing a mixed anhydride that acetylated cellulose. Other acylating reagents such as benzoyl chloride, chloroacetyl chloride can also work similarly. 2D NMR characterization suggested that 6-mono-O-acetyl moiety, 3,6-di-O-acetylcellulose and 2,6-di-O-acetyl cellulose were all synthesized and the reactivity of hydroxyl groups in anhydro-glucose units was in the order C-6>C-3>C-2. This work provides an alternative way to make WSCA, meanwhile, also services as a reminder that the activity of EmimAc toward carbohydrate as acylating reagents could be a problem, because the expected acylated products may not be resulted and recycling of this ionic liquid could also be difficult.

Liquid-Solid Self-Lubricated Coatings

NASA Astrophysics Data System (ADS)

Armada, S.; Schmid, R.; Equey, S.; Fagoaga, I.; Espallargas, N.

2013-02-01

Self-lubricated coatings have been a major topic of interest in thermal spray in the last decades. Self-lubricated coatings obtained by thermal spray are exclusively based on solid lubricants (PTFE, h-BN, graphite, MoS2, etc.) embedded in the matrix. Production of thermal spray coatings containing liquid lubricants has not yet been achieved because of the complexity of keeping a liquid in a solid matrix during the spraying process. In the present article, the first liquid-solid self-lubricating thermal spray coatings are presented. The coatings are produced by inserting lubricant-filled capsules inside a polymeric matrix. The goal of the coating is to release lubricant to the system when needed. The first produced coatings consisted solely of capsules for confirming the feasibility of the process. For obtaining such a coating, the liquid-filled capsules were injected in the thermal spray flame without any other feedstock material. Once the concept and the idea were proven, a polymer was co-sprayed together with the capsules to obtain a coating containing the lubricant-filled capsules distributed in the solid polymeric matrix. The coatings and the self-lubricated properties have been investigated by means of optical microscopy, Scanning Electron Microscopy, and tribological tests.

Stability of dense liquid carbon dioxide.

PubMed

Boates, Brian; Teweldeberhan, Amanuel M; Bonev, Stanimir A

2012-09-11

We present ab initio calculations of the phase diagram of liquid CO(2) and its melting curve over a wide range of pressure and temperature conditions, including those relevant to the Earth. Several distinct liquid phases are predicted up to 200 GPa and 10,000 K based on their structural and electronic characteristics. We provide evidence for a first-order liquid-liquid phase transition with a critical point near 48 GPa and 3,200 K that intersects the mantle geotherm; a liquid-liquid-solid triple point is predicted near 45 GPa and 1,850 K. Unlike known first-order transitions between thermodynamically stable liquids, the coexistence of molecular and polymeric CO(2) phases predicted here is not accompanied by metallization. The absence of an electrical anomaly would be unique among known liquid-liquid transitions. Furthermore, the previously suggested phase separation of CO(2) into its constituent elements at lower mantle conditions is examined by evaluating their Gibbs free energies. We find that liquid CO(2) does not decompose into carbon and oxygen up to at least 200 GPa and 10,000 K.

Nonperturbative Renormalization Group Approach to Polymerized Membranes

NASA Astrophysics Data System (ADS)

Essafi, Karim; Kownacki, Jean-Philippe; Mouhanna, Dominique

2014-03-01

Membranes or membrane-like materials play an important role in many fields ranging from biology to physics. These systems form a very rich domain in statistical physics. The interplay between geometry and thermal fluctuations lead to exciting phases such flat, tubular and disordered flat phases. Roughly speaking, membranes can be divided into two group: fluid membranes in which the molecules are free to diffuse and thus no shear modulus. On the other hand, in polymerized membranes the connectivity is fixed which leads to elastic forces. This difference between fluid and polymerized membranes leads to a difference in their critical behaviour. For instance, fluid membranes are always crumpled, whereas polymerized membranes exhibit a phase transition between a crumpled phase and a flat phase. In this talk, I will focus only on polymerized phantom, i.e. non-self-avoiding, membranes. The critical behaviour of both isotropic and anisotropic polymerized membranes are studied using a nonperturbative renormalization group approach (NPRG). This allows for the investigation of the phase transitions and the low temperature flat phase in any internal dimension D and embedding d. Interestingly, graphene behaves just as a polymerized membrane in its flat phase.

Formation of nanoscale networks: selectively swelling amphiphilic block copolymers with CO2-expanded liquids

NASA Astrophysics Data System (ADS)

Gong, Jianliang; Zhang, Aijuan; Bai, Hua; Zhang, Qingkun; Du, Can; Li, Lei; Hong, Yanzhen; Li, Jun

2013-01-01

Polymeric films with nanoscale networks were prepared by selectively swelling an amphiphilic diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), with the CO2-expanded liquid (CXL), CO2-methanol. The phase behavior of the CO2-methanol system was investigated by both theoretical calculation and experiments, revealing that methanol can be expanded by CO2, forming homogeneous CXL under the experimental conditions. When treated with the CO2-methanol system, the spin cast compact PS-b-P4VP film was transformed into a network with interconnected pores, in a pressure range of 12-20 MPa and a temperature range of 45-60 °C. The formation mechanism of the network, involving plasticization of PS and selective swelling of P4VP, was proposed. Because the diblock copolymer diffusion process is controlled by the activated hopping of individual block copolymer chains with the thermodynamic barrier for moving PVP segments from one to another, the formation of the network structures is achieved in a short time scale and shows ``thermodynamically restricted'' character. Furthermore, the resulting polymer networks were employed as templates, for the preparation of polypyrrole networks, by an electrochemical polymerization process. The prepared porous polypyrrole film was used to fabricate a chemoresistor-type gas sensor which showed high sensitivity towards ammonia.Polymeric films with nanoscale networks were prepared by selectively swelling an amphiphilic diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), with the CO2-expanded liquid (CXL), CO2-methanol. The phase behavior of the CO2-methanol system was investigated by both theoretical calculation and experiments, revealing that methanol can be expanded by CO2, forming homogeneous CXL under the experimental conditions. When treated with the CO2-methanol system, the spin cast compact PS-b-P4VP film was transformed into a network with interconnected pores, in a pressure range of 12-20 MPa and a

Cause Relationships of Collisions and Groundings - Research Project Conclusions,

DTIC Science & Technology

1980-10-01

comparing with the airline industry , tie lack of a safety philosophy in shipping is notable, and there shoul-I be no reason why the demands on safety...KRISTIANSEN UNLSSIFIED 80-PO31 L 1.0 ~2 1.5IIIJI 2 0.KE "PAPER SERIES *r ’$H.O NO .: 80-P031 OCTOBER 1980 CAUSE RELATIONSHIPS OF COLLISIONS AND GROUNDINGS...RELATIONSHIPS PROJECT: OF COLLISIONS AND GROUNDINGS OBJECT: [MEASURES THAT CAN REDUCE THE NO . OF ACCIDENTS WORK ANALYSISIOANA&LYSIS ALF I MODEL INN

Anionic polymerization of oxadiazole-containing 2-vinylpyridine by precisely tuning nucleophilicity and the polyelectrolyte characteristics of the resulting polymers

DOE PAGES

Goodwin, Andrew; Goodwin, Kimberly M.; Wang, Weiyu; ...

2016-09-01

Anionic polymerization is one of the most powerful techniques for preparation of well-defined polymers. However, this well-known and widely employed polymerization technique encounters major limitations for the polymerization of functional monomers containing heteroatoms. This work presents the anionic polymerization of 2-phenyl-5-(6-vinylpyridin-3-yl)-1,3,4-oxadiazole (VPyOzP), a heteroatom monomer that contains both oxadiazole and pyridine substituents within the same pendant group, using various initiating systems based on diphenylmethyl potassium (DPM-K) and triphenylmethyl potassium (TPM-K). Remarkably, well-defined poly(2-phenyl-5-(6-vinylpyridin-3-yl)-1,3,4-oxadiazole) (PVPyOzP) polymers having predicted molecular weights (MW) ranging from 2200 to 21 100 g/mol and polydispersity indices (PDI) ranging from 1.11 to 1.15 were prepared with TPM-K,more » without any additional additives, at –78 °C. The effect of temperature on the polymerization of PVPyOzP was also studied at –78, –45, 0, and 25 °C, and it was observed that increasing the polymerization temperature produced materials with unpredictable MW’s and broader molecular weight distributions. Furthermore, the nucleophilicity of PVPyOzP was investigated through copolymerization with methyl methacrylate and acrylonitrile, where only living poly(methyl methacrylate) (PMMA) prepared by DPM-K/VPPy and in the absence of additives such as lithium chloride (LiCl) and diethyl zinc (ZnEt 2) could be used to produce the well-defined block copolymer of PMMA-b-PVPyOzP. It was also demonstrated by sequential monomer addition that the nucleophilicity of living PVPyOzP is located between that of living PMMA and polyacrylonitrile (PAN). Here, the pyridine moiety of the pendant group also allowed for quaternization and produced PQVPyOzP homopolymer using methyl iodide (CH 3I) and bis(trifluoromethylsulfonyl)amide [Tf 2N –]. The resulting charged polymer and counterion complexes were manipulated and

Anionic polymerization of oxadiazole-containing 2-vinylpyridine by precisely tuning nucleophilicity and the polyelectrolyte characteristics of the resulting polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goodwin, Andrew; Goodwin, Kimberly M.; Wang, Weiyu

Anionic polymerization is one of the most powerful techniques for preparation of well-defined polymers. However, this well-known and widely employed polymerization technique encounters major limitations for the polymerization of functional monomers containing heteroatoms. This work presents the anionic polymerization of 2-phenyl-5-(6-vinylpyridin-3-yl)-1,3,4-oxadiazole (VPyOzP), a heteroatom monomer that contains both oxadiazole and pyridine substituents within the same pendant group, using various initiating systems based on diphenylmethyl potassium (DPM-K) and triphenylmethyl potassium (TPM-K). Remarkably, well-defined poly(2-phenyl-5-(6-vinylpyridin-3-yl)-1,3,4-oxadiazole) (PVPyOzP) polymers having predicted molecular weights (MW) ranging from 2200 to 21 100 g/mol and polydispersity indices (PDI) ranging from 1.11 to 1.15 were prepared with TPM-K,more » without any additional additives, at –78 °C. The effect of temperature on the polymerization of PVPyOzP was also studied at –78, –45, 0, and 25 °C, and it was observed that increasing the polymerization temperature produced materials with unpredictable MW’s and broader molecular weight distributions. Furthermore, the nucleophilicity of PVPyOzP was investigated through copolymerization with methyl methacrylate and acrylonitrile, where only living poly(methyl methacrylate) (PMMA) prepared by DPM-K/VPPy and in the absence of additives such as lithium chloride (LiCl) and diethyl zinc (ZnEt 2) could be used to produce the well-defined block copolymer of PMMA-b-PVPyOzP. It was also demonstrated by sequential monomer addition that the nucleophilicity of living PVPyOzP is located between that of living PMMA and polyacrylonitrile (PAN). Here, the pyridine moiety of the pendant group also allowed for quaternization and produced PQVPyOzP homopolymer using methyl iodide (CH 3I) and bis(trifluoromethylsulfonyl)amide [Tf 2N –]. The resulting charged polymer and counterion complexes were manipulated and

Do nuclear collisions create a locally equilibrated quark–gluon plasma?

DOE PAGES

Romatschke, P.

2017-01-10

Experimental results on azimuthal correlations in high energy nuclear collisions (nucleus–nucleus, proton–nucleus, and proton–proton) seem to be well described by viscous hydrodynamics. It is often argued that this agreement implies either local thermal equilibrium or at least local isotropy. In this note, I present arguments why this is not the case. Neither local near-equilibrium nor near-isotropy are required in order for hydrodynamics to offer a successful and accurate description of experimental results. However, I predict the breakdown of hydrodynamics at momenta of order seven times the temperature, corresponding to a smallest possible QCD liquid drop size of 0.15 fm.

Surfactant-Induced Ordering and Wetting Transitions of Droplets of Thermotropic Liquid Crystals “Caged” Inside Partially Filled Polymeric Capsules

PubMed Central

2015-01-01

We report a study of the wetting and ordering of thermotropic liquid crystal (LC) droplets that are trapped (or “caged”) within micrometer-sized cationic polymeric microcapsules dispersed in aqueous solutions of surfactants. When they were initially dispersed in water, we observed caged, nearly spherical droplets of E7, a nematic LC mixture, to occupy ∼40% of the interior volume of the polymeric capsules [diameter of 6.7 ± 0.3 μm, formed via covalent layer-by-layer assembly of branched polyethylenimine and poly(2-vinyl-4,4-dimethylazlactone)] and to contact the interior surface of the capsule wall at an angle of ∼157 ± 11°. The internal ordering of LC within the droplets corresponded to the so-called bipolar configuration (distorted by contact with the capsule walls). While the effects of dodecyltrimethylammonium bromide (DTAB) and sodium dodecyl sulfate (SDS) on the internal ordering of “free” LC droplets are similar, we observed the two surfactants to trigger strikingly different wetting and configurational transitions when LC droplets were caged within polymeric capsules. Specifically, upon addition of SDS to the aqueous phase, we observed the contact angles (θ) of caged LC on the interior surface of the capsule to decrease, resulting in a progression of complex droplet shapes, including lenses (θ ≈ 130 ± 10°), hemispheres (θ ≈ 89 ± 5°), and concave hemispheres (θ < 85°). The wetting transitions induced by SDS also resulted in changes in the internal ordering of the LC to yield states topologically equivalent to axial and radial configurations. Although topologically equivalent to free droplets, the contributions that surface anchoring, LC elasticity, and topological defects make to the free energy of caged LC droplets differ from those of free droplets. Overall, these results and others reported herein lead us to conclude that caged LC droplets offer a platform for new designs of LC-droplet-based responsive soft matter that cannot

Revealing the Charge Transport Mechanism in Polymerized Ionic Liquids: Insight from High Pressure Conductivity Studies

DOE PAGES

Wojnarowska, Zaneta; Feng, Hongbo; Diaz, Mariana; ...

2017-09-05

Polymerized ionic liquids (polyILs), composed mostly of organic ions covalently bonded to the polymer backbone and free counterions, are considered as an ideal electrolytes for various electrochemical devices, including fuel cells, supercapacitors and batteries. Despite large structural diversity of these systems, all of them reveal a universal but poorly understood feature - a charge transport faster than the segmental dynamics. Here, to address this issue, we have studied three novel polymer electrolyte membrane for fuel cells as well as four single-ion conductors including highly conductive siloxane-based polyIL. Our ambient and high pressure studies revealed fundamental differences in the conducting propertiesmore » of the examined systems. Finally, we demonstrate that the proposed methodology is a powerful tool to identify the charge transport mechanism in polyILs in general and thereby contribute to unraveling the microscopic nature of the decoupling phenomenon in these materials.« less

Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity

DOE PAGES

Gainaru, Catalin P.; Technische Univ. Dortmund, Dortmund; Stacy, Eric W.; ...

2016-09-28

Combining broadband impedance spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance we analyzed charge and mass transport in two polymerized ionic liquids and one of their monomeric precursors. In order to establish a general procedure for extracting single-particle diffusivity from their conductivity spectra, we critically assessed several approaches previously employed to describe the onset of diffusive charge dynamics and of the electrode polarization in ion conducting materials. Based on the analysis of the permittivity spectra, we demonstrate that the conductivity relaxation process provides information on ion diffusion and the magnitude of cross-correlation effects between ionic motions. A new approach ismore » introduced which is able to estimate ionic diffusivities from the characteristic times of conductivity relaxation and ion concentration without any adjustable parameters. Furthermore, this opens the venue for a deeper understanding of charge transport in concentrated and diluted electrolyte solutions.« less

Revealing the Charge Transport Mechanism in Polymerized Ionic Liquids: Insight from High Pressure Conductivity Studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wojnarowska, Zaneta; Feng, Hongbo; Diaz, Mariana

Polymerized ionic liquids (polyILs), composed mostly of organic ions covalently bonded to the polymer backbone and free counterions, are considered as an ideal electrolytes for various electrochemical devices, including fuel cells, supercapacitors and batteries. Despite large structural diversity of these systems, all of them reveal a universal but poorly understood feature - a charge transport faster than the segmental dynamics. Here, to address this issue, we have studied three novel polymer electrolyte membrane for fuel cells as well as four single-ion conductors including highly conductive siloxane-based polyIL. Our ambient and high pressure studies revealed fundamental differences in the conducting propertiesmore » of the examined systems. Finally, we demonstrate that the proposed methodology is a powerful tool to identify the charge transport mechanism in polyILs in general and thereby contribute to unraveling the microscopic nature of the decoupling phenomenon in these materials.« less

Characterization of the aroma profile of novel Brazilian wines by solid-phase microextraction using polymeric ionic liquid sorbent coatings.

PubMed

Crucello, Juliana; Miron, Luiz F O; Ferreira, Victor H C; Nan, He; Marques, Marcia O M; Ritschel, Patricia S; Zanus, Mauro C; Anderson, Jared L; Poppi, Ronei J; Hantao, Leandro W

2018-05-28

In this study, a series of polymeric ionic liquid (PIL) sorbent coatings is evaluated for the extraction of polar volatile organic compounds (VOCs) from Brazilian wines using headspace solid-phase microextraction (HS-SPME), including samples from 'Isabella' and 'BRS Magna' cultivars-the latter was recently introduced by the Brazilian Agricultural Research Corporation - National Grape & Wine Research Center. The structurally tuned SPME coatings were compared to the commercial SPME phases, namely poly(acrylate) (PA) and divinylbenzene/carboxen/poly(dimethylsiloxane) (DVB/CAR/PDMS). The separation, detection and identification of the aroma profiles were obtained using comprehensive two-dimensional gas chromatography mass spectrometry (GC×GC-MS). The best performing PIL-based SPME fiber, namely 1-hexadecyl-3-vinylimidazolium bis[(trifluoromethyl)sulfonyl]imide with 1,12-di(3-vinylimidazolium)dodecane dibis[(trifluoromethyl)sulfonyl]imide incorporated cross-linker supported on an elastic nitinol wire, exhibited superior performance to DVB/CAR/PDMS regarding the average number of extracted peaks and extracted more polar analytes providing additional insight into the aroma profile of 'BRS Magna' wines. Four batches of wine were evaluated, namely 'Isabella' and 'BRS Magna' vintages 2015 and 2016, using highly selective PIL-based SPME coatings and enabled the detection of 350+ peaks. Furthermore, this is the first report evaluating the aroma of 'BRS Magna' wines. A hybrid approach that combined pixel-based Fisher ratio and peak table-based data comparison was used for data handling. This proof-of-concept experiment provided reliable and statistically valid distinction of wines that may guide regulation agencies to create high sample throughput protocols to screen wines exported by Brazilian vintners. Graphical abstract Highly selective extraction of wine aroma using polymeric ionic liquid.

Molecular continua for polymeric liquids in large-amplitude oscillatory shear flow

NASA Astrophysics Data System (ADS)

Giacomin, A. Jeffrey; Saengow, Chaimongkol

2018-05-01

In this paper, we connect a molecular description of the rheology of a polymeric liquid to a continuum description, and then test this connection for large-amplitude oscillatory shear (LAOS) flow. Specifically, for the continuum description, we use the 6-constant Oldroyd framework, and for the molecular, we use the simplest relevant molecular model, the suspension of rigid dumbbells. By relevant, we mean predicting at least higher harmonics in the shear stress response in LAOS. We call this connection a molecular continuum, and we examine two ways of arriving at this connection. The first goes through the retarded motion expansion, and the second expands each of a set of specific material functions (complex, steady shear, and steady uniaxial extensional viscosities). Both ways involve in comparing the coefficients of expansions and then solve for the six constants of the continuum framework in terms of the two constants of the rigid dumbbell suspension. The purpose of a molecular continuum is that many well-known results for rigid dumbbell suspensions in other flow fields can also be easily obtained, without having to firstly find the orientation distribution function. In this paper, we focus on the recent result for the rigid dumbbell suspension in LAOS. We compare the accuracies of the retarded motion molecular continuum (RMMC) with the material function molecular continuum (MFMC). We find the RMMC to be the most accurate for LAOS.

Electro-Optical Characterization of Bistable Smectic A Liquid Crystal Displays

NASA Astrophysics Data System (ADS)

Buyuktanir, Ebru Aylin

My dissertation focuses the characterization and optimization of the electro-optical properties of smectic A (SmA) based liquid crystal (LC) displays. I present the development of robust and flexible bistable SmA LC displays utilizing polymer dispersed liquid crystal (PDLC) technology. The SmA PDLC displays produced on plastic substrates present electrically reversible memory, high contrast ratio, paper-like sunlight readability, and wide viewing angle characteristics. In order to optimize the SmA PDLC display, I investigated polymerization conditions, such as polymer concentration effect, polymerization temperature, and UV-light intensity variations. I characterized the electro-optical responses-such as static-response, time-response, threshold characteristics, and contrast ratio values' of the optimized SmA PDLC display and compared them to those of the pure SmA LC. The best electro-optical performance of SmA PDLC formulation was obtained using the combination of low mW/cm 2 and high mW/cm2 UV-light curing intensity. The contrast ratio of the optimum SmA PDLC at a 5o collection angle was 83% of that of the pure SmA material on plastic substrates. I fabricated 2.5 x 2.5 in., 4 x 4 in., and 6 x 6 in. sized monochrome flexible SmA PDLC displays, as well as red, yellow, and fluorescent dyes colored SmA PDLC displays on plastic substrates. The electro-optic performance of the bistable SmA LC display consisting of a patterned field-induced polymer wall infrastructure was also studied and compared to those of pure SmA material. I found that the contrast ratio of the SmA LC encapsulated between polymer walls was much greater than that of the SmA PDLC system, approaching the contrast ratio value of the pure SmA material. I also improved the electro-optical characteristics of bistable SmA LC displays by adding ferroparticles into the system. Finally, I illustrated the unique capabilities of polarized confocal Raman microscopy (CRM) to resolve the orientational order of Sm

A novel task specific magnetic polymeric ionic liquid for selective preconcentration of potassium in oil samples using centrifuge-less dispersive liquid-liquid microextraction technique and its determination by flame atomic emission spectroscopy.

PubMed

Beiraghi, Asadollah; Shokri, Masood

2018-02-01

In the present study a new centrifuge-less dispersive liquid-liquid microextraction technique based on application of a new task specific magnetic polymeric ionic liquid (TSMPIL) as a chelating and extraction solvent for selective preconcentration of trace amounts of potassium from oil samples is developed, for the first time. After extraction, the fine droplets of TSMPIL were transferred into an eppendorf tube and diluted to 500µL using distilled water. Then, the enriched analyte was determined by flame atomic emission spectroscopy (FAES). Several important factors affecting both the complexation and extraction efficiency including extraction time, rate of vortex agitator, amount of carbonyl iron powder, pH of sample solution, volume of ionic liquid as well as effects of interfering species were investigated and optimized. Under the optimal conditions, the limits of detection (LOD) and quantification (LOQ) were 0.5 and 1.6µgL -1 respectively with the preconcentration factor of 128. The precision (RSD %) for seven replicate determinations at 10µgL -1 of potassium was better than 3.9%. The relative recoveries for the spiked samples were in the acceptable range of 95-104%. The results demonstrated that no remarkable interferences are created by other various ions in the determination of potassium, so that the tolerance limits (W Ion /W K ) of major cations and anions were in the range of 2500-10,000. The purposed method was successfully applied for the analysis of potassium in some oil samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Facile preparation of a stable and functionalizable hybrid monolith via ring-opening polymerization for capillary liquid chromatography.

PubMed

Lin, Hui; Ou, Junjie; Tang, Shouwan; Zhang, Zhenbin; Dong, Jing; Liu, Zhongshan; Zou, Hanfa

2013-08-02

An organic-inorganic hybrid monolith was prepared by a single-step ring-opening polymerization of octaglycidyldimethylsilyl polyhedral oligomeric silsesquioxane (POSS) with poly(ethylenimine) (PEI). The obtained hybrid monoliths possessed high ordered 3D skeletal microstructure with dual retention mechanism that exhibits reversed-phase (RP) mechanism under polar mobile phase and hydrophilic-interaction liquid chromatography (HILIC) retention mechanism under less polar mobile phase. The high column efficiencies of 110,000N/m can be achieved for separation of alkylbenzenes in capillary reversed-phase liquid chromatography (cLC). Due to the robust property of hybrid monolith and the rich primary and secondary amino groups on its surface, the resulting hybrid monolith was easily modified with γ-gluconolactone and physically coated with cellulose tris(3,5-dimethylphenylcarbamate) (CDMPC), respectively. The former was successfully applied for HILIC separation of neutral, basic and acidic polar compounds as well as small peptides, and the latter for enantioseparation of racemates in cLC. The high column efficiencies were achieved in all of those separations. These results demonstrated that the hybrid monolith (POSS-PEI) possessed high stability and good surface tailorbility, potentially being applied for other research fields. Copyright © 2013 Elsevier B.V. All rights reserved.

Liquid Crystalline Polymers Containing Heterocycloalkane Mesogens. 1. Side-Chain Liquid Crystalline Polymethacrylates and Polycrylates Containing 2,5-Disubstituted-1,3-Dioxane Mesogens.

DTIC Science & Technology

1986-10-01

Report No. 2 Liquid Crystalline Polymers Containing Heterocycloalkane Mesogeus 1. Side-Chain Liquid Crystalline Polymethacrylates and . Polyacrylates...8217. " "-"-"-" " "" ’CS" i Liquid Crystalline Polymers Containing Heterocycloalkane Mesogens 1. Side-Chain Liquid Crystalline Polymethacrylates and Polyacrylates...University Cleveland, OH 44106 ABSTRACT Polymethacrylates and polyacrylates containing 2-(p-hydroxyphenyl)-5-(p-meth- oxyphenyl)-1,3-dioxane as a

Wind collisions in three massive stars of Cygnus OB2

NASA Astrophysics Data System (ADS)

Cazorla, Constantin; Nazé, Yaël; Rauw, Gregor

2014-01-01

Aims: We wish to study the origin of the X-ray emission of three massive stars in the Cyg OB2 association: Cyg OB2 #5, Cyg OB2 #8A, and Cyg OB2 #12. Methods: To this aim, dedicated X-ray observations from XMM-Newton and Swift are used, as well as archival ROSAT and Suzaku data. Results: Our results on Cyg OB2 #8A improve the phase coverage of the orbit and confirm previous studies: the signature of a wind-wind collision is conspicuous. In addition, signatures of a wind-wind collision are also detected in Cyg OB2 #5, but the X-ray emission appears to be associated with the collision between the inner binary and the tertiary component orbiting it with a 6.7 yr period, without a putative collision inside the binary. The X-ray properties strongly constrain the orbital parameters, notably allowing us to discard some proposed orbital solutions. To improve the knowledge of the orbit, we revisit the light curves and radial velocity of the inner binary, looking for reflex motion induced by the third star. Finally, the X-ray emission of Cyg OB2 #12 is also analyzed. It shows a marked decrease in recent years, compatible with either a wind-wind collision in a wide binary or the aftermath of a recent eruption. Based on observations collected at the Observatoire de Haute Provence (OHP) as well as with Swift and XMM-Newton.Tables 1-3 and 5 are available in electronic form at http://www.aanda.org

Influence of Chain Rigidity and Dielectric Constant on the Glass Transition Temperature in Polymerized Ionic Liquids

DOE PAGES

Bocharova, V.; Wojnarowska, Z.; Cao, Peng-Fei; ...

2017-11-28

Polymerized ionic liquids (PolyILs) are promising candidates for a wide range of technological applications due to their single ion conductivity and good mechanical properties. Tuning the glass transition temperature (T g) in these materials constitutes a major strategy to improve room temperature conductivity while controlling their mechanical properties. In this paper, we show experimental and simulation results demonstrating that in these materials T g does not follow a universal scaling behavior with the volume of the structural units V m (including monomer and counterion). Instead, T g is significantly influenced by the chain flexibility and polymer dielectric constant. We proposemore » a simplified empirical model that includes the electrostatic interactions and chain flexibility to describe T g in PolyILs. Finally, our model enables design of new functional PolyILs with the desired T g.« less

Influence of Chain Rigidity and Dielectric Constant on the Glass Transition Temperature in Polymerized Ionic Liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bocharova, V.; Wojnarowska, Z.; Cao, Peng-Fei

Polymerized ionic liquids (PolyILs) are promising candidates for a wide range of technological applications due to their single ion conductivity and good mechanical properties. Tuning the glass transition temperature (T g) in these materials constitutes a major strategy to improve room temperature conductivity while controlling their mechanical properties. In this paper, we show experimental and simulation results demonstrating that in these materials T g does not follow a universal scaling behavior with the volume of the structural units V m (including monomer and counterion). Instead, T g is significantly influenced by the chain flexibility and polymer dielectric constant. We proposemore » a simplified empirical model that includes the electrostatic interactions and chain flexibility to describe T g in PolyILs. Finally, our model enables design of new functional PolyILs with the desired T g.« less

Dicationic polymeric ionic-liquid-based magnetic material as an adsorbent for the magnetic solid-phase extraction of organophosphate pesticides and polycyclic aromatic hydrocarbons.

PubMed

Jiang, Qiong; Liu, Qin; Chen, Qiliang; Zhao, Wenjie; Xiang, Guoqiang; He, Lijun; Jiang, Xiuming; Zhang, Shusheng

2016-08-01

Magnetic particles modified with a dicationic polymeric ionic liquid are described as a new adsorbent in magnetic solid-phase extraction. They were obtained through the copolymerization of a 1,8-di(3-vinylimidazolium)octane-based ionic liquid with vinyl-modified SiO2 @Fe3 O4 , and were characterized by FTIR spectroscopy, X-ray diffraction, and vibrating sample magnetometry. The modified magnetic particles are effective in the extraction of organophosphate pesticides and polycyclic aromatic hydrocarbons. Also, they can provide different extraction performance for the selected analytes including fenitrothion, parathion, fenthion, phoxim, phenanthrene, and fluoranthene, where the extraction efficiency is found to be in agreement with the hydrophobicity of analytes. Various factors influencing the extraction efficiency, such as, the amount of adsorbent, extraction, and desorption time, and type and volume of the desorption solvent, were optimized. Under the optimized conditions, a good linearity ranging from 1-100 μg/L is obtained for all analytes, except for parathion (2-200 μg/L), where the correlation coefficients varied from 0.9960 to 0.9998. The limits of detection are 0.2-0.8 μg/L, and intraday and interday relative standard deviations are 1.7-7.4% (n = 5) and 3.8-8.0% (n = 3), respectively. The magnetic solid-phase extraction combined with high-performance liquid chromatography can be applied for the detection of trace targets in real water samples with satisfactory relative recoveries and relative standard deviations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of amine structure on CO2 capture by polymeric membranes.

PubMed

Taniguchi, Ikuo; Kinugasa, Kae; Toyoda, Mariko; Minezaki, Koki

2017-01-01

Poly(amidoamine)s (PAMAMs) incorporated into a cross-linked poly(ethylene glycol) exhibited excellent CO 2 separation properties over H 2 . However, the CO 2 permeability should be increased for practical applications. Monoethanolamine (MEA) used as a CO 2 determining agent in the current CO 2 capture technology at demonstration scale was readily immobilized in poly(vinyl alcohol) (PVA) matrix by solvent casting of aqueous mixture of PVA and the amine. The resulting polymeric membranes can be self-standing with the thickness above 3 μm and the amine fraction less than 80 wt%. The gas permeation properties were examined at 40 °C and under 80% relative humidity. The CO 2 separation performance increased with increase of the amine content in the polymeric membranes. When the amine fraction was 80 wt%, the CO 2 permeability coefficient of MEA containing membrane was 604 barrer with CO 2 selectivity of 58.5 over H 2 , which was much higher than the PAMAM membrane (83.7 barrer and 51.8, respectively) under the same operation conditions. On the other hand, ethylamine (EA) was also incorporated into PVA matrix to form a thin membrane. However, the resulting polymeric membranes exhibited slight CO 2 -selective gas permeation properties. The hydroxyl group of MEA was crucial for high CO 2 separation performance.

Effect of amine structure on CO2 capture by polymeric membranes

PubMed Central

Taniguchi, Ikuo; Kinugasa, Kae; Toyoda, Mariko; Minezaki, Koki

2017-01-01

Abstract Poly(amidoamine)s (PAMAMs) incorporated into a cross-linked poly(ethylene glycol) exhibited excellent CO2 separation properties over H2. However, the CO2 permeability should be increased for practical applications. Monoethanolamine (MEA) used as a CO2 determining agent in the current CO2 capture technology at demonstration scale was readily immobilized in poly(vinyl alcohol) (PVA) matrix by solvent casting of aqueous mixture of PVA and the amine. The resulting polymeric membranes can be self-standing with the thickness above 3 μm and the amine fraction less than 80 wt%. The gas permeation properties were examined at 40 °C and under 80% relative humidity. The CO2 separation performance increased with increase of the amine content in the polymeric membranes. When the amine fraction was 80 wt%, the CO2 permeability coefficient of MEA containing membrane was 604 barrer with CO2 selectivity of 58.5 over H2, which was much higher than the PAMAM membrane (83.7 barrer and 51.8, respectively) under the same operation conditions. On the other hand, ethylamine (EA) was also incorporated into PVA matrix to form a thin membrane. However, the resulting polymeric membranes exhibited slight CO2-selective gas permeation properties. The hydroxyl group of MEA was crucial for high CO2 separation performance. PMID:29383045

Polyphosphoester-Camptothecin Prodrug with Reduction-Response Prepared via Michael Addition Polymerization and Click Reaction.

PubMed

Du, Xueqiong; Sun, Yue; Zhang, Mingzu; He, Jinlin; Ni, Peihong

2017-04-26

Polyphosphoesters (PPEs), as potential candidates for biocompatible and biodegradable polymers, play an important role in material science. Various synthetic methods have been employed in the preparation of PPEs such as polycondensation, polyaddition, ring-opening polymerization, and olefin metathesis polymerization. In this study, a series of linear PPEs has been prepared via one-step Michael addition polymerization. Subsequently, camptothecin (CPT) derivatives containing disulfide bonds and azido groups were linked onto the side chain of the PPE through Cu(I)-catalyzed azidealkyne cyclo-addition "click" chemistry to yield a reduction-responsive polymeric prodrug P(EAEP-PPA)-g-ss-CPT. The chemical structures were characterized by nuclear magnetic resonance spectroscopy, gel permeation chromatography, Fourier transform infrared, ultraviolet-visible spectrophotometer, and high performance liquid chromatograph analyses, respectively. The amphiphilic prodrug could self-assemble into micelles in aqueous solution. The average particle size and morphology of the prodrug micelles were measured by dynamic light scattering and transmission electron microscopy, respectively. The results of size change under different conditions indicate that the micelles possess a favorable stability in physiological conditions and can be degraded in reductive medium. Moreover, the studies of in vitro drug release behavior confirm the reduction-responsive degradation of the prodrug micelles. A methyl thiazolyl tetrazolium assay verifies the good biocompatibility of P(EAEP-PPA) not only for normal cells, but also for tumor cells. The results of cytotoxicity and the intracellular uptake about prodrug micelles further demonstrate that the prodrug micelles can efficiently release CPT into 4T1 or HepG2 cells to inhibit the cell proliferation. All these results show that the polyphosphoester-based prodrug can be used for triggered drug delivery system in cancer treatment.

Rotational and translational effects in collisions of electronically excited diatomic hydrides

NASA Technical Reports Server (NTRS)

Crosley, David R.

1988-01-01

Collisional quenching and vibrational energy proceed competitively with rotational energy transfer for several excited states of the diatomic radicals OH, NH, and CH. This occurs for a wide variety of molecular collision partners. This phenomenon permits the examination of the influence of rotational motion on the collision dynamics of these theoretically tractable species. Measurements can also be made as a function of temperature, i.e., collision velocity. In OH (sup 2 sigma +), both vibrational transfer and quenching are found to decrease with an increase in rotational level, while quenching decreases with increasing temperature. This behavior indicates that for OH, anisotropic attractive forces govern the entrance channel dynamics for these collisions. The quenching of NH (sup 3 pi sub i) by many (although not all) collision partners also decreases with increasing rotational and translational energy, and NH (sup 1 pi) behaves much like OH (sup 2 sigma +). However, the quenching of CH (sup 2 delta) appears to decrease with increasing rotation but increases with increasing temperature, suggesting in this case anisotropic forces involving a barrier or repulsive wall. Such similarities and differences should furnish useful comparisons with both simple and detailed theoretical pictures of the appropriate collision dynamics.

Polymerization of Building Blocks of Life on Europa and Other Icy Moons

PubMed Central

Kitadai, Norio

2015-01-01

Abstract The outer Solar System may provide a potential habitat for extraterrestrial life. Remote sensing data from the Galileo spacecraft suggest that the jovian icy moons—Europa, Ganymede, and possibly Callisto—may harbor liquid water oceans underneath their icy crusts. Although compositional information required for the discussion of habitability is limited because of significantly restricted observation data, organic molecules are ubiquitous in the Universe. Recently, in situ spacecraft measurements and experiments suggest that amino acids can be formed abiotically on interstellar ices and comets. These amino acids could be continuously delivered by meteorite or comet impacts to icy moons. Here, we show that polymerization of organic monomers, in particular amino acids and nucleotides, could proceed spontaneously in the cold environment of icy moons, in particular the jovian icy moon Europa as a typical example, based on thermodynamic calculations, though kinetics of formation are not addressed. Observed surface temperature on Europa is 120 and 80 K in the equatorial region and polar region, respectively. At such low temperatures, Gibbs energies of polymerization become negative, and the estimated thermal structure of the icy crust should contain a shallow region (i.e., at a depth of only a few kilometers) favorable for polymerization. Investigation of the possibility of organic monomer polymerization on icy moons could provide good constraints on the origin and early evolution of extraterrestrial life. Key Words: Planetary science—Europa—Planetary habitability and biosignatures—Extraterrestrial life—Extraterrestrial organic compounds. Astrobiology 15, 430–441. PMID:26060981

Probing nanoscale ion dynamics in ultrathin films of polymerized ionic liquids by broadband dielectric spectroscopy

NASA Astrophysics Data System (ADS)

Sangoro, Joshua; Heres, Maximilian; Cosby, Tyler

Continuous progress in energy storage and conversion technologies necessitates novel experimental approaches that can provide fundamental insights regarding the impact of reduced dimensions on the functional properties of materials. In this talk, a nondestructive experimental approach to probe nanoscale ion dynamics in ultrathin films of polymerized ionic liquids over a broad frequency range spanning over six orders of magnitude by broadband dielectric spectroscopy will be presented. The approach involves using an electrode configuration with lithographically patterned silica nanostructures, which allow for an air gap between the confined ion conductor and one of the electrodes. It is observed that the characteristic ion dynamics rates significantly slow down with decreasing film thicknesses above the calorimetric glass transition of the bulk polymer. However, the mean rates remain bulk-like at lower temperatures. These results highlight the increasing influence of the polymer/substrate interactions with decreasing film thickness on ion dynamics. The authors gratefully acknowledge the National Science Foundation for financial support through the Polymers Program award DMR-1508394.

Sampling trace-level organic solutes with polymeric tubing. Part 2: Dynamic studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parker, L.V.; Ranney, T.A.

1998-12-31

This is the second part of a study conducted to determine whether polymeric sampling tubing can affect organic analyte concentrations during a sampling event. In this part of the study, the authors looked for sorption and desorption of trichloroethylene (TCE) and leaching of organic constituents in water pumped through five types of polymeric tubing. The materials tested were a rigid fluoropolymer, a flexible fluoropolymer, low-density polyethylene (LDPE), and two plasticized polypropylene tubings. The effects of tubing length and flow rate were examined. The least sorptive tubings, both initially and at equilibrium, were the fluoropolymers. However, in some instances the LDPEmore » tubing had little effect on TCE concentrations. This was when a slow flow rate was used to sample relatively shallow wells (50 feet [15 m] or less) or when a faster flow rate (1 L/min) was used to sample wells that are less than 500 feet (152 m). Further testing is recommended using more sorptive analytes. Using high performance liquid chromatography (HPLC), the authors were unable to detect any constituents leaching from any of the tubings used in these studies, even when a slow flow rate was used. However, desorption of sorbed analytes is a concern for all the tubings tested, including the rigid fluoropolymer.« less

A novel function of twins, B subunit of protein phosphatase 2A, in regulating actin polymerization.

PubMed

Yeh, Po-An; Chang, Ching-Jin

2017-01-01

Actin is an important component of the cytoskeleton and its polymerization is delicately regulated by several kinases and phosphatases. Heterotrimeric protein phosphatase 2A (PP2A) is a potent phosphatase that is crucial for cell proliferation, apoptosis, tumorigenesis, signal transduction, cytoskeleton arrangement, and neurodegeneration. To facilitate these varied functions, different regulators determine the different targets of PP2A. Among these regulators of PP2A, the B subunits in particular may be involved in cytoskeleton arrangement. However, little is known about the role of PP2A in actin polymerization in vivo. Using sophisticated fly genetics, we demonstrated a novel function for the fly B subunit, twins, to promote actin polymerization in varied tissue types, suggesting a broad and conserved effect. Furthermore, our genetic data suggest that twins may act upstream of the actin-polymerized-proteins, Moesin and Myosin-light-chain, and downstream of Rho to promote actin polymerization. This work opens a new avenue for exploring the biological functions of a PP2A regulator, twins, in cytoskeleton regulation.

A novel function of twins, B subunit of protein phosphatase 2A, in regulating actin polymerization

PubMed Central

Chang, Ching-Jin

2017-01-01

Actin is an important component of the cytoskeleton and its polymerization is delicately regulated by several kinases and phosphatases. Heterotrimeric protein phosphatase 2A (PP2A) is a potent phosphatase that is crucial for cell proliferation, apoptosis, tumorigenesis, signal transduction, cytoskeleton arrangement, and neurodegeneration. To facilitate these varied functions, different regulators determine the different targets of PP2A. Among these regulators of PP2A, the B subunits in particular may be involved in cytoskeleton arrangement. However, little is known about the role of PP2A in actin polymerization in vivo. Using sophisticated fly genetics, we demonstrated a novel function for the fly B subunit, twins, to promote actin polymerization in varied tissue types, suggesting a broad and conserved effect. Furthermore, our genetic data suggest that twins may act upstream of the actin-polymerized-proteins, Moesin and Myosin-light-chain, and downstream of Rho to promote actin polymerization. This work opens a new avenue for exploring the biological functions of a PP2A regulator, twins, in cytoskeleton regulation. PMID:28977036

Photoinitiated polymerization of 1-vinylimidazole

DOE Office of Scientific and Technical Information (OSTI.GOV)

Joshi, M.G.; Rodriguez, F.

1984-04-01

The photoinitiated polymerization of 1-vinylimidazole (VI) does not follow the classical kinetic scheme for free radical polymerization. Kinetic results for VI suggest a degradative addition reaction between the macroradical and the monomer to produce a relatively stable, unreactive radical, which does not reinitiate polymerization, is low, 1.5 kcal/mol. Among the 3 photoinitiators used, the highest quantum efficiency was demonstrated by 2,2'-diethoxyacetophenone followed by bezoin methyl ether and benzoin isopropyl ether. Under the experimental conditions used, the polymerization of VI does not proceed to complete conversion, and the phenomenon of dead-end polymerization is observed.

Comparison of pediatric motor vehicle collision injury outcomes at Level I trauma centers.

PubMed

Dreyfus, Jill; Flood, Andrew; Cutler, Gretchen; Ortega, Henry; Kreykes, Nathan; Kharbanda, Anupam

2016-10-01

Examine the association of American College of Surgeons Level I pediatric trauma center designation with outcomes of pediatric motor vehicle collision-related injuries. Observational study of the 2009-2012 National Trauma Data Bank, including n=28,145 patients <18years directly transported to a Level I trauma center. Generalized estimating equations estimated odds ratios (ORs) for injury outcomes, comparing freestanding pediatric trauma centers (PTCs) with adult centers having added Level I pediatric qualifications (ATC+PTC) and general adult trauma centers (ATC). Models were stratified by age following PTC designation guidelines, and adjusted for demographic and clinical risk factors. Analyses included n=16,643 children <15 and n=11,502 adolescents 15-17years. Among children, odds of laparotomy (OR=1.88, 95% CI 1.28-2.74) and pneumonia (OR=2.13, 95% CI 1.32-3.46) were greater at ATCs vs. freestanding PTCs. Adolescents treated at ATC+PTCs or ATCs experienced greater odds of death (OR=2.18, 95% CI 1.30-3.67; OR=1.98, 95% CI 1.37-2.85, respectively) and laparotomy (OR=4.33, 95% CI 1.56-12.02; OR=5.11, 95% CI 1.92-13.61, respectively). Compared with freestanding PTCs, children treated at general ATCs experienced more complications; adolescents treated at ATC+PTCs or general ATCs had greater odds of death. Identification and sharing of best practices among Level I trauma centers may reduce variation in care and improve outcomes for children. Copyright © 2016 Elsevier Inc. All rights reserved.

A Model-based B2B (Batch to Batch) Control for An Industrial Batch Polymerization Process

NASA Astrophysics Data System (ADS)

Ogawa, Morimasa

This paper describes overview of a model-based B2B (batch to batch) control for an industrial batch polymerization process. In order to control the reaction temperature precisely, several methods based on the rigorous process dynamics model are employed at all design stage of the B2B control, such as modeling and parameter estimation of the reaction kinetics which is one of the important part of the process dynamics model. The designed B2B control consists of the gain scheduled I-PD/II2-PD control (I-PD with double integral control), the feed-forward compensation at the batch start time, and the model adaptation utilizing the results of the last batch operation. Throughout the actual batch operations, the B2B control provides superior control performance compared with that of conventional control methods.

Application of Symmetry-Broken H2-H2 Potential Energy Surface to Low Energy o-/p-H2+HD Collisions of Astrophysical Interest

NASA Astrophysics Data System (ADS)

Sultanov, R. A.; Guster, D.; Adhukari, S. K.

2011-05-01

A possibility of correct description of non-symmetrical HD+H2 collision at low temperatures (T≤300 K) is considered by applying symmetrical H2-H2 potential energy surface (PES) [Diep, P. & Johnson, K. 2000, J. Chem. Phys. 113, 3480 (DJ PES)]. With the use of a special mathematical transformation technique, which was applied to this surface, and a quantum dynamical method we obtained a quite satisfactory agreement with previous results when another H2-H2 PES was used [Boothroyd, A.I. et al. 2002, J. Chem. Phys. 116, 666 (BMKP PES)].

Chemical dynamics simulations of the monohydrated OH-(H2O) + CH3I reaction. Atomic-level mechanisms and comparison with experiment

NASA Astrophysics Data System (ADS)

Xie, Jing; Otto, Rico; Wester, Roland; Hase, William L.

2015-06-01

Direct dynamics simulations, with B97-1/ECP/d theory, were performed to study the role of microsolvation for the OH-(H2O) + CH3I reaction. The SN2 reaction dominates at all reactant collision energies, but at higher collision energies proton transfer to form CH2I-, and to a lesser extent CH2I- (H2O), becomes important. The SN2 reaction occurs by direct rebound and stripping mechanisms, and 28 different indirect atomistic mechanisms, with the latter dominating. Important components of the indirect mechanisms are the roundabout and formation of SN2 and proton transfer pre-reaction complexes and intermediates, including [CH3--I--OH]-. In contrast, for the unsolvated OH- + CH3I SN2 reaction, there are only seven indirect atomistic mechanisms and the direct mechanisms dominate. Overall, the simulation results for the OH-(H2O) + CH3IߙSN2 reaction are in good agreement with experiment with respect to reaction rate constant, product branching ratio, etc. Differences between simulation and experiment are present for the SN2 velocity scattering angle at high collision energies and the proton transfer probability at low collision energies. Equilibrium solvation by the H2O molecule is unimportant. The SN2 reaction is dominated by events in which H2O leaves the reactive system as CH3OH is formed or before CH3OH formation. Formation of solvated products is unimportant and participation of the (H2O)CH3OH---I- post-reaction complex for the SN2 reaction is negligible.

Nanoparticles and nonlinear thermal radiation properties in the rheology of polymeric material

NASA Astrophysics Data System (ADS)

Awais, M.; Hayat, T.; Muqaddass, N.; Ali, A.; Aqsa; Awan, Saeed Ehsan

2018-03-01

The present analysis is related to the dynamics of polymeric liquids (Oldroyd-B model) with the presence of nanoparticles. The rheological system is considered under the application of nonlinear thermal radiations. Energy and concentration equations are presented when thermophoresis and Brownian motion effects are present. Bidirectional form of stretching is considered to interpret the three-dimensional flow dynamics of polymeric liquid. Making use of the similarity transformations, problem is reduced into ordinary differential system which is approximated by using HAM. Influence of physical parameters including Deborah number, thermophoresis and Brownian motion on velocity, temperature and mass fraction expressions are plotted and analyzed. Numerical values for local Sherwood and Nusselt numbers are presented and discussed.

Incorporation of ionic liquid into porous polymer monoliths to enhance the separation of small molecules in reversed-phase high-performance liquid chromatography.

PubMed

Wang, Jiafei; Bai, Ligai; Wei, Zhen; Qin, Junxiao; Ma, Yamin; Liu, Haiyan

2015-06-01

An ionic liquid was incorporated into the porous polymer monoliths to afford stationary phases with enhanced chromatographic performance for small molecules in reversed-phase high-performance liquid chromatography. The effect of the ionic liquid in the polymerization mixture on the performance of the monoliths was studied in detail. While monoliths without ionic liquid exhibited poor resolution and low efficiency, the addition of ionic liquid to the polymerization mixture provides highly increased resolution and high efficiency. The chromatographic performances of the monoliths were demonstrated by the separations of various small molecules including aromatic hydrocarbons, isomers, and homologues using a binary polar mobile phase. The present column efficiency reached 27 000 plates/m, which showed that the ionic liquid monoliths are alternative stationary phases in the separation of small molecules by high-performance liquid chromatography. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The dynamics of milk droplet-droplet collisions

NASA Astrophysics Data System (ADS)

Finotello, Giulia; Kooiman, Roeland F.; Padding, Johan T.; Buist, Kay A.; Jongsma, Alfred; Innings, Fredrik; Kuipers, J. A. M.

2018-01-01

Spray drying is an important industrial process to produce powdered milk, in which concentrated milk is atomized into small droplets and dried with hot gas. The characteristics of the produced milk powder are largely affected by agglomeration, combination of dry and partially dry particles, which in turn depends on the outcome of a collision between droplets. The high total solids (TS) content and the presence of milk proteins cause a relatively high viscosity of the fed milk concentrates, which is expected to largely influence the collision outcomes of drops inside the spray. It is therefore of paramount importance to predict and control the outcomes of binary droplet collisions. Only a few studies report on droplet collisions of high viscous liquids and no work is available on droplet collisions of milk concentrates. The current study therefore aims to obtain insight into the effect of viscosity on the outcome of binary collisions between droplets of milk concentrates. To cover a wide range of viscosity values, three milk concentrates (20, 30 and 46% TS content) are investigated. An experimental set-up is used to generate two colliding droplet streams with consistent droplet size and spacing. A high-speed camera is used to record the trajectories of the droplets. The recordings are processed by Droplet Image Analysis in MATLAB to determine the relative velocities and the impact geometries for each individual collision. The collision outcomes are presented in a regime map dependent on the dimensionless impact parameter and Weber ( We) number. The Ohnesorge ( Oh) number is introduced to describe the effect of viscosity from one liquid to another and is maintained constant for each regime map by using a constant droplet diameter ( d ˜ 700 μ m). In this work, a phenomenological model is proposed to describe the boundaries demarcating the coalescence-separation regimes. The collision dynamics and outcome of milk concentrates are compared with aqueous glycerol

"Liquid-liquid-solid"-type superoleophobic surfaces to pattern polymeric semiconductors towards high-quality organic field-effect transistors.

PubMed

Wu, Yuchen; Su, Bin; Jiang, Lei; Heeger, Alan J

2013-12-03

Precisely aligned organic-liquid-soluble semiconductor microwire arrays have been fabricated by "liquid-liquid-solid" type superoleophobic surfaces directed fluid drying. Aligned organic 1D micro-architectures can be built as high-quality organic field-effect transistors with high mobilities of >10 cm(2) ·V(-1) ·s(-1) and current on/off ratio of more than 10(6) . All these studies will boost the development of 1D microstructures of organic semiconductor materials for potential application in organic electronics. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Isospecific propylene polymerization with in situ generated bis(phenoxy-amine)zirconium and hafnium single site catalysts.

PubMed

Makio, Haruyuki; Prasad, Aitha Vishwa; Terao, Hiroshi; Saito, Junji; Fujita, Terunori

2013-07-07

Bis(phenoxy-imine) Zr and Hf complexes were activated with (i)Bu3Al or (i)Bu2AlH in conjunction with Ph3CB(C6F5)4 and tested as catalysts for propylene polymerization with emphasis on the enantioselectivity of the isospecific species and the single site polymerization characteristics. The isoselective species was identified as the in situ generated bis(phenoxy-amine) complex whose isoselectivity was sensitive to subtle changes in ligand structure. By employing specific substituents at certain key positions the isotacticity reached an extremely high level comparable to high-end commercial isotactic polypropylenes (Tm > 160 °C). Single site polymerization characteristics depended upon the efficiency and selectivity of the in situ imine reduction which is sensitive to the substituent on the imine nitrogen and the reaction conditions. By using (i)Bu2AlH as a reducing agent, quantitative imine reduction can be achieved with a stoichiometric amount of the reducing agent. This lower alkylaluminum loading is beneficial for the catalyst and significantly enhances the polymerization activity and the molecular weight of the resultant polymer.

Effect of leaching residual methyl methacrylate concentrations on in vitro cytotoxicity of heat polymerized denture base acrylic resin processed with different polymerization cycles

PubMed Central

BURAL, Canan; AKTAŞ, Esin; DENIZ, Günnur; ÜNLÜÇERÇI, Yeşim; BAYRAKTAR, Gülsen

2011-01-01

Objectives Residual methyl methacrylate (MMA) may leach from the acrylic resin denture bases and have adverse effects on the oral mucosa. This in vitro study evaluated and correlated the effect of the leaching residual MMA concentrations ([MMA]r) on in vitro cytotoxicity of L-929 fibroblasts. Material and Methods A total of 144 heat-polymerized acrylic resin specimens were fabricated using 4 different polymerization cycles: (1) at 74ºC for 9 h, (2) at 74ºC for 9 h and terminal boiling (at 100ºC) for 30 min, (3) at 74ºC for 9 h and terminal boiling for 3 h, (4) at 74ºC for 30 min and terminal boiling for 30 min. Specimens were eluted in a complete cell culture medium at 37ºC for 1, 2, 5 and 7 days. [MMA]r in eluates was measured using high-performance liquid chromatography. In vitro cytotoxicity of eluates on L-929 fibroblasts was evaluated by means of cell proliferation using a tetrazolium salt XTT (sodium 3´-[1-phenyl-aminocarbonyl)-3,4-tetrazolium]bis(4-methoxy-6-nitro)benzenesulphonic acid) assay. Differences in [MMA]r of eluates and cell proliferation values between polymerization cycles were statistically analyzed by Kruskal-Wallis, Friedman and Dunn's multiple comparison tests. The correlation between [MMA]r of eluates and cell proliferation was analyzed by Pearson's correlation test (p<0.05). Results [MMA]r was significantly (p≤0.001) higher in eluates of specimens polymerized with cycle without terminal boiling after elution of 1 and 2 days. Cell proliferation values for all cycles were significantly (p<0.01) lower in eluates of 1 day than those of 2 days. The correlation between [MMA]r and cell proliferation values was negative after all elution periods, showing significance (p<0.05) for elution of 1 and 2 days. MMA continued to leach from acrylic resin throughout 7 days and leaching concentrations markedly reduced after elution of 1 and 2 days. Conclusion Due to reduction of leaching residual MMA concentrations, use of terminal boiling in the

Ocean acidification hampers sperm-egg collisions, gamete fusion, and generation of Ca2+ oscillations of a broadcast spawning bivalve, Tegillarca granosa.

PubMed

Shi, Wei; Han, Yu; Guo, Cheng; Zhao, Xinguo; Liu, Saixi; Su, Wenhao; Wang, Yichen; Zha, Shanjie; Chai, Xueliang; Liu, Guangxu

2017-09-01

Although the effect of ocean acidification on fertilization success of marine organisms is increasingly well documented, the underlying mechanisms are not completely understood. The fertilization success of broadcast spawning invertebrates depends on successful sperm-egg collisions, gamete fusion, and standard generation of Ca 2+ oscillations. Therefore, the realistic effects of future ocean pCO 2 levels on these specific aspects of fertilization of Tegillarca granosa were investigated in the present study through sperm velocity trials, fertilization kinetics model analysis, and intracellular Ca 2+ assays, respectively. Results obtained indicated that ocean acidification significantly reduced the fertilization success of T. granosa, which could be accountable by (i) decreased sperm velocity hence reducing the probability for sperm-egg collisions; (ii) lowered probability of gamete fusion for each gamete collision event; and (iii) disrupted intracellular Ca 2+ oscillations. Copyright © 2017 Elsevier Ltd. All rights reserved.

Rotational and vibrational transitions for Li + H2 collisions

NASA Technical Reports Server (NTRS)

Choi, B. H.; Poe, R. T.; Tang, K. T.

1977-01-01

Close coupling calculations for integral and differential cross sections have been carried out for Li + H2 collisions with an ab initio Hartree-Fock potential energy surface. Rotational, vibrational, and vib-rotational excitation cross sections are reported at 0.4336 eV, 0.7 eV, and 0.8673 eV in the center of mass system. For pure rotational excitations, which dominate the inelastic scattering, coupling with vibrational states is not very important. For vibrational transitions, the influence of large multiquantum rotational transitions is far less than that found for Li(+) + H2 collisions.

Preparation of Transparent Bulk TiO2/PMMA Hybrids with Improved Refractive Indices via an in Situ Polymerization Process Using TiO2 Nanoparticles Bearing PMMA Chains Grown by Surface-Initiated Atom Transfer Radical Polymerization.

PubMed

Maeda, Satoshi; Fujita, Masato; Idota, Naokazu; Matsukawa, Kimihiro; Sugahara, Yoshiyuki

2016-12-21

Transparent TiO 2 /PMMA hybrids with a thickness of 5 mm and improved refractive indices were prepared by in situ polymerization of methyl methacrylate (MMA) in the presence of TiO 2 nanoparticles bearing poly(methyl methacrylate) (PMMA) chains grown using surface-initiated atom transfer radical polymerization (SI-ATRP), and the effect of the chain length of modified PMMA on the dispersibility of modified TiO 2 nanoparticles in the bulk hybrids was investigated. The surfaces of TiO 2 nanoparticles were modified with both m-(chloromethyl)phenylmethanoyloxymethylphosphonic acid bearing a terminal ATRP initiator and isodecyl phosphate with a high affinity for common organic solvents, leading to sufficient dispersibility of the surface-modified particles in toluene. Subsequently, SI-ATRP of MMA was achieved from the modified surfaces of the TiO 2 nanoparticles without aggregation of the nanoparticles in toluene. The molecular weights of the PMMA chains cleaved from the modified TiO 2 nanoparticles increased with increases in the prolonging of the polymerization period, and these exhibited a narrow distribution, indicating chain growth controlled by SI-ATRP. The nanoparticles bearing PMMA chains were well-dispersed in MMA regardless of the polymerization period. Bulk PMMA hybrids containing modified TiO 2 nanoparticles with a thickness of 5 mm were prepared by in situ polymerization of the MMA dispersion. The transparency of the hybrids depended significantly on the chain length of the modified PMMA on the nanoparticles, because the modified PMMA of low molecular weight induced aggregation of the TiO 2 nanoparticles during the in situ polymerization process. The refractive indices of the bulk hybrids could be controlled by adjusting the TiO 2 content and could be increased up to 1.566 for 6.3 vol % TiO 2 content (1.492 for pristine PMMA).

Threshold collision-induced dissociation of diatomic molecules: a case study of the energetics and dynamics of O2- collisions with Ar and Xe.

PubMed

Ahu Akin, F; Ree, Jongbaik; Ervin, Kent M; Kyu Shin, Hyung

2005-08-08

The energetics and dynamics of collision-induced dissociation of O2- with Ar and Xe targets are studied experimentally using guided ion-beam tandem mass spectrometry. The cross sections and the collision dynamics are modeled theoretically by classical trajectory calculations. Experimental apparent threshold energies are 2.1 and 1.1 eV in excess of the thermochemical O2- bond dissociation energy for argon and xenon, respectively. Classical trajectory calculations confirm the observed threshold behavior and the dependence of cross sections on the relative kinetic energy. Representative trajectories reveal that the bond dissociation takes place on a short time scale of about 50 fs in strong direct collisions. Collision-induced dissociation is found to be remarkably restricted to the perpendicular approach of ArXe to the molecular axis of O2-, while collinear collisions do not result in dissociation. The higher collisional energy-transfer efficiency of xenon compared with argon is attributed to both mass and polarizability effects.

Preparation of a polymeric ionic liquid-coated solid-phase microextraction fiber by surface radical chain-transfer polymerization with stainless steel wire as support.

PubMed

Feng, Juanjuan; Sun, Min; Xu, Lili; Li, Jubai; Liu, Xia; Jiang, Shengxiang

2011-10-28

Polymeric 1-vinyl-3-octylimidazolium hexafluorophosphate was synthesized in situ on stainless steel wire by surface radical chain-transfer polymerization and used as sensitive coatings in solid-phase microextraction. The outer surface of the stainless steel wire was firstly coated with microstructured silver layer via silver mirror reaction and then functionalized with self-assembled monolayers of 1,8-octanedithiol, which acted as chain transfer agent in the polymerization. Coupled to gas chromatography, extraction performance of the fiber was studied with both headspace and direct-immersion modes using benzene, toluene, ethylbenzene and xylenes (BTEX), phenols and polycyclic aromatic hydrocarbon (PAHs) as model analytes. In combination with the microstructured silver layer, the PIL-coated fiber exhibited high extraction efficiency. Linear ranges for BTEX with headspace mode were in the range of 0.2-1000 μg L(-1) for benzene, and 0.1-1000 μg L(-1) for toluene, ethylbenzene and xylenes. Limits of detection (LODs) were from 0.02 to 0.05 μg L(-1). Wide linear ranges of direct-immersion mode for the extraction of several phenols and PAHs were also obtained with correlation coefficients (R) from 0.9943 to 0.9997. The proposed fiber showed good durability with long lifetime. RSDs of 56 times extraction were still in an acceptable range, from 8.85 to 22.8%. Copyright © 2011 Elsevier B.V. All rights reserved.

Lewis acid catalyzed ring-opening polymerization of natural epoxy oil (Euphorbia oil) in carbon dioxide media

USDA-ARS?s Scientific Manuscript database

In an attempt to build up useful application of plant oil based polymers, natural epoxy oil (euphorbia oil-EuO) was polymerized in liquid carbon dioxide in the presence of Lewis acid catalyst [Boron trifluoride diethyl etherate (BF3•OEt2)]. The resulting polymers (RPEuO) were characterized by FTIR ...

Collision-energy-resolved angular distribution of Penning electrons for N 2-He ∗(2 3S)

NASA Astrophysics Data System (ADS)

Hanzawa, Yoshinori; Kishimoto, Naoki; Yamazaki, Masakazu; Ohno, Koichi

2006-07-01

The collision-energy-resolved angular distributions of Penning electrons for individual ionic state of N 2-He ∗(2 3S) were measured. The angular distributions showed increasing intensity in the backward (rebounding) directions with respect to initial He ∗(2 3S) beam vector because Penning ionization occurs with a collision against repulsive interaction wall followed by the electron emission from 2s orbital of He ∗. We also analyzed internal angular distribution by means of fitting parameters using classical trajectory calculations for N 2-He ∗(2 3S) on the modified interaction potential. These internal angular distributions suggested the electron emission from 2s orbital of He ∗ and they depended on collision energy and electron kinetic energy.

Polymeric ionic liquid-based portable tip microextraction device for on-site sample preparation of water samples.

PubMed

Chen, Lei; Pei, Junxian; Huang, Xiaojia; Lu, Min

2018-06-05

On-site sample preparation is highly desired because it avoids the transportation of large-volume samples and ensures the accuracy of the analytical results. In this work, a portable prototype of tip microextraction device (TMD) was designed and developed for on-site sample pretreatment. The assembly procedure of TMD is quite simple. Firstly, polymeric ionic liquid (PIL)-based adsorbent was in-situ prepared in a pipette tip. After that, the tip was connected with a syringe which was driven by a bidirectional motor. The flow rates in adsorption and desorption steps were controlled accurately by the motor. To evaluate the practicability of the developed device, the TMD was used to on-site sample preparation of waters and combined with high-performance liquid chromatography with diode array detection to measure trace estrogens in water samples. Under the most favorable conditions, the limits of detection (LODs, S/N = 3) for the target analytes were in the range of 4.9-22 ng/L, with good coefficients of determination. Confirmatory study well evidences that the extraction performance of TMD is comparable to that of the traditional laboratory solid-phase extraction process, but the proposed TMD is more simple and convenient. At the same time, the TMD avoids complicated sampling and transferring steps of large-volume water samples. Copyright © 2018 Elsevier B.V. All rights reserved.

2DCOS and PCMW2D analysis of FT-IR/ATR spectra measured at variable temperatures on-line to a polyurethane polymerization

NASA Astrophysics Data System (ADS)

Schuchardt, Patrick; Unger, Miriam; Siesler, Heinz W.

2018-01-01

In the present communication the potential of 2DCOS analysis and the spin-off technique perturbation-correlation moving window 2D (PCMW2D) analysis is illustrated with reference to spectroscopic changes observed in a data set recorded by in-line fiber-coupled FT-IR spectroscopy in the attenuated total reflection (ATR) mode during a polyurethane solution polymerization at different temperatures. In view of the chemical functionalities involved, hydrogen bonding plays an important role in this polymerization reaction. Based on the 2DCOS and PCMW2D analysis, the sequence of hydrogen bonding changes accompanying the progress of polymerization and precipitation of solid polymer can be determined. Complementary to the kinetic data derived from the original variable-temperature spectra in a previous publication the results provide a more detailed picture of the investigated solution polymerization.

Relocking of intrinsic angular momenta in collisions of diatoms with ions: Capture of H2(j = 0,1) by H2+

NASA Astrophysics Data System (ADS)

Dashevskaya, E. I.; Litvin, I.; Nikitin, E. E.; Troe, J.

2016-12-01

Rate coefficients for capture of H2(j = 0,1) by H2+ are calculated in perturbed rotor approximation, i.e., at collision energies considerably lower than Bhc (where B denotes the rotational constant of H2). The results are compared with the results from an axially nonadiabatic channel (ANC) approach, the latter providing a very good approximation from the low-temperature Bethe-Wigner to the high temperature Langevin limit. The classical ANC approximation performs satisfactorily at temperatures above 0.1 K. At 0.1 K, the rate coefficient for j =1 is about 25% higher than that for j = 0 while the latter is close to the Langevin rate coefficient. The Bethe-Wigner limit of the rate coefficient for j = 1 is about twice that for j = 0. The analysis of the relocking of the intrinsic angular momentum of H2 during the course of the collision illustrates the significance of relocking in capture dynamics in general.

Born-Oppenheimer and Renner-Teller coupled-channel quantum reaction dynamics of O((3)P) + H2(+)(X(2)Σg(+)) collisions.

PubMed

Gamallo, Pablo; Defazio, Paolo; González, Miguel; Paniagua, Miguel; Petrongolo, Carlo

2015-09-28

We present Born-Oppenheimer (BO) and Renner-Teller (RT) time dependent quantum dynamics studies of the reactions O((3)P) + H2(+)(X(2)Σg(+)) → OH(+)(X(3)Σ(-)) + H((2)S) and OH(X(2)Π) + H(+). We consider the OH2(+) X[combining tilde](2)A'' and Ã(2)A' electronic states that correlate with a linear (2)Π species. The electronic angular momenta operators L[combining circumflex] and L[combining circumflex](2) are considered in nonadiabatic coupled-channel calculations, where the associated RT effects are due to diagonal V(RT) potentials that add up to the PESs and to off-diagonal C(RT) couplings between the potential energy surfaces (PESs). Initial-state-resolved reaction probabilities PI, integral cross sections σI, and rate constants kI are obtained using recent ab initio PESs and couplings and the real wavepacket formalism. Because the PESs are strongly attractive, PI have no threshold energy and are large, σI decrease with collision energy, and kI depend little on the temperature. The X[combining tilde](2)A'' PES is up to three times more reactive than the Ã(2)A' PES and H2(+) rotational effects (j0 = 0, 1) are negligible. The diagonal V(RT) potentials are strongly repulsive at the collinearity and nearly halve all low-energy observables with respect to the BO ones. The off-diagonal C(RT) couplings are important at low partial waves, where they mix the X[combining tilde](2)A'' and Ã(2)A' states up to ∼20%. However, V(RT) effects predominate over the C(RT) ones that change at most by ∼19% the BO values of σI and kI. The reaction O((3)P) + H2(+)(X(2)Σg(+)) → OH(+)(X(3)Σ(-)) + H((2)S) is probably one of the most reactive atom + diatom collisions because its RT rate constant at room temperature is equal to 2.26 × 10(-10) cm(3) s(-1). Within the BO approximation, the present results agree rather well with recent quasiclassical and centrifugal-sudden data using the same PESs.

NIF Double Shell outer/inner shell collision experiments

NASA Astrophysics Data System (ADS)

Merritt, E. C.; Loomis, E. N.; Wilson, D. C.; Cardenas, T.; Montgomery, D. S.; Daughton, W. S.; Dodd, E. S.; Desjardins, T.; Renner, D. B.; Palaniyappan, S.; Batha, S. H.; Khan, S. F.; Smalyuk, V.; Ping, Y.; Amendt, P.; Schoff, M.; Hoppe, M.

2017-10-01

Double shell capsules are a potential low convergence path to substantial alpha-heating and ignition on NIF, since they are predicted to ignite and burn at relatively low temperatures via volume ignition. Current LANL NIF double shell designs consist of a low-Z ablator, low-density foam cushion, and high-Z inner shell with liquid DT fill. Central to the Double Shell concept is kinetic energy transfer from the outer to inner shell via collision. The collision determines maximum energy available for compression and implosion shape of the fuel. We present results of a NIF shape-transfer study: two experiments comparing shape and trajectory of the outer and inner shells at post-collision times. An outer-shell-only target shot measured the no-impact shell conditions, while an `imaging' double shell shot measured shell conditions with impact. The `imaging' target uses a low-Z inner shell and is designed to perform in similar collision physics space to a high-Z double shell but can be radiographed at 16keV, near the viable 2DConA BL energy limit. Work conducted under the auspices of the U.S. DOE by LANL under contract DE-AC52-06NA25396.

Nanoporous array anodic titanium-supported co-polymeric ionic liquids as high performance solid-phase microextraction sorbents for hydrogen bonding compounds.

PubMed

Jia, Jing; Liang, Xiaojing; Wang, Licheng; Guo, Yong; Liu, Xia; Jiang, Shengxiang

2013-12-13

A nanoporous array anodic titanium-supported co-polymeric ionic liquids (NAAT/PILs) solid-phase microextraction (SPME) fiber was prepared in situ on the titanium wire. NAAT was selected as the substrate, in view of its high surface-to-volume ratio, easy preparation, mechanical stability, and rich titanol groups on its surface which can anchor silica coupling agent containing vinyl and then introduce ionic liquid copolymers as sorbents. In this work, 1-vinyl-3-nonanol imidazolium bromide ([C9OHVIm]Br) and 1,4-di(3-vinylimidazolium) butane dibromide ([(VIM)2C4]2[Br]) were synthesized and used as monomer and crosslinker, respectively. Extraction properties of the NAAT/PILs fiber for polar alcohols and volatile fatty acids (VFAs) in aqueous matrix were examined using gaseous sampling-SPME (GS-SPME) and headspace SPME (HS-SPME) mode, respectively. Combining the superior properties of NAAT substrate and the strong hydrogen bond interaction of PILs to polar compounds, the NAAT/PILs SPME fiber showed much higher adsorption affinity to aliphatic alcohols than bare NAAT and pure PILs fibers. The detection limits (LOD) of established GS-SPME-GC-FID method are in the range of 0.35-17.30ngL(-1) with a linear range from 0.01 to 500ngmL(-1). Also, it showed high extraction performance toward volatile fatty acids (VFAs) compounds from aqueous matrix. Under the optimized SPME conditions, wide linear ranges were obtained with correlation coefficients (R(2)) greater than 0.99 and limits of detection were in the range of 0.85-8.74ngL(-1). Moreover, real-world samples were analyzed and good results were obtained. Copyright © 2013. Published by Elsevier B.V.

Liquid-liquid separation in solutions of normal and sickle cell hemoglobin

NASA Astrophysics Data System (ADS)

Galkin, Oleg; Chen, Kai; Nagel, Ronald L.; Elison Hirsch, Rhoda; Vekilov, Peter G.

2002-06-01

We show that in solutions of human hemoglobin (Hb)oxy- and deoxy-Hb A or Sof near-physiological pH, ionic strength, and Hb concentration, liquid-liquid phase separation occurs reversibly and reproducibly at temperatures between 35 and 40°C. In solutions of deoxy-HbS, we demonstrate that the dense liquid droplets facilitate the nucleation of HbS polymers, whose formation is the primary pathogenic event for sickle cell anemia. In view of recent results that shifts of the liquid-liquid separation phase boundary can be achieved by nontoxic additives at molar concentrations up to 30 times lower than the protein concentrations, these findings open new avenues for the inhibition of the HbS polymerization.

Controlled crosslinking of trimethylolpropane trimethacrylate for preparation of organic monolithic columns for capillary liquid chromatography.

PubMed

Gama, Mariana R; Aggarwal, Pankaj; Lee, Milton L; Bottoli, Carla B G

2017-11-01

Organic monolithic columns based on single crosslinking of trimethylolpropane trimethacrylate (TRIM) monomer were prepared in a single step by living/controlled free-radical polymerization. Full optimization of the preparation, such as using different percentages of TRIM and different amounts of radical promoter as well as various porogen solvents were explored. The resulting monolithic columns were characterized by scanning electronic microscopy and nitrogen sorption for structure morphology studies and surface area measurements, respectively. Using capillary liquid chromatography, 150 μm i.d. columns were applied to separate a mixture of small hydrophobic molecules. The results indicated that column performance is highly sensitive to the type and the amount of porogen solvents used in the polymerization mixture composition. Good resolution factors and methylene selectivity were obtained, indicating the promising potential of this material for capillary liquid chromatography separations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Separation and characterization of allergic polymerized impurities in cephalosporins by 2D-HPSEC×LC-IT-TOF MS.

PubMed

Xu, Yu; Wang, DanDan; Tang, Lan; Wang, Jian

2017-10-25

Eleven unknown allergic impurities in cefodizime, cefmenoxime and cefonicid were separated and characterized by a trap-free two-dimensional high performance size exclusion chromatography (HPSEC) and reversed phase liquid chromatography (RP-HPLC) coupled to high resolution ion trap/time-of-flight mass spectrometry (2D-HPSEC×LC-IT-TOF MS) with positive and negative modes of electrospray ionization method. Separation and characterization the allergic polymerized impurities in β-lactam antibiotics were on the basis of column-switching technique which effectively combined the advantages of HPSEC and the ability of RP-HPLC to identify the special impurities. In the first dimension HPSEC, the column was Xtimate SEC-120 analytical column (7.8mm×30cm, 5μm), and the gradient elution used pH 7.0 buffer-acetonitrile as mobile phase And the second dimension analytical column was ZORBAX SB-C18 (4.6×150mm, 3.5μm) with ammonium formate solution (10mM) and ammonium formate (8mM) in [acetonitrile-water (4:1, v/v)] solution as mobile phase. Structures of eleven unknown impurities were deduced based on the high resolution MS n data with both positive and negative modes, in which nine impurities were polymerized impurities. The forming mechanism of β-lactam antibiotic polymerization in cephalosporins was also studied. The question on incompatibility between non-volatile salt mobile phase and mass spectrometry was solved completely by multidimensional heart-cutting approaches and online demineralization technique, which was worthy of widespread use and application for the advantages of stability and repeatability. Copyright © 2017. Published by Elsevier B.V.

A Novel Polymeric Organosilazane Precursor to Si3N4/SiC Ceramics.

DTIC Science & Technology

1985-02-06

prepared by pyrolysis of the appropriately-shaped polymeric precursor. These polysilazanes also may prove to be useful as dispersants for SiC and Si3N4...I[AD-Ri58 748 A NOVEL POLYMERIC ORGANOSILAZANE PRECURSOR TO S13N4/ SIC i/I CERRMICS(U) MASSACHUSETTS INST OF TECH CAMBRIDGE DEPT OF CHEMISTRY D...Security C ificatlion" 0322 A Novel Polymeric Organosilazane Precursor to Si3N/ SiC C_ramics._I 12. PERSONAL AUTHOR(S) Dietmar Seyferth and Gary H. Wiseman 13

The Effect of Surface Pressure on the Langmuir-Blodgett Polymerization of 2-Pentadecyl Aniline

DTIC Science & Technology

1992-05-19

the mean molecular area was decreasing during the polymerization of 2-pentadecyl aniline . Also no polymer was found when the reaction was run at low...and polymer, we suppose, is the cause of Mma decrease during the polymerization of 2-pentadecyl aniline . Compared with the area of a long alkyl ...is put into changing its conformation at the surface. In the case of 2-pentadecyl aniline , the work done upon compressing the monolayer, we suppose, is

RHIC The Perfect Liquid

ScienceCinema

BNL

2017-12-09

Evidence to date suggests that gold-gold collisions the Relativistic Heavy Ion Collider at Brookhaven are indeed creating a new state of hot, dense matter, but one quite different and even more remarkable than had been predicted. Instead of behaving like a gas of free quarks and gluons, as was expected, the matter created in RHIC's heavy ion collisions appears to be more like a "perfect" liquid.

Non-equilibrium supramolecular polymerization.

PubMed

Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M

2017-09-18

Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term "non-equilibrium self-assembly" by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.

Cellulose biogenesis: Polymerization and crystallization are coupled processes in Acetobacter xylinum.

PubMed

Benziman, M; Haigler, C H; Brown, R M; White, A R; Cooper, K M

1980-11-01

Calcofluor White ST, stilbene derivative used commerically as an optical brightener for cellulose, increased the rate of glucose polymerization into cellulose by resting cells of the gram-negative bacterium Acetobacter xylinum. This bacterium normally produces a ribbon of cellulose that is a composite of crystalline microfibrils. In concentrations above 0.1 mM, Calcofluor disrupts the assembly of crystalline cellulose I microfibrils and their integration into a composite ribbon by stoichiometric binding to glucose residues of newly polymerized glucan chains. Under these conditions, the rate of glucose polymerization increases up to 4 times the control rate, whereas oxygen uptake increases only 10-15%. These observed effects are readily reversible. If free Calcofluor is washed away or depleted below the threshold value by binding to cellulose as polymerization continues, ribbon production and the normal rate of polymerization resume. It is concluded that polymerization and crystallization are cell-directed, coupled processes and that the rate of crystallization determines the rate of polymerization. It is suggested that coupling must be maintained for biogenesis of crystalline cellulose I.

Evaporation and condensation at a liquid surface. I. Argon

NASA Astrophysics Data System (ADS)

Yasuoka, Kenji; Matsumoto, Mitsuhiro; Kataoka, Yosuke

1994-11-01

Molecular dynamics computer simulations were carried out to investigate the dynamics of evaporation and condensation for argon at the temperature of 80 and 100 K. From the decrease of the survival probability of vapor molecules, the ratio of self reflection to collision is estimated to be 12%-15%, only weakly dependent on the temperature. This suggests that argon vapor molecules are in the condition of almost complete capture, and the condensation is considered to be a barrierless process. The total ratio of reflection which is evaluated with the flux correlation of condensation and evaporation is 20% at both temperature. The difference between these two ratios of reflection is ascribed to a phenomenon that vapor molecules colliding with the surface drive out other liquid molecules. This molecule exchange at the surface is as important as the self-reflection, and the conventional picture of condensation as a unimolecular chemical reaction is not appropriate.

Experimental study of oblique impact between dry spheres and liquid layers

NASA Astrophysics Data System (ADS)

Ma, Jiliang; Liu, Daoyin; Chen, Xiaoping

2013-09-01

Liquid addition is common in industrial fluidization-based processes. A detailed understanding of collision mechanics of particles with liquid layers is helpful to optimize these processes. The normal impact with liquid has been studied extensively; however, the studies on oblique impact with liquid are scarce. In this work, experiments are conducted to trace Al2O3 spheres obliquely impacting on a surface covered by liquid layers, in which the free-fall spheres are disturbed initially by a horizontal gas flow. The oblique impact exhibits different rebound behaviors from normal collision due to the occurrence of strong rotation. The normal and tangential restitution coefficients (en and et) and liquid bridge rupture time (trup) are analyzed. With increase in liquid layer thickness and viscosity, en and et decline, and trup increases. With increase in tangential velocity, et decreases first and then increases, whereas en remains nearly unchanged, and trup decreases constantly. A modified Stokes number is proposed to further explore the relation between restitution coefficients and the impact parameters. Finally, an analysis of energy dissipation shows that the contact deformation and liquid phase are the two main sources of total energy dissipation. Unexpectedly, the dissipative energy caused by the liquid phase is independent of tangential velocity.

Crosslinked structurally-tuned polymeric ionic liquids as stationary phases for the analysis of hydrocarbons in kerosene and diesel fuels by comprehensive two-dimensional gas chromatography.

PubMed

Zhang, Cheng; Park, Rodney A; Anderson, Jared L

2016-04-01

Structurally-tuned ionic liquids (ILs) have been previously applied as the second dimension column in comprehensive two-dimensional gas chromatography (GC×GC) and have demonstrated high selectivity in the separation of individual aliphatic hydrocarbons from other aliphatic hydrocarbons. However, the maximum operating temperatures of these stationary phases limit the separation of analytes with high boiling points. In order to address this issue, a series of polymeric ionic liquid (PIL)-based stationary phases were prepared in this study using imidazolium-based IL monomers via in-column free radical polymerization. The IL monomers were functionalized with long alkyl chain substituents to provide the needed selectivity for the separation of aliphatic hydrocarbons. Columns were prepared with different film thicknesses to identify the best performing stationary phase for the separation of kerosene. The bis[(trifluoromethyl)sulfonyl]imide ([NTf2](-))-based PIL stationary phase with larger film thickness (0.28μm) exhibited higher selectivity for aliphatic hydrocarbons and showed a maximum allowable operating temperature of 300°C. PIL-based stationary phases containing varied amount of IL-based crosslinker were prepared to study the effect of the crosslinker on the selectivity and thermal stability of the resulting stationary phase. The optimal resolution of aliphatic hydrocarbons was achieved when 50% (w/w) of crosslinker was incorporated into the PIL-based stationary phase. The resulting stationary phase exhibited good selectivity for different groups of aliphatic hydrocarbons even after being conditioned at 325°C. Finally, the crosslinked PIL-based stationary phase was compared with SUPELCOWAX 10 and DB-17 columns for the separation of aliphatic hydrocarbons in diesel fuel. Better resolution of aliphatic hydrocarbons was obtained when employing the crosslinked PIL-based stationary phase as the second dimension column. Copyright © 2016 Elsevier B.V. All rights

Full-dimensional quantum dynamics of CO in collision with H{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Benhui; Stancil, P. C.; Balakrishnan, N.

Inelastic scattering computations are presented for collisions of vibrationally and rotationally excited CO with H{sub 2} in full dimension. The computations utilize a newly developed six-dimensional potential energy surface (PES) and the previously reported four-dimensional V12 PES [P. Jankowski et al., J. Chem. Phys. 138, 084307 (2013)] and incorporate full angular-momentum coupling. At low collision energies, pure rotational excitation cross sections of CO by para-, ortho-, and normal-H{sub 2} are calculated and convolved to compare with recent measurements. Good agreement with the measured data is shown except for j{sub 1} = 0 → 1 excitation of CO for very low-energymore » para-H{sub 2} collisions. Rovibrational quenching results are presented for initially excited CO(v{sub 1}j{sub 1}) levels with v{sub 1} = 1, j{sub 1} = 1–5 and v{sub 1} = 2, j{sub 1} = 0 for collisions with para-H{sub 2} (v{sub 2} = 0, j{sub 2} = 0) and ortho-H{sub 2} (v{sub 2} = 0, j{sub 2} = 1) over the kinetic energy range 0.1–1000 cm{sup −1}. The total quenching cross sections are found to have similar magnitudes, but increase (decrease) with j{sub 1} for collision energies above ∼300 cm{sup −1} (below ∼10 cm{sup −1}). Only minor differences are found between para- and ortho-H{sub 2} colliders for rovibrational and pure rotational transitions, except at very low collision energies. Likewise, pure rotational deexcitation of CO yields similar cross sections for the v{sub 1} = 0 and v{sub 1} = 1 vibrational levels, while rovibrational quenching from v{sub 1} = 2, j{sub 1} = 0 is a factor of ∼5 larger than that from v{sub 1} = 1, j{sub 1} = 0. Details on the PES, computed at the CCSD(T)/aug-cc-pV5Z level, and fitted with an invariant polynomial method, are also presented.« less

Titanium isopropoxide complexes of a series of sterically demanding aryloxo based [N2O2]2- ligands as precatalysts for ethylene polymerization.

PubMed

Panda, Manas K; Kaur, Sukhdeep; Reddy, Annapureddy Rajasekhar; Shaikh, Mobin M; Butcher, Ray J; Gupta, Virendrakumar; Ghosh, Prasenjit

2010-12-07

Several titanium isopropoxide complexes [N,N'-bis(2-oxo-3-R(1)-5-R(2)-phenylmethyl)-N,N'-bis(methylene-p-R(3)-C(6)H(4))-ethylenediamine]Ti(O(i)Pr)(2) [R(1) = t-Bu, R(2) = Me, R(3) = H (1b); R(1) = R(2) = t-Bu, R(3) = H, (2b); R(1) = R(2) = Cl, R(3) = H, (3b), R(1) = t-Bu, R(2) = Me, R(3) = Cl (4b); R(1) = R(2) = t-Bu, R(3) = Cl, (5b); R(1) = R(2) = R(3) = Cl, (6b)] supported over sterically demanding aryloxy based [N(2)O(2)]H(2) ligands have been designed as precatalysts for the ethylene polymerization. Specifically, the 1b-6b complexes, when treated with methylaluminoxane (MAO) under 88 ± 0.5 psi of ethylene at 30 °C for 3 h, produced polyethylene polymers of high molecular weight (M(w) = ca. 7.2-8.3 × 10(5) g mol(-1)) having broad molecular weight distribution (PDI = ca. 13.1-14.6). The 1b-6b complexes were conveniently synthesized from the direct reaction of the [N(2)O(2)]H(2) ligands, 1a-6a, with Ti(O(i)Pr)(4) in 69-86% yield.

Ionic liquid marbles.

PubMed

Gao, Lichao; McCarthy, Thomas J

2007-10-09

Liquid marbles have been reported during this decade and have been argued to be potentially useful for microfluidic and lab-on-a-chip applications. The liquid marbles described to date have been composed of either water or glycerol as the liquid and hydrophobized lycopodium or silica as the stabilizing particles. Both of these components are potentially reactive and do not permit the use of organic chemistry; the liquids are volatile. We report the use of perfluoroalkyl particles (oligomeric (OTFE) and polymeric (PTFE) tetrafluoroethylene, which are unreactive) to support/stabilize a range of ionic liquid marbles. Ionic liquids are not volatile and have been demonstrated to be versatile solvents for chemical transformations. Water marbles prepared with OTFE are much more robust than those prepared with hydrophobized lycopodium or silica.

Electron Capture in Slow Collision of He^2++H : Revisited

NASA Astrophysics Data System (ADS)

Krstic, Ps

2003-05-01

Very early experimental data (Fite et al. al., Proc. R. Soc. A 268, 527 (1962)) for He^2++H, recent ORNL measurements for Ne^2+ + H and our theoretical estimates suggest that the electron capture cross sections for these strongly exoergic collision systems drop slower toward low collision energies than expected from previous theories. We perform a theoretical study to establish and understand the true nature of this controversy. The calculations are based on the Hidden Crossings MOCC method, augmented with rotational and turning point effects.

Switchable focus using a polymeric lenticular microlens array and a polarization rotator.

PubMed

Ren, Hongwen; Xu, Su; Liu, Yifan; Wu, Shin-Tson

2013-04-08

We demonstrate a flat polymeric lenticular microlens array using a mixture of rod-like diacrylate monomer and positive dielectric anisotropy nematic liquid crystal (LC). To create gradient refractive index profile in one microlens, we generate fringing fields from a planar top electrode and two striped bottom electrodes. After UV stabilization, the film is optically anisotropic and can stand alone. We then laminate this film on a 90° twisted-nematic LC cell, which works as a dynamic polarization rotator. The static polymeric lenticular lens exhibits focusing effect only to the extraordinary ray, but no optical effect to the ordinary ray. Such an integrated lens system offers several advantages, such as low voltage, fast response time, and temperature insensitivity, and can be used for switchable 2D/3D displays.

Evaluation of Mercury in Liquid Waste Processing Facilities - Phase I Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jain, V.; Occhipinti, J.; Shah, H.

2015-07-01

This report provides a summary of Phase I activities conducted to support an Integrated Evaluation of Mercury in Liquid Waste System (LWS) Processing Facilities. Phase I activities included a review and assessment of the liquid waste inventory and chemical processing behavior of mercury using a system by system review methodology approach. Gaps in understanding mercury behavior as well as action items from the structured reviews are being tracked. 64% of the gaps and actions have been resolved.

Evaluation of mercury in liquid waste processing facilities - Phase I report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jain, V.; Occhipinti, J. E.; Shah, H.

2015-07-01

This report provides a summary of Phase I activities conducted to support an Integrated Evaluation of Mercury in Liquid Waste System (LWS) Processing Facilities. Phase I activities included a review and assessment of the liquid waste inventory and chemical processing behavior of mercury using a system by system review methodology approach. Gaps in understanding mercury behavior as well as action items from the structured reviews are being tracked. 64% of the gaps and actions have been resolved.

Liquid-liquid phase transition and anomalous diffusion in simulated liquid GeO 2

NASA Astrophysics Data System (ADS)

Hoang, Vo Van; Anh, Nguyen Huynh Tuan; Zung, Hoang

2007-03-01

We perform molecular dynamics (MD) simulation of diffusion in liquid GeO 2 at the temperatures ranged from 3000 to 5000 K and densities ranged from 3.65 to 7.90 g/cm 3. Simulations were done in a model containing 3000 particles with the new interatomic potentials for liquid and amorphous GeO 2, which have weak Coulomb interaction and Morse-type short-range interaction. We found a liquid-liquid phase transition in simulated liquid GeO 2 from a tetrahedral to an octahedral network structure upon compression. Moreover, such phase transition accompanied with an anomalous diffusion of particles in liquid GeO 2 that the diffusion constant of both Ge and O particles strongly increases with increasing density (e.g. with increasing pressure) and it shows a maximum at the density around 4.95 g/cm 3. The possible relation between anomalous diffusion of particles and structural phase transition in the system has been discussed.

Dense Carbon Monoxide to 160 GPa: Stepwise Polymerization to Two-Dimensional Layered Solid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryu, Young-Jay; Kim, Minseob; Lim, Jinhyuk

Carbon monoxide (CO) is the first molecular system found to transform into a nonmolecular “polymeric” solid above 5.5 GPa, yet been studied beyond 10 GPa. Here, we show a series of pressure-induced phase transformations in CO to 160 GPa: from a molecular solid to a highly colored, low-density polymeric phase I to translucent, high-density phase II to transparent, layered phase III. The properties of these phases are consistent with those expected from recently predicted 1D P2 1/m, 3D I2 12 12 1, and 2D Cmcm structures, respectively. Thus, the present results advocate a stepwise polymerization of CO triple bonds tomore » ultimately a 2D singly bonded layer structure with an enhanced ionic character.« less

Theoretical investigation of exchange and recombination reactions in O(3P)+NO(2Π) collisions

NASA Astrophysics Data System (ADS)

Ivanov, M. V.; Zhu, H.; Schinke, R.

2007-02-01

We present a detailed dynamical study of the kinetics of O(P3)+NO(Π2) collisions including O atom exchange reactions and the recombination of NO2. The classical trajectory calculations are performed on the lowest A'2 and A″2 potential energy surfaces, which were calculated by ab initio methods. The calculated room temperature exchange reaction rate coefficient, kex, is in very good agreement with the measured one. The high-pressure recombination rate coefficient, which is given by the formation rate coefficient and to a good approximation equals 2kex, overestimates the experimental data by merely 20%. The pressure dependence of the recombination rate, kr, is described within the strong-collision model by assigning a stabilization probability to each individual trajectory. The measured falloff curve is well reproduced over five orders of magnitude by a single parameter, i.e., the strong-collision stabilization frequency. The calculations also yield the correct temperature dependence, kr∝T-1.5, of the low-pressure recombination rate coefficient. The dependence of the rate coefficients on the oxygen isotopes are investigated by incorporating the difference of the zero-point energies between the reactant and product NO radicals, ΔZPE, into the potential energy surface. Similar isotope effects as for ozone are predicted for both the exchange reaction and the recombination. Finally, we estimate that the chaperon mechanism is not important for the recombination of NO2, which is in accord with the overall T-1.4 dependence of the measured recombination rate even in the low temperature range.

Development and characterization of a rapid polymerizing collagen for soft tissue augmentation

PubMed Central

Devore, Dale; Zhu, Jiaxun; Brooks, Robert; McCrate, Rebecca Rone; Grant, David A.

2015-01-01

Abstract A liquid collagen has been developed that fibrilizes upon injection. Rapid polymerizing collagen (RPC) is a type I porcine collagen that undergoes fibrillization upon interaction with ionic solutions, such as physiological solutions. The ability to inject liquid collagen would be beneficial for many soft tissue augmentation applications. In this study, RPC was synthesized and characterized as a possible dermal filler. Transmission electron microscopy, ion induced RPC fibrillogenesis tests, collagenase resistance assay, and injection force studies were performed to assess RPC's physicochemical properties. An in vivo study was performed which consisted of a 1‐, 3‐, and 6‐month study where RPC was injected into the ears of miniature swine. The results demonstrated that the liquid RPC requires low injection force (<7 N); fibrillogenesis and banding of collagen occurs when RPC is injected into ionic solutions, and RPC has enhanced resistance to collagenase breakdown. The in vivo study demonstrated long‐term biocompatibility with low irritation scores. In conclusion RPC possesses many of the desirable properties of a soft tissue augmentation material. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 758–767, 2016. PMID:26488368

Hydrophilic crosslinked-polymeric surface capable of effective suppression of protein adsorption

NASA Astrophysics Data System (ADS)

Kamon, Yuri; Inoue, Naoko; Mihara, Erika; Kitayama, Yukiya; Ooya, Tooru; Takeuchi, Toshifumi

2016-08-01

We investigated the nonspecific adsorption of proteins towards three hydrophilic crosslinked-polymeric thin layers prepared by surface-initiated atom transfer radical polymerization using N,N‧-methylenebisacrylamide, 2-(methacryloyloxy)ethyl-[N-(2-methacryloyloxy)ethyl]phosphorylcholine (MMPC), or 6,6‧-diacryloyl-trehalose crosslinkers. Protein binding experiments were performed by surface plasmon resonance with six proteins of different pI values including α-lactalbumin, bovine serum albumin (BSA), myoglobin, ribonuclease A, cytochrome C, and lysozyme in buffer solution at pH 7.4. All of the obtained crosslinked-polymeric thin layers showed low nonspecific adsorption of negatively charged proteins at pH 7.4 such as α-lactalbumin, BSA, and myoglobin. Nonspecific adsorption of positively charged proteins including ribonuclease A, cytochrome C, and lysozyme was the lowest for poly(MMPC). These results suggest poly(MMPC) can effectively reduce nonspecific adsorption of a wide range of proteins that are negatively or positively charged at pH 7.4. MMPC is a promising crosslinker for a wide range of polymeric materials requiring low nonspecific protein binding.

Selective sorption of lead, cadmium and zinc ions by a polymeric cation exchanger containing nano-Zr(HPO3S)2.

PubMed

Zhang, Qingrui; Pan, Bingcai; Pan, Bingjun; Zhang, Weiming; Jia, Kun; Zhang, Quanxing

2008-06-01

A novel polymeric hybrid sorbent, namely ZrPS-001, was fabricated for enhanced sorption of heavy metal ions by impregnating Zr(HPO3S)2 (i.e., ZrPS) nanoparticles within a porous polymeric cation exchanger D-001. The immobilized negatively charged groups bound to the polymeric matrix D-001 would result in preconcentration and permeation enhancement of target metal ions prior to sequestration, and ZrPS nanoparticles are expected to sequester heavy metals selectively through an ion-exchange process. Highly effective sequestration of lead, cadmium, and zinc ions from aqueous solution can be achieved by ZrPS-001 even in the presence of competing calcium ion at concentration several orders of magnitude greater than the target species. The exhausted ZrPS-001 beads are amenable to regeneration with 6 M HCI solution for repeated use without any significant capacity loss. Fixed-bed column treatment of simulated waters containing heavy metals at high or trace levels was also performed. The content of heavy metals in treated effluent approached or met the WHO drinking water standard.

Aqueous dispersion polymerization: a new paradigm for in situ block copolymer self-assembly in concentrated solution.

PubMed

Sugihara, Shinji; Blanazs, Adam; Armes, Steven P; Ryan, Anthony J; Lewis, Andrew L

2011-10-05

Reversible addition-fragmentation chain transfer polymerization has been utilized to polymerize 2-hydroxypropyl methacrylate (HPMA) using a water-soluble macromolecular chain transfer agent based on poly(2-(methacryloyloxy)ethylphosphorylcholine) (PMPC). A detailed phase diagram has been elucidated for this aqueous dispersion polymerization formulation that reliably predicts the precise block compositions associated with well-defined particle morphologies (i.e., pure phases). Unlike the ad hoc approaches described in the literature, this strategy enables the facile, efficient, and reproducible preparation of diblock copolymer spheres, worms, or vesicles directly in concentrated aqueous solution. Chain extension of the highly hydrated zwitterionic PMPC block with HPMA in water at 70 °C produces a hydrophobic poly(2-hydroxypropyl methacrylate) (PHPMA) block, which drives in situ self-assembly to form well-defined diblock copolymer spheres, worms, or vesicles. The final particle morphology obtained at full monomer conversion is dictated by (i) the target degree of polymerization of the PHPMA block and (ii) the total solids concentration at which the HPMA polymerization is conducted. Moreover, if the targeted diblock copolymer composition corresponds to vesicle phase space at full monomer conversion, the in situ particle morphology evolves from spheres to worms to vesicles during the in situ polymerization of HPMA. In the case of PMPC(25)-PHPMA(400) particles, this systematic approach allows the direct, reproducible, and highly efficient preparation of either block copolymer vesicles at up to 25% solids or well-defined worms at 16-25% solids in aqueous solution.

Biological phosphorus removal in an extended ASM2 model: Roles of extracellular polymeric substances and kinetic modeling.

PubMed

Yang, Shan-Shan; Pang, Ji-Wei; Guo, Wan-Qian; Yang, Xiao-Yin; Wu, Zhong-Yang; Ren, Nan-Qi; Zhao, Zhi-Qing

2017-05-01

This paper presents the results of an extended ASM2 model for the modeling and calibration of the role of extracellular polymeric substances (EPS) in phosphorus (P) removal in an anaerobic-aerobic process. In this extended ASM2 model, two new components, the bound EPS (X EPS ) and the soluble EPS (S EPS ), are introduced. Compared with the ASM2, 7.71, 8.53, and 9.28% decreases in polyphosphate (polyP) were observed in the extended ASM2 in three sequencing batch reactors feeding with different COD/P ratios, indicating that 7.71-9.28% of P in the liquid was adsorbed by EPS. Sensitive analysis indicated that, five parameters were the significant influential parameters and had been chosen for further model calibration by using the least square method to simulate by MATLAB. This extended ASM2 has been successfully established to simulate the output variables and provides a useful reference for the mathematic simulations of the role of EPS in biological phosphorus removal process. Copyright © 2017. Published by Elsevier Ltd.

Application of Ionic Liquids in Pot-in-Pot Reactions.

PubMed

Çınar, Simge; Schulz, Michael D; Oyola-Reynoso, Stephanie; Bwambok, David K; Gathiaka, Symon M; Thuo, Martin

2016-02-26

Pot-in-pot reactions are designed such that two reaction media (solvents, catalysts and reagents) are isolated from each other by a polymeric membrane similar to matryoshka dolls (Russian nesting dolls). The first reaction is allowed to progress to completion before triggering the second reaction in which all necessary solvents, reactants, or catalysts are placed except for the starting reagent for the target reaction. With the appropriate trigger, in most cases unidirectional flux, the product of the first reaction is introduced to the second medium allowing a second transformation in the same glass reaction pot--albeit separated by a polymeric membrane. The basis of these reaction systems is the controlled selective flux of one reagent over the other components of the first reaction while maintaining steady-state catalyst concentration in the first "pot". The use of ionic liquids as tools to control chemical potential across the polymeric membranes making the first pot is discussed based on standard diffusion models--Fickian and Payne's models. Besides chemical potential, use of ionic liquids as delivery agent for a small amount of a solvent that slightly swells the polymeric membrane, hence increasing flux, is highlighted. This review highlights the critical role ionic liquids play in site-isolation of multiple catalyzed reactions in a standard pot-in-pot reaction.

Microwave-assisted ionic liquid-mediated rapid catalytic conversion of non-edible lignocellulosic Sunn hemp fibres to biofuels.

PubMed

Paul, Souvik Kumar; Chakraborty, Saikat

2018-04-01

Sunn hemp fibre - a cellulose-rich crystalline non-food energy crop, containing 75.6% cellulose, 10.05% hemicellulose, 10.32% lignin, with high crystallinity (80.17%) and degree of polymerization (650) - is identified as a new non-food substrate for lignocellulosic biofuel production. Microwave irradiation is employed to rapidly rupture the cellulose's glycosidic bonds and enhance glucose yield to 78.7% at 160 °C in only 46 min. The reactants - long-chain cellulose, ionic liquid, transition metal catalyst, and water - form a polar supramolecular complex that rotates under the microwave's alternating polarity and rapidly dissipates the electromagnetic energy through molecular collisions, thus accelerating glycosidic bond breakage. In 46 min, 1 kg of Sunn hemp fibres containing 756 g of cellulose produces 595 g of glucose at 160 °C, and 203 g of hydroxymethyl furfural (furanic biofuel precursor) at 180 °C. Yeast mediated glucose fermentation produces 75.6% bioethanol yield at 30 °C, and the ionic liquid is recycled for cost-effectiveness. Copyright © 2018 Elsevier Ltd. All rights reserved.

Surface and Electrochemical Properties of Polymer Brush-Based Redox Poly(Ionic Liquid).

PubMed

Bui-Thi-Tuyet, Van; Trippé-Allard, Gaëlle; Ghilane, Jalal; Randriamahazaka, Hyacinthe

2016-10-26

Redox-active poly(ionic liquid) poly(3-(2-methacryloyloxy ethyl)-1-(N-(ferrocenylmethyl) imidazolium bis(trifluoromethylsulfonyl)imide deposited onto electrode surfaces has been prepared using surface-initiated atom transfer radical polymerization SI-ATRP. The process starts by electrochemical immobilization of initiator layer, and then methacrylate monomer carrying ferrocene and imidazolium units is polymerized in ionic liquid media via SI-ATRP process. The surfaces analyses of the polymer exhibit a well-defined polymer brushlike structure and confirm the presence of ferrocene and ionic moieties within the film. Furthermore, the electrochemical investigations of poly(redox-active ionic liquid) in different media demonstrate that the electron transfer is not restricted by the rate of counterion migration into/out of the polymer. The attractive electrochemical performance of these materials is further demonstrated by performing electrochemical measurement, of poly(ferrocene ionic liquid), in solvent-free electrolyte. The facile synthesis of such highly ordered electroactive materials based ionic liquid could be useful for the fabrication of nanostructured electrode suitable for performing electrochemistry in solvent free electrolyte. We also demonstrate possible applications of the poly(FcIL) as electrochemically reversible surface wettability system and as electrochemical sensor for the catalytic activity toward the oxidation of tyrosine.

Click polymerization for the synthesis of reduction-responsive polymeric prodrug

NASA Astrophysics Data System (ADS)

Zhang, Xiaojin; Wang, Hongquan; Dai, Yu

2018-05-01

Click polymerization is a powerful polymerization technique for the construction of new macromolecules with well-defined structures and multifaceted functionalities. Here, we synthesize reduction-responsive polymeric prodrug PEG- b-(PSS- g-MTX)- b-PEG containing disulfide bonds and pendant methotrexate (MTX) via two-step click polymerization followed by conjugating MTX to pendant hydroxyl. MTX content in polymeric prodrug is 13.5%. Polymeric prodrug is able to form polymeric micelles by self-assembly in aqueous solution. Polymeric micelles are spherical nanoparticles with tens of nanometers in size. Of note, polymeric micelles are reduction-responsive due to disulfide bonds in the backbone of PEG- b-(PSS- g-MTX)- b-PEG and could release pendant drugs in the presence of the reducing agents such as dl-dithiothreitol (DTT).

Novel (meth)acrylate monomers for ultrarapid polymerization and enhanced polymer properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beckel, E. R.; Berchtold, K. A.; Nie, J.

2002-01-01

Ultraviolet light is known to be one of the most efficient methods to initiatc polymeric reactions in the presence of a photonitiator. Photopolymerizations are advantageous because the chemistry of the materials can be tailored to design liquid monomers for ultrarapid polymerization into a solid polymer material. One way to achieve rapid photopolymerizations is to utilize multifunctional (meth)acrylate monomers. which form highly crosslinked polymers; however, these monomers typically do not achieve complete functional group conversion. Recently, Decker et al. developed novel monovinyl acrylate monomers that display polyriicrization kinetics that rival those of multifunctional acrylate monomers. These novel acrylate monomers incorporate secondarymore » functionalities and end groups such as carbonates, carbamates, cyclic carbonates and oxazolidone which promote the increased polymerization kinetics of these monomers. In addition to thc polynierization kinetics, these novel monovinyl monomers form crosslinked polymers, which are characterized by having high strength and high flexibility. Unfortunately, the exact mechanism or mechanisms responsible for the polymerization kinetics and crosslinking are not well understood.« less

Molecular characteristics of stress overshoot for polymer melts under start-up shear flow.

PubMed

Jeong, Sohdam; Kim, Jun Mo; Baig, Chunggi

2017-12-21

Stress overshoot is one of the most important nonlinear rheological phenomena exhibited by polymeric liquids undergoing start-up shear at sufficient flow strengths. Despite considerable previous research, the fundamental molecular characteristics underlying stress overshoot remain unknown. Here, we analyze the intrinsic molecular mechanisms behind the overshoot phenomenon using atomistic nonequilibrium molecular dynamics simulations of entangled linear polyethylene melts under shear flow. Through a detailed analysis of the transient rotational chain dynamics, we identify an intermolecular collision angular regime in the vicinity of the chain orientation angle θ ≈ 20° with respect to the flow direction. The shear stress overshoot occurs via strong intermolecular collisions between chains in the collision regime at θ = 15°-25°, corresponding to a peak strain of 2-4, which is an experimentally well-known value. The normal stress overshoot appears at approximately θ = 10°, at a corresponding peak strain roughly equivalent to twice that for the shear stress. We provide plausible answers to several basic questions regarding the stress overshoot, which may further help understand other nonlinear phenomena of polymeric systems.

Novel double-confined polymeric ionic liquids as sorbents for solid-phase microextraction with enhanced stability and durability in high-ionic-strength solution.

PubMed

Feng, Juanjuan; Sun, Min; Xu, Lili; Wang, Shuai; Liu, Xia; Jiang, Shengxiang

2012-12-14

Because of the occurrence of ion exchange between high-ionic-strength solution and anions of polymeric ionic liquids (PILs), PILs based solid-phase microextraction (SPME) fibers were rarely used in direct immersion mode to high-salt-added samples. In this work, a novel double-confined PIL sorbent was prepared by co-polymerization of cation and anion of 1-vinyl-3-octylimidzaolium p-styrenesulfonate (VOIm(+)SS(-)). The poly(VOIm(+)-SS(-)) was chemically bonded onto functionalized stainless steel wire via surface radical chain-transfer reaction. Stability of poly(VOIm(+)-SS(-)) in high-ionic-strength solution was investigated and compared with that of poly(1-vinyl-3-octylimidzaolium benzenesulfonate) (poly(VOIm(+)BS(-))) by elemental analysis of sulfur element, and results turned out that the poly(VOIm(+)-SS(-)) was more stable. Coupled to gas chromatography (GC), the poly(VOIm(+)-SS(-)) fiber was used to extract three sorts of compounds including anilines, phenols and phthalate esters in aqueous solution. The as-established method showed good linearity, low detection limits, and acceptable repeatability. The direct immersion SPME-GC method was applied to determine the model phthalate esters in bottled mineral water. The determination results were satisfactory. Copyright © 2012 Elsevier B.V. All rights reserved.

Polyimides containing oxyethylene units. Part 4: Polymerization of dianhydrides containing ether linkages

NASA Technical Reports Server (NTRS)

Harris, F. W.; Karnavas, A. J.; Das, S.; Cucuras, C. N.; Hergenrother, P. M.

1986-01-01

The development of new composite resins for various aerospace applications is attempted. Although it is highly desirable that these polymers be soluble in order to facilitate processing, they must display considerable solvent-resistance in use. A recent approach has involved the synthesis of a new series of polyimides containing flexible linkages. The polymers were prepared by the polymerization of aromatic dianhydrides with diamines containing oxyethylene linkages. For example, the polymerization of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) with 1,2-bis(4-aminophenoxy)ethane (1a) and bis2-(4-aminophenoxy)ethylether (lb), afforded highly crystalline polyimides that were completely insoluble. However, a polyimide that was amorphous and soluble was obtained from the polymerization of BTDA and an isomer of lb, i.e., bis2-(3-aminophenoxy)ethyl ether (4b). In an attempt to obtain a soluble, amorphous polyimide that could be annealed into a crysalline state, block copolymers of 1b and 4b and BTDA were prepared. Copolymers containing less than 20 weight % 1b were soluble in organic solvents. However, these polymers did not crystallize when heated above their Tg's. Copolymers containing higher levels of 1b were semicrystalline and insoluble. The polymerization of the diamines containing oxyethylene linkages with 4,4'-oxydiphthalic anhydride (ODPA) and a new dianhydride, i.e., 4,4'-oxyethyleneoxyethyleneoxydiphthalic anhydride (OEDA) was investigated. It was postulated that the use of these more flexible dianhydrides would result in more processable polyimides.

Fabrication of superhydrophobic fluorinated silica nanoparticles for multifunctional liquid marbles

NASA Astrophysics Data System (ADS)

Shang, Qianqian; Hu, Lihong; Hu, Yun; Liu, Chengguo; Zhou, Yonghong

2018-01-01

A facile one-pot method for the fabrication of superhydrophobic fluorinated silica nanoparticles is reported. Fluorinated aggregated silica (A-SiO2/FAS) nanoparticles were synthesized by controlling the nanoparticles assembly, in situ fixation and overgrowth of particle seeds with the assist of tetraethoxysilane (TEOS) in ethanol/water solution and then modification with fluoroalkylsilane (FAS) molecules. Such kind of A-SiO2/FAS nanoparticles showed superhydrophobicity and was not wetted by water, thus it could be served as the encapsulating shells to manipulate liquid droplets. Liquid marbles fabricated from A-SiO2/FAS nanoparticles were used for ammonia gas sensing or emitting by taking advantage of the porosity and superhydrophobicity of the liquid marble shells. In addition, the posibility of A-SiO2/FAS-based liquid marbles as microreactor for dopamine polymerization also was explored.

Non-equilibrium supramolecular polymerization

PubMed Central

Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J.

2017-01-01

Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term “non-equilibrium self-assembly” by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization. PMID:28349143

Hydrophobic Coatings on Cotton Obtained by in Situ Plasma Polymerization of a Fluorinated Monomer in Ethanol Solutions.

PubMed

Molina, Ricardo; Teixidó, Josep Maria; Kan, Chi-Wai; Jovančić, Petar

2017-02-15

Plasma polymerization using hydrophobic monomers in the gas phase is a well-known technology to generate hydrophobic coatings. However, synthesis of functional hydrophobic coatings using plasma technology in liquids has not yet been accomplished. This work is consequently focused on polymerization of a liquid fluorinated monomer on cotton fabric initiated by atmospheric plasma in a dielectric barrier discharge configuration. Functional hydrophobic coatings on cotton were successfully achieved using in situ atmospheric plasma-initiated polymerization of fluorinated monomer dissolved in ethanol. Gravimetric measurements reveal that the amount of polymer deposited on cotton substrates can be modulated with the concentration of monomer in ethanol solution, and cross-linking reactions occur during plasma polymerization of a fluorinated monomer even without the presence of a cross-linking agent. FTIR and XPS analysis were used to study the chemical composition of hydrophobic coatings and to get insights into the physicochemical processes involved in plasma treatment. SEM analysis reveals that at high monomer concentration, coatings possess a three-dimensional pattern with a characteristic interconnected porous network structure. EDX analysis reveals that plasma polymerization of fluorinated monomers takes place preferentially at the surface of cotton fabric and negligible polymerization takes place inside the cotton fabric. Wetting time measurements confirm the hydrophobicity of cotton coatings obtained although equilibrium moisture content was slightly decreased. Additionally, the abrasion behavior and resistance to washing of plasma-coated cotton has been evaluated.

A physically-based retrieval of cloud liquid water from SSM/I measurements

NASA Technical Reports Server (NTRS)

Greenwald, Thomas J.; Stephens, Graeme L.; Vonder Haar, Thomas H.

1992-01-01

A simple physical scheme is proposed for retrieving cloud liquid water over the ice-free global oceans from Special Sensor Microwave/Imager (SSM/I) observations. Details of the microwave retrieval scheme are discussed, and the microwave-derived liquid water amounts are compared with the ground radiometer and AVHRR-derived liquid water for stratocumulus clouds off the coast of California. Global distributions of the liquid water path derived by the method proposed here are presented.

IONIC LIQUID-CATALYZED ALKYLATION OF ISOBUTANE WITH 2-BUTENE

EPA Science Inventory

A detailed study of the alkylation of isobutane with 2-butene in ionic liquid media has been conducted using 1-alkyl-3-methylimidazolium halides?aluminum chloride encompassing various alkyl groups (butyl-, hexyl-, and octyl-) and halides (Cl, Br, and I) on its cations and anions,...

Polymer-Based Black Phosphorus (bP) Hybrid Materials by in Situ Radical Polymerization: An Effective Tool To Exfoliate bP and Stabilize bP Nanoflakes

PubMed Central

2018-01-01

Black phosphorus (bP) has been recently investigated for next generation nanoelectronic multifunctional devices. However, the intrinsic instability of exfoliated bP (the bP nanoflakes) toward both moisture and air has so far overshadowed its practical implementation. In order to contribute to fill this gap, we report here the preparation of new hybrid polymer-based materials where bP nanoflakes (bPn) exhibit a significantly improved stability. The new materials have been prepared by different synthetic paths including: (i) the mixing of conventionally liquid-phase exfoliated bP (in dimethyl sulfoxide, DMSO) with poly(methyl methacrylate) (PMMA) solution; (ii) the direct exfoliation of bP in a polymeric solution; (iii) the in situ radical polymerization after exfoliating bP in the liquid monomer (methyl methacrylate, MMA). This last methodology concerns the preparation of stable suspensions of bPn–MMA by sonication-assisted liquid-phase exfoliation (LPE) of bP in the presence of MMA followed by radical polymerization. The hybrids characteristics have been compared in order to evaluate the bP dispersion and the effectiveness of the bPn interfacial interactions with polymer chains aimed at their long-term environmental stabilization. The passivation of the bPn is particularly effective when the hybrid material is prepared by in situ polymerization. By using this synthetic methodology, the nanoflakes, even if with a gradient of dispersion (size of aggregates), preserve their chemical structure from oxidation (as proved by both Raman and 31P-solid state NMR studies) and are particularly stable to air and UV light exposure. The feasibility of this approach, capable of efficiently exfoliating bP while protecting the bPn, has been then verified by using different vinyl monomers (styrene and N-vinylpyrrolidone), thus obtaining hybrids where the nanoflakes are embedded in polymer matrices with a variety of intriguing thermal, mechanical, and solubility characteristics.

DISPERSION POLYMERIZATION OF 2-HYDROXYETHYL METHACRYLATE IN SUPERCRITICAL CARBON DIOXIDE. (R826115)

EPA Science Inventory

Herein we report a successful dispersion polymerization of 2-hydroxyethyl methacrylate (HEMA) in a carbon dioxide continuous phase with a block copolymer consisting of polystyrene and poly(1,1-dihydroperfluorooctyl acrylate) as a stabilizer. Poly(2-hydroxyethyl methacrylate) was ...

HPLC separation of triacylglycerol positional isomers on a polymeric ODS column.

PubMed

Kuroda, Ikuma; Nagai, Toshiharu; Mizobe, Hoyo; Yoshimura, Nobuhito; Gotoh, Naohiro; Wada, Shun

2008-07-01

A polymeric ODS column was applied to the resolution of triacylglycerol positional isomers (TAG-PI), i.e. 1,3-dioleoyl-2-palmitoyl-glycerol (OPO) and 1,2-dioleoyl-3-palmitoyl-rac-glycerol (OOP), with a recycle HPLC system. To investigate the ODS column species and the column temperatures for the resolution of a TAG-PI pair, a mixture of OPO and OOP was subjected to an HPLC system equipped with a non-endcapped polymeric, endcapped monomeric, endcapped intermediate, or non-endcapped monomeric ODS column at three different column temperatures (40, 25, or 10 degrees C). Only the non-endcapped polymeric ODS column achieved the separation of OPO and OOP, and the lowest column temperature (10 degrees C) showed the best resolution for them. The other pair of TAG-PI, a mixture of 1,3-dipalmitoyl-2-oleoyl-glycerol (POP) and 1,2-dipalmitoyl-3-oleoyl-rac-glycerol (PPO) was also subjected to the system equipped with a non-endcapped polymeric or monomeric ODS column at five different column temperatures (40, 32, 25, 17, and 10 degrees C). Thus, POP and PPO were also separated on only the non-endcapped polymeric ODS column at 25 degrees C. However, no clear peak appeared at 10 degrees C. These results would indicate that the polymeric ODS stationary phase has an ability to recognize the structural differences between TAG-PI pairs. Also, the column temperature is a very important factor for separating the TAG-PI pair, and the optimal temperature would relate to the solubility of TAG-PI in the mobile phase. Furthermore, the recycle HPLC system provided measurements for the separation and analysis of TAG-PI pairs.

Photocatalytic CO2 conversion by polymeric carbon nitrides.

PubMed

Fang, Yuanxing; Wang, Xinchen

2018-05-10

CO2 is a vital compond for life, and its concentration significantly affects the living environment of the Earth. Extensive effort has been devoted to balance its concentration. Among the developed approaches, photocatalytic CO2 conversion is considered as an ideal option. Previous reports suggest polymeric carbon nitride (PCN) can be effectively used as a metal-free photocatalyst to convert CO2. Herein, the recent developments of PCN and the related photocatalysts for CO2 conversion are summarized from the fundamental of using PCN, and their extended applications through molecular modification and physical/chemical coupling with other substances. The concluding remarks finally indicate the future challenges of using PCN materials for relevant solar-driven applications.

Asymmetric reduction of benzil to (S)-benzoin with Penicillium claviforme IAM 7294 in a liquid-liquid interface bioreactor (L-L IBR).

PubMed

Oda, Shinobu; Isshiki, Kunio

2008-05-01

The asymmetric reduction of benzyl to (S)-benzoin with Penicillium claviforme IAM 7294 was applied to a liquid-liquid interface bioreactor (L-L IBR) using a unique polymeric material, ballooned microsphere (MS). The L-L IBR showed superior performance, as compared with suspension, organic-aqueous two-liquid-phase, and solid-liquid interface bioreactor (S-L IBR) systems, affording 14.4 g/l-organic phase of (S)-benzoin (99.0% ee).

AgPO2F2 and Ag9(PO2F2)14: the first Ag(i) and Ag(i)/Ag(ii) difluorophosphates with complex crystal structures.

PubMed

Malinowski, Przemysław J; Kurzydłowski, Dominik; Grochala, Wojciech

2015-12-07

The reaction of AgF2 with P2O3F4 yields a mixed valence Ag(I)/Ag(II) difluorophosphate salt with AgAg(PO2F2)14 stoichiometry - the first Ag(ii)-PO2F2 system known. This highly moisture sensitive brown solid is thermally stable up to 120 °C, which points at further feasible extension of the chemistry of Ag(ii)-PO2F2 systems. The crystal structure shows a very complex bonding pattern, comprising of polymeric Ag(PO2F2)14(4-) anions and two types of Ag(I) cations. One particular Ag(II) site present in the crystal structure of Ag9(PO2F2)14 is the first known example of square pyramidal penta-coordinated Ag(ii) in an oxo-ligand environment. Ag(i)PO2F2 - the product of the thermal decomposition of Ag9(PO2F2)14 - has also been characterized by thermal analysis, IR spectroscopy and X-ray powder diffraction. It has a complicated crystal structure as well, which consists of infinite 1D [Ag(I)O4/2] chains which are linked to more complex 3D structures via OPO bridges. The PO2F2(-) anions bind to cations in both compounds as bidentate oxo-ligands. The terminal F atoms tend to point inside the van der Waals cavities in the crystal structure of both compounds. All important structural details of both title compounds were corroborated by DFT calculations.

Enhanced dual-frequency operation of a polymerized liquid crystal microplate by liquid crystal infiltration

NASA Astrophysics Data System (ADS)

Kumagai, Takayuki; Yoshida, Hiroyuki; Ozaki, Masanori

2017-04-01

The electric-field-induced switching behavior of a polymer microplate is investigated. A microplate fabricated with a photopolymerizable dual-frequency liquid crystal was surrounded by an unpolymerized photopolymerizable dual-frequency liquid crystal in the isotropic phase. As an electric field was applied along the plane of the microplate, the microplate switched to set its interior molecular orientation to be either parallel or perpendicular to the field, depending on the frequency. Analysis of the rotational behavior, as well as numerical calculations, showed that the surrounding unpolymerized photopolymerizable dual-frequency liquid crystal infiltrated into the microplate, which enhanced the dielectric properties of the microplate. To the best of our knowledge, this is the first report of an enhanced dual-frequency dielectric response of a polymer microplate induced by liquid crystal infiltration.

Dynamics of CO2 scattering off a perfluorinated self-assembled monolayer. Influence of the incident collision energy, mass effects, and use of different surface models.

PubMed

Nogueira, Juan J; Vázquez, Saulo A; Mazyar, Oleg A; Hase, William L; Perkins, Bradford G; Nesbitt, David J; Martínez-Núñez, Emilio

2009-04-23

The dynamics of collisions of CO2 with a perfluorinated alkanethiol self-assembled monolayer (F-SAM) on gold were investigated by classical trajectory calculations using explicit atom (EA) and united atom (UA) models to represent the F-SAM surface. The CO2 molecule was directed perpendicularly to the surface at initial collision energies of 1.6, 4.7, 7.7, and 10.6 kcal/mol. Rotational distributions of the scattered CO2 molecules are in agreement with experimental distributions determined for collisions of CO2 with liquid surfaces of perfluoropolyether. The agreement is especially good for the EA model. The role of the mass in the efficiency of the energy transfer was investigated in separate simulations in which the mass of the F atoms was replaced by either that of hydrogen or chlorine, while keeping the potential energy function unchanged. The calculations predict the observed trend that less energy is transferred to the surface as the mass of the alkyl chains increases. Significant discrepancies were found between results obtained with the EA and UA models. The UA surface leads to an enhancement of the energy transfer efficiency in comparison with the EA surface. The reason for this is in the softer structure of the UA surface, which facilitates transfer from translation to interchain vibrational modes.

Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. I. Structural properties.

PubMed

Costa, Luciano T; Ribeiro, Mauro C C

2006-05-14

Molecular dynamics (MD) simulations have been performed for prototype models of polymer electrolytes in which the salt is an ionic liquid based on 1-alkyl-3-methylimidazolium cations and the polymer is poly(ethylene oxide), PEO. The MD simulations were performed by combining the previously proposed models for pure ionic liquids and polymer electrolytes containing simple inorganic ions. A systematic investigation of ionic liquid concentration, temperature, and the 1-alkyl- chain length, [1,3-dimethylimidazolium]PF6, and [1-butyl-3-methylimidazolium]PF6, effects on resulting equilibrium structure is provided. It is shown that the ionic liquid is dispersed in the polymeric matrix, but ionic pairs remain in the polymer electrolyte. Imidazolium cations are coordinated by both the anions and the oxygen atoms of PEO chains. Probability density maps of occurrences of nearest neighbors around imidazolium cations give a detailed physical picture of the environment experienced by cations. Conformational changes on PEO chains upon addition of the ionic liquid are identified. The equilibrium structure of simulated systems is also analyzed in reciprocal space by using the static structure factor, S(k). Calculated S(k) display a low wave-vector peak, indicating that spatial correlation in an extended-range order prevail in the ionic liquid polymer electrolytes. Long-range correlations are assigned to nonuniform distribution of ionic species within the simulation box.

Determination of cloud liquid water content using the SSM/I

NASA Technical Reports Server (NTRS)

Alishouse, John C.; Snider, Jack B.; Westwater, Ed R.; Swift, Calvin T.; Ruf, Christopher S.

1990-01-01

As part of a calibration/validation effort for the special sensor microwave/imager (SSM/I), coincident observations of SSM/I brightness temperatures and surface-based observations of cloud liquid water were obtained. These observations were used to validate initial algorithms and to derive an improved algorithm. The initial algorithms were divided into latitudinal-, seasonal-, and surface-type zones. It was found that these initial algorithms, which were of the D-matrix type, did not yield sufficiently accurate results. The surface-based measurements of channels were investigated; however, the 85V channel was excluded because of excessive noise. It was found that there is no significant correlation between the SSM/I brightness temperatures and the surface-based cloud liquid water determination when the background surface is land or snow. A high correlation was found between brightness temperatures and ground-based measurements over the ocean.

Chain Reaction Polymerization.

ERIC Educational Resources Information Center

McGrath, James E.

1981-01-01

The salient features and importance of chain-reaction polymerization are discussed, including such topics as the thermodynamics of polymerization, free-radical polymerization kinetics, radical polymerization processes, copolymers, and free-radical chain, anionic, cationic, coordination, and ring-opening polymerizations. (JN)

Widely tunable chiral nematic liquid crystal optical filter with microsecond switching time.

PubMed

Mohammadimasoudi, Mohammad; Beeckman, Jeroen; Shin, Jungsoon; Lee, Keechang; Neyts, Kristiaan

2014-08-11

A wavelength shift of the photonic band gap of 141 nm is obtained by electric switching of a partly polymerized chiral liquid crystal. The devices feature high reflectivity in the photonic band gap without any noticeable degradation or disruption and have response times of 50 µs and 20 µs for switching on and off. The device consists of a mixture of photo-polymerizable liquid crystal, non-reactive nematic liquid crystal and a chiral dopant that has been polymerized with UV light. We investigate the influence of the amplitude of the applied voltage on the width and the depth of the reflection band.

In vitro comparison of autoclave polymerization on the transverse strength of denture base resins.

PubMed

Durkan, Rukiye; Ozel, Mehmet Birol; Bağiş, Bora; Usanmaz, Ali

2008-07-01

The aim of this study was to determine the effect of autoclave polymerization on the transverse strength of denture base polymers. To this end, 30 rectangular test specimens were fabricated of two heat-polymerized denture base polymers. The test groups were: (I) control, i.e., conventional water bath to polymerize resins by heat at 100 degrees C for 30 minutes; (II) autoclave polymerization at 60 degrees C for 30 minutes followed by 130 degrees C for 10 minutes; and (III) autoclave polymerization at 60 degrees C for 30 minutes followed by 130 degrees C for 20 minutes. The specimens were tested with three-point bending test at a crosshead speed of 5 mm/min. It was revealed that the transverse strength of specimens increased with statistical significance when the autoclave was used for polymerization.

A NOVEL ENVIRONMENT FRIENDLY METHOD FOR EXPANSION AND MOLDING OF POLYMERIC FOAM

EPA Science Inventory

The objective of the project is to develop an environment friendly, novel and efficient alternative process for expansion and molding of polymeric foam. Spherical, expandable polymer beads are prepared from liquid monomer suspended in an aqueous medium, containing an expansion...

Hyperfine excitation of C2H in collisions with ortho- and para-H2

NASA Astrophysics Data System (ADS)

Dagdigian, Paul J.

2018-06-01

Accurate estimation of the abundance of the ethynyl (C2H) radical requires accurate radiative and collisional rate coefficients. Hyperfine-resolved rate coefficients for (de-)excitation of C2H in collisions with ortho- and para-H2 are presented in this work. These rate coefficients were computed in time-independent close-coupling quantum scattering calculations that employed a potential energy surface recently computed at the coupled-clusters level of theory that describes the interaction of C2H with H2. Rate coefficients for temperatures from 10 to 300 K were computed for all transitions among the first 40 hyperfine energy levels of C2H in collisions with ortho- and para-H2. These rate coefficients were employed in simple radiative transfer calculations to simulate the excitation of C2H in typical molecular clouds.

Frontal Polymerization of Dicyclopentadiene: A Numerical Study.

PubMed

Goli, Elyas; Robertson, Ian D; Geubelle, Philippe H; Moore, Jeffrey S

2018-04-26

As frontal polymerization is being considered as a faster and more energy efficient manufacturing technique for polymer-matrix fiber-reinforced composites, we perform a finite-element-based numerical study of the initiation and propagation of a polymerization front in dicyclopentadiene (DCPD). The transient thermochemical simulations are complemented by an analytical study of the steady-state propagation of the polymerization front, allowing to draw a direct link between the cure kinetics model and the key characteristics of the front, i.e., front velocity and characteristic length scales. The second part of this study focuses on the prediction of the temperature spike associated with the merger of two polymerization fronts. The thermal peak, which might be detrimental to the properties of the polymerized material, is due to the inability of the heat associated with the highly exothermic reaction to be dissipated when the two fronts merge. The analysis investigates how the amplitude of the thermal spike is affected by the degree of cure at the time of the front merger.

12 CFR 563b.470 - Must I adjust liquidation sub-accounts?

Code of Federal Regulations, 2010 CFR

2010-01-01

... 12 Banks and Banking 5 2010-01-01 2010-01-01 false Must I adjust liquidation sub-accounts? 563b... liquidation sub-accounts? (a)(1) You must reduce the balance of an eligible account holder's or supplemental eligible account holder's sub-account if the deposit balance in the account holder's savings account at the...

Light-driven liquid microlenses

NASA Astrophysics Data System (ADS)

Angelini, A.; Pirani, F.; Frascella, F.; Ricciardi, S.; Descrovi, E.

2017-02-01

We propose a liquid polymeric compound based on photo-responsive azo-polymers to be used as light-activated optical element with tunable and reversible functionalities. The interaction of a laser beam locally modifies the liquid density thus producing a refractive index gradient. The laser induced refractive index profiles are observed along the optical axis of the microscope to evaluate the total phase shift induced and along the orthogonal direction to provide the axial distribution of the refractive index variation. The focusing and imaging properties of the liquid lenses as functions of the light intensity are illustrated.

Particle Production in Strong Electromagnetic Fields in Relativistic Heavy-Ion Collisions

DOE PAGES

Tuchin, Kirill

2013-01-01

I reviewmore » the origin and properties of electromagnetic fields produced in heavy-ion collisions. The field strength immediately after a collision is proportional to the collision energy and reaches ~ m π 2 at RHIC and ~ 10 m π 2 at LHC. I demonstrate by explicit analytical calculation that after dropping by about one-two orders of magnitude during the first fm/c of plasma expansion, it freezes out and lasts for as long as quark-gluon plasma lives as a consequence of finite electrical conductivity of the plasma. Magnetic field breaks spherical symmetry in the direction perpendicular to the reaction plane, and therefore all kinetic coefficients are anisotropic. I examine viscosity of QGP and show that magnetic field induces azimuthal anisotropy on plasma flow even in spherically symmetric geometry. Very strong electromagnetic field has an important impact on particle production. I discuss the problem of energy loss and polarization of fast fermions due to synchrotron radiation, consider photon decay induced by magnetic field, elucidate J / ψ dissociation via Lorentz ionization mechanism, and examine electromagnetic radiation by plasma. I conclude that all processes in QGP are affected by strong electromagnetic field and call for experimental investigation.« less

Failure Mechanisms of Hollow Fiber Supported Ionic Liquid Membranes

PubMed Central

Zeh, Matthew; Wickramanayake, Shan; Hopkinson, David

2016-01-01

Hollow fiber supported ionic liquid membranes (SILMs) were tested using the bubble point method to investigate potential failure modes, including the maximum transmembrane pressure before loss of the ionic liquid from the support. Porous hollow fiber supports were fabricated with different pore morphologies using Matrimid® and Torlon® as the polymeric material and 1-hexyl-3-methylimidalzolium bis(trifluoromethylsulfonyl)imide ([C6mim][Tf2N]) as the ionic liquid (IL) component. Hollow fiber SILMs were tested for their maximum pressure before failure, with pressure applied either from the bore side or shell side. It was found that the membranes exhibited one or more of three different modes of failure when pressurized: liquid loss (occurring at the bubble point), rupture, and collapse. PMID:27023620

InChIKey collision resistance: an experimental testing

PubMed Central

2012-01-01

InChIKey is a 27-character compacted (hashed) version of InChI which is intended for Internet and database searching/indexing and is based on an SHA-256 hash of the InChI character string. The first block of InChIKey encodes molecular skeleton while the second block represents various kinds of isomerism (stereo, tautomeric, etc.). InChIKey is designed to be a nearly unique substitute for the parent InChI. However, a single InChIKey may occasionally map to two or more InChI strings (collision). The appearance of collision itself does not compromise the signature as collision-free hashing is impossible; the only viable approach is to set and keep a reasonable level of collision resistance which is sufficient for typical applications. We tested, in computational experiments, how well the real-life InChIKey collision resistance corresponds to the theoretical estimates expected by design. For this purpose, we analyzed the statistical characteristics of InChIKey for datasets of variable size in comparison to the theoretical statistical frequencies. For the relatively short second block, an exhaustive direct testing was performed. We computed and compared to theory the numbers of collisions for the stereoisomers of Spongistatin I (using the whole set of 67,108,864 isomers and its subsets). For the longer first block, we generated, using custom-made software, InChIKeys for more than 3 × 1010 chemical structures. The statistical behavior of this block was tested by comparison of experimental and theoretical frequencies for the various four-letter sequences which may appear in the first block body. From the results of our computational experiments we conclude that the observed characteristics of InChIKey collision resistance are in good agreement with theoretical expectations. PMID:23256896

InChIKey collision resistance: an experimental testing.

PubMed

Pletnev, Igor; Erin, Andrey; McNaught, Alan; Blinov, Kirill; Tchekhovskoi, Dmitrii; Heller, Steve

2012-12-20

InChIKey is a 27-character compacted (hashed) version of InChI which is intended for Internet and database searching/indexing and is based on an SHA-256 hash of the InChI character string. The first block of InChIKey encodes molecular skeleton while the second block represents various kinds of isomerism (stereo, tautomeric, etc.). InChIKey is designed to be a nearly unique substitute for the parent InChI. However, a single InChIKey may occasionally map to two or more InChI strings (collision). The appearance of collision itself does not compromise the signature as collision-free hashing is impossible; the only viable approach is to set and keep a reasonable level of collision resistance which is sufficient for typical applications.We tested, in computational experiments, how well the real-life InChIKey collision resistance corresponds to the theoretical estimates expected by design. For this purpose, we analyzed the statistical characteristics of InChIKey for datasets of variable size in comparison to the theoretical statistical frequencies. For the relatively short second block, an exhaustive direct testing was performed. We computed and compared to theory the numbers of collisions for the stereoisomers of Spongistatin I (using the whole set of 67,108,864 isomers and its subsets). For the longer first block, we generated, using custom-made software, InChIKeys for more than 3 × 1010 chemical structures. The statistical behavior of this block was tested by comparison of experimental and theoretical frequencies for the various four-letter sequences which may appear in the first block body.From the results of our computational experiments we conclude that the observed characteristics of InChIKey collision resistance are in good agreement with theoretical expectations.

Optimization of Carbon and Nitrogen Sources for Extracellular Polymeric Substances Production by Chryseobacterium indologenes MUT.2.

PubMed

Khani, Mojtaba; Bahrami, Ali; Chegeni, Asma; Ghafari, Mohammad Davoud; Mansouran Zadeh, ALi

2016-06-01

Bacterial Extracellular Polymeric Substances (EPS) are environmental friendly and versatile polymeric materials that are used in a wide range of industries such as: food, textile, cosmetics, and pharmaceuticals. To make the production process of the EPS cost-effective, improvements in the production yield is required which could be implemented through application of processes such as optimized culture conditions, and development of the strains with higher yield ( e.g . through genetic manipulation), or using low-cost substrates. In this work, the effects of carbon and nitrogen sources were studied in order to improve the EPS production by the submerged cultivation of Chryseobacterium indologenes MUT.2. The mesophilic microorganism Chryseobacterium indologenes MUT.2, was grown and maintained in the Luria Bertani agar. The initial basal medium contained: glucose (20 g.L -1 ), yeast extracts (5 g.L -1 ), K 2 HPO 4 (6 g.L -1 ), NaH 2 PO 4 (7 g.L -1 ), NH 4 CL (0.7 g.L -1 ), and MgSO 4 (0.5 g.L -1 ). For evaluating the carbon and nitrogen sources' effect on the fermentation performance, cultures were prepared in 500 mL flasks filled with 300 mL of the medium. The single-factor experiments based on statistics was employed to evaluate and optimize the carbon and nitrogen sources for EPS production in the liquid culture medium of Chryseobacterium indologenes MUT.2. The preferred carbon-sources, sucrose and glucose, commonly gave the highest EPS production of 8.32 and 6.37 g.L -1 , respectively, and the maximum EPS production of 8.87 g.L -1 was achieved when glutamic acid (5 g.L -1 ) was employed as the nitrogen source. In this work, the culture medium for production of EPS by Chryseobacterium indologenes MUT.2 was optimized. Compared to the basal culture medium in shake-flasks and stirred tank bioreactor, the use of optimized culture medium has resulted in a 53% and 73% increase in the EPS production, respectively.

Optimization of Carbon and Nitrogen Sources for Extracellular Polymeric Substances Production by Chryseobacterium indologenes MUT.2

PubMed Central

Khani, Mojtaba; Bahrami, Ali; Chegeni, Asma; Ghafari, Mohammad Davoud; Mansouran Zadeh, ALi

2016-01-01

Background Bacterial Extracellular Polymeric Substances (EPS) are environmental friendly and versatile polymeric materials that are used in a wide range of industries such as: food, textile, cosmetics, and pharmaceuticals. To make the production process of the EPS cost-effective, improvements in the production yield is required which could be implemented through application of processes such as optimized culture conditions, and development of the strains with higher yield (e.g. through genetic manipulation), or using low-cost substrates. Objectives In this work, the effects of carbon and nitrogen sources were studied in order to improve the EPS production by the submerged cultivation of Chryseobacterium indologenes MUT.2. Materials and Methods The mesophilic microorganism Chryseobacterium indologenes MUT.2, was grown and maintained in the Luria Bertani agar. The initial basal medium contained: glucose (20 g.L-1), yeast extracts (5 g.L-1), K2HPO4 (6 g.L-1), NaH2PO4 (7 g.L-1), NH4CL (0.7 g.L-1), and MgSO4 (0.5 g.L-1). For evaluating the carbon and nitrogen sources’ effect on the fermentation performance, cultures were prepared in 500 mL flasks filled with 300 mL of the medium. The single-factor experiments based on statistics was employed to evaluate and optimize the carbon and nitrogen sources for EPS production in the liquid culture medium of Chryseobacterium indologenes MUT.2. Results The preferred carbon-sources, sucrose and glucose, commonly gave the highest EPS production of 8.32 and 6.37 g.L-1, respectively, and the maximum EPS production of 8.87 g.L-1 was achieved when glutamic acid (5 g.L-1) was employed as the nitrogen source. Conclusions In this work, the culture medium for production of EPS by Chryseobacterium indologenes MUT.2 was optimized. Compared to the basal culture medium in shake-flasks and stirred tank bioreactor, the use of optimized culture medium has resulted in a 53% and 73% increase in the EPS production, respectively. PMID:28959321

Auto Collision Technician: An Instructional Guide for Teachers.

ERIC Educational Resources Information Center

Ohio State Univ., Columbus. Vocational Instructional Materials Lab.

This guide is designed to help teachers in auto collision technician programs for grades 11 and 12 teach the critical competencies of the program. The critical competencies covered are the High Priority-Individual (HP-I) competencies in Ohio's Occupational Competency Assessment Profile (OCAP) for Auto Collision Technician. HP-I competencies are…

Dual drug release from hydrogels covalently containing polymeric micelles that possess different drug release properties.

PubMed

Murata, Mari; Uchida, Yusuke; Takami, Taku; Ito, Tomoki; Anzai, Ryosuke; Sonotaki, Seiichi; Murakami, Yoshihiko

2017-05-01

In the present study, we designed hydrogels for dual drug release: the hydrogels that covalently contained the polymeric micelles that possess different drug release properties. The hydrogels that were formed from polymeric micelles possessing a tightly packed (i.e., well-entangled) inner core exhibited a higher storage modulus than the hydrogels that were formed from the polymeric micelles possessing a loosely packed structure. Furthermore, we conducted release experiments and fluorescent observations to evaluate the profiles depicting the release of two compounds, rhodamine B and auramine O, from either polymeric micelles or hydrogels. According to our results, (1) hydrogels that covalently contains polymeric micelles that possess different drug release properties successfully exhibit the independent release behaviors of the two compounds and (2) fluorescence microscopy can greatly facilitate efforts to evaluate drug release properties of materials. Copyright © 2017 Elsevier B.V. All rights reserved.

Advancing Polymer-Supported Ionogel Electrolytes Formed via Radical Polymerization

NASA Astrophysics Data System (ADS)

Visentin, Adam F.

Applications ranging from consumer electronics to the electric grid have placed demands on current energy storage technologies. There is a drive for devices that store more energy for rapid consumption in the case of electric cars and the power grid, and safer, versatile design options for consumer electronics. Electrochemical double-layer capacitors (EDLCs) are an option that has garnered attention as a means to address these varied energy storage demands. EDLCs utilize charge separation in electrolytes to store energy. This energy storage mechanism allows for greater power density (W kg -1) than batteries and higher energy density (Wh kg-1) than conventional capacitors - along with a robust lifetime in the range of thousands to millions of charge-discharge cycles. Safety and working voltage windows of EDLCs currently on the market are limited by the organic solvents utilized in the electrolyte. A potential solution lies in the replacement of the organic solvents with ionic liquids, or room-temperature molten salts. Ionic liquids possess many superior properties in comparison to conventional solvents: wide electrochemical window, low volatility, nonflammability, and favorable ionic conductivity. It has been an endeavor of this work to exploit these advantages while altering the liquid form factor into a gel. An ionic liquid/solid support scaffold composite electrolyte, or ionogel, adds additional benefits: flexible device design, lower encapsulation weight, and elimination of electrolyte leakage. This work has focused on investigations of a UV-polymerizable monomer, poly(ethylene glycol) diacrylate, as a precursor for forming ionogels in situ. The trade-off between gaining mechanical stability at the cost of ionic conductivity has been investigated for numerous ionogel systems. While gaining a greater understanding of the interactions between the gel scaffold and ionic liquid, an ionogel with the highest known ionic conductivity to date (13.1 mS cm-1) was

Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)

NASA Astrophysics Data System (ADS)

Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)' providing data from direct measurement of pressure and mole fraction in vapor phase at variable mole fraction in liquid phase and constant temperature.

Multiple monolithic fiber solid-phase microextraction based on a polymeric ionic liquid with high-performance liquid chromatography for the determination of steroid sex hormones in water and urine.

PubMed

Liao, Keren; Mei, Meng; Li, Haonan; Huang, Xiaojia; Wu, Cuiqin

2016-02-01

The development of a simple and sensitive analytical approach that combines multiple monolithic fiber solid-phase microextraction with liquid desorption followed by high-performance liquid chromatography with diode array detection is proposed for the determination of trace levels of seven steroid sex hormones (estriol, 17β-estradiol, testosterone, ethinylestradiol, estrone, progesterone and mestranol) in water and urine matrices. To extract the target analytes effectively, multiple monolithic fiber solid-phase microextraction based on a polymeric ionic liquid was used to concentrate hormones. Several key extraction parameters including desorption solvent, extraction and desorption time, pH value and ionic strength in sample matrix were investigated in detail. Under the optimal experimental conditions, the limits of detection were found to be in the range of 0.027-0.12 μg/L. The linear range was 0.10-200 μg/L for 17β-estradiol, 0.25-200 μg/L estriol, ethinylestradiol and estrone, and 0.50-200 μg/L for the other hormones. Satisfactory linearities were achieved for analytes with the correlation coefficients above 0.99. Acceptable method reproducibility was achieved by evaluating the repeatability and intermediate precision with relative standard deviations of both less than 8%. The enrichment factors ranged from 54- to 74-fold. Finally, the proposed method was successfully applied to the analysis of steroid sex hormones in environmental water samples and human urines with spiking recoveries ranged from 75.6 to 116%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical dynamics simulations of the monohydrated OH{sup −}(H{sub 2}O) + CH{sub 3}I reaction. Atomic-level mechanisms and comparison with experiment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Jing; Hase, William L., E-mail: bill.hase@ttu.edu; Otto, Rico

2015-06-28

Direct dynamics simulations, with B97-1/ECP/d theory, were performed to study the role of microsolvation for the OH{sup −}(H{sub 2}O) + CH{sub 3}I reaction. The S{sub N}2 reaction dominates at all reactant collision energies, but at higher collision energies proton transfer to form CH{sub 2}I{sup −}, and to a lesser extent CH{sub 2}I{sup −} (H{sub 2}O), becomes important. The S{sub N}2 reaction occurs by direct rebound and stripping mechanisms, and 28 different indirect atomistic mechanisms, with the latter dominating. Important components of the indirect mechanisms are the roundabout and formation of S{sub N}2 and proton transfer pre-reaction complexes and intermediates, includingmore » [CH{sub 3}--I--OH]{sup −}. In contrast, for the unsolvated OH{sup −} + CH{sub 3}I S{sub N}2 reaction, there are only seven indirect atomistic mechanisms and the direct mechanisms dominate. Overall, the simulation results for the OH{sup −}(H{sub 2}O) + CH{sub 3}I S{sub N}2 reaction are in good agreement with experiment with respect to reaction rate constant, product branching ratio, etc. Differences between simulation and experiment are present for the S{sub N}2 velocity scattering angle at high collision energies and the proton transfer probability at low collision energies. Equilibrium solvation by the H{sub 2}O molecule is unimportant. The S{sub N}2 reaction is dominated by events in which H{sub 2}O leaves the reactive system as CH{sub 3}OH is formed or before CH{sub 3}OH formation. Formation of solvated products is unimportant and participation of the (H{sub 2}O)CH{sub 3}OH---I{sup −} post-reaction complex for the S{sub N}2 reaction is negligible.« less

Elastic collisions of low-energy electrons with SiY4 (Y = Cl, Br, I) molecules

NASA Astrophysics Data System (ADS)

Bettega, M. H. F.

2011-11-01

We employed the Schwinger multichannel method to compute elastic integral, differential, and momentum transfer cross sections for low-energy electron collisions with SiY4 (Y = Cl, Br, I) molecules. The calculations were carried out in the static-exchange and static-exchange plus polarization approximations for energies up to 10 eV. The elastic integral cross section for SiCl4 and SiBr4, computed in the static-exchange plus polarization approximation, shows two shape resonances belonging to the T2 and E symmetries of the Td group, and for SiI4 shows one shape resonance belonging to the E symmetry of the Td group. The present results agree well in shape with experimental total cross sections. The positions of the resonances observed in the calculated integral cross sections are also in agreement with the experimental positions. We have found the presence of a virtual state for SiCl4 and a Ramsauer-Townsend minimum for SiI4 at 0.5 eV. The present results show that the proper inclusion of polarization effects is crucial in order to correctly describe the resonance spectra of these molecules and also to identify a Ramsauer-Townsend minimum for SiI4 and a virtual state for SiCl4.

Influence of inelastic collisions with hydrogen atoms on the non-LTE modelling of Ca I and Ca II lines in late-type stars

NASA Astrophysics Data System (ADS)

Mashonkina, L.; Sitnova, T.; Belyaev, A. K.

2017-09-01

We performed the non-local thermodynamic equilibrium (non-LTE, NLTE) calculations for Ca I-II with the updated model atom that includes new quantum-mechanical rate coefficients for Ca I + H I collisions from two recent studies and investigated the accuracy of calcium abundance determinations using the Sun, Procyon, and five metal-poor (MP, -2.6 ≤ [Fe/H] ≤-1.3) stars with well-determined stellar parameters. Including H I collisions substantially reduces over-ionisation of Ca I in the line formation layers compared with the case of pure electronic collisions and thus the NLTE effects on abundances derived from Ca I lines. We show that both collisional recipes lead to very similar NLTE results. As for Ca II, the classical Drawinian rates scaled by SH = 0.1 are still applied. When using the subordinate lines of Ca I and the high-excitation lines of Ca II, NLTE provides the smaller line-to-line scatter compared with the LTE case for each star. For Procyon, NLTE removes a steep trend with line strength among strong Ca I lines seen in LTE and leads to consistent [Ca/H] abundances from the two ionisation stages. In the MP stars, the NLTE abundance from Ca II 8498 Å agrees well with the abundance from the Ca I subordinate lines, in contrast to LTE, where the abundance difference grows towards lower metallicity and reaches 0.46 dex in BD -13°3442 ([Fe/H] = -2.62). NLTE largely removes abundance discrepancies between the high-excitation lines of Ca II and Ca II 8498 Å obtained for our four [Fe/H] < -2 stars under the LTE assumption. We investigated the formation of the Ca I resonance line in the [Fe/H] < -2 stars. When the calcium abundance varies between [Ca/H] ≃ -1.8 and -2.3, photon loss in the resonance line itself in the uppermost atmospheric layers drives the strengthening of the line core compared with the LTE case, and this effect prevails over the weakening of the line wings, resulting in negative NLTE abundance correction and underestimation of the

Shear Driven Synthesis of Polymeric Micro- and Nanomaterials

NASA Astrophysics Data System (ADS)

Tian, Tian

Polymeric micro- and nanomaterials play a significant role in various current and emerging technologies. A liquid shear based method was developed to fabricate a wide range of polymeric materials, which include fibers, sheets, ribbons, rods and spheres in a scalable, cost-effective and simple way. During the process, droplet shearing, droplet deformation, droplet breaking up and polymer precipitation occur simultaneously. The size and morphology of the resultant structures are determined by the dominating process which is further controlled by the experimental parameters including polymer concentration, polymer molecular weight and antisolvent concentration. Among all of these structures, nanofibers have attracted the latest research interest due to the unique properties. Current leading fiber production approaches in the market possess certain drawbacks. For example, the throughput of electrospinning is limited to around 2.5 kg/hr and the diameter of fiber produced by wet spinning cannot be below micrometer while melt spinning is only applicable to melt-processable polymers. The breakthrough of our liquid shear driven technique for fiber synthesis is that it produces fibers with diameter from 200 nm to several micrometers from a wide range of liquid- processable polymers with high commercial yield (up to 12 kg/hr). Thus in Chapter 2, the optimum parameters range for fiber formation is established and the effects of those parameters on fiber size are investigated. In the original liquid shear method, medium with high viscosity is needed to exert strong shear stress on the droplet and to stretch the droplets to long strand. However, the viscous medium complicates the post sample washing procedure and introduces the potential slippery danger in the working area. Thus a non-viscous medium shearing method is developed in Chapter 3 and it is the first time proposed that the synthesis of PLA or PS nanofibers can be completed in the aqueous ethanol medium. Colloid science

Investigation of CO2 capture mechanisms of liquid-like nanoparticle organic hybrid materials via structural characterization.

PubMed

Park, Youngjune; Decatur, John; Lin, Kun-Yi Andrew; Park, Ah-Hyung Alissa

2011-10-28

Nanoparticle organic hybrid materials (NOHMs) have been recently developed that comprise an oligomeric or polymeric canopy tethered to surface-modified nanoparticles via ionic or covalent bonds. It has already been shown that the tunable nature of the grafted polymeric canopy allows for enhanced CO(2) capture capacity and selectivity via the enthalpic intermolecular interactions between CO(2) and the task-specific functional groups, such as amines. Interestingly, for the same amount of CO(2) loading NOHMs have also exhibited significantly different swelling behavior compared to that of the corresponding polymers, indicating a potential structural effect during CO(2) capture. If the frustrated canopy species favor spontaneous ordering due to steric and/or entropic effects, the inorganic cores of NOHMs could be organized into unusual structural arrangements. Likewise, the introduction of small gaseous molecules such as CO(2) could reduce the free energy of the frustrated canopy. This entropic effect, the result of unique structural nature, could allow NOHMs to capture CO(2) more effectively. In order to isolate the entropic effect, NOHMs were synthesized without the task-specific functional groups. The relationship between their structural conformation and the underlying mechanisms for the CO(2) absorption behavior were investigated by employing NMR and ATR FT-IR spectroscopies. The results provide fundamental information needed for evaluating and developing novel liquid-like CO(2) capture materials and give useful insights for designing and synthesizing NOHMs for more effective CO(2) capture. This journal is © the Owner Societies 2011

Novel amphiphilic polymeric ionic liquid-solid phase micro-extraction membrane for the preconcentration of aniline as degradation product of azo dye Orange G under sonication by liquid chromatography-tandem mass spectrometry.

PubMed

Cai, Mei-Qiang; Wei, Xiao-Qing; Du, Chun-Hui; Ma, Xu-Ming; Jin, Mi-Cong

2014-07-04

A novel amphiphilic polymeric ionic liquid membrane containing a hydrophilic bromide anion and a hydrophobic carbonyl group was synthesized in dimethylformamide (DMF) systems using the ionic liquid 1-butyl-3-vinylimidazolium bromide (BVImBr) and the methylmethacrylate (MMA) as monomers. The prepared amphiphilic ploy-methylmethacrylate-1-butyl-3-vinylimidazolium bromide (MMA-BVImBr) was characterized by a scanning electron microscope and an infrared spectrum instrument. The results of solid-phase micro-extraction membrane (SPMM) experiments showed that the adsorption capacity of membrane was about 0.76μgμg(-1) for aniline. Based on this, a sensitive method for the determination of trace aniline, as a degradation product of azo dye Orange G under sonication, was developed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The calibration curve showed a good linearity ranging from 0.5 to 10.0μgL(-1) with a correlation coefficient value of 0.9998. The limit of quantification was 0.5μgL(-1). The recoveries ranged from 90.6% to 96.1%. The intra- and inter-day relative standard deviations were less than 8.3% and 10.9%. The developed SPMM-LC-MS/MS method was used successfully for preconcentration of trace aniline produced during the sonication of Orange G solution. Copyright © 2014 Elsevier B.V. All rights reserved.

Jet-like correlations with neutral pion triggers in pp and central Pb–Pb collisions at 2.76 TeV

DOE PAGES

Adam, J.; Adamová, D.; Aggarwal, M. M.; ...

2016-10-24

We present measurements of two-particle correlations with neutral pion trigger particles of transverse momenta 8 > pmore » $$trig\\atop{T}$$ > 16 GeV/c and associated charged particles of 0.5 > p $$assoc\\atop{T}$$ > 10 GeV/c versus the azimuthal angle difference Δφ at midrapidity in pp and central Pb–Pb collisions at s NN =2.76 TeV with ALICE. The new measurements exploit associated charged hadrons down to 0.5 GeV/c, which significantly extends our previous measurement that only used charged hadrons above 3 GeV/c. After subtracting the contributions of the flow background, v 2 to v 5 , the per-trigger yields are extracted for |Δφ| > 0.7 on the near and for |Δφ-π| > 1.1 on the away side. The ratio of per-trigger yields in Pb–Pb to those in pp collisions, I AA , is measured on the near and away side for the 0–10% most central Pb–Pb collisions. On the away side, the per-trigger yields in Pb–Pb are strongly suppressed to the level of I AA ≈0.6 for p $$assoc\\atop{T}$$ < 3 GeV/c, while with decreasing momenta an enhancement develops reaching about 5 at low p $$assoc\\atop{T}$$. On the near side, an enhancement of I AA between 1.2 at the highest to 1.8 at the lowest p T assoc is observed. The data are compared to parton-energy-loss predictions of the JEWEL and AMPT event generators, as well as to a perturbative QCD calculation with medium-modified fragmentation functions. All calculations qualitatively describe the away-side suppression at high p $$assoc\\atop{T}$$ . Only AMPT captures the enhancement at low p $$assoc\\atop{T}$$ , both on the near and away side. However, it also underpredicts I AA above 5 GeV/c, in particular on the near-side.« less

Jet-like correlations with neutral pion triggers in pp and central Pb–Pb collisions at 2.76 TeV

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adam, J.; Adamová, D.; Aggarwal, M. M.

We present measurements of two-particle correlations with neutral pion trigger particles of transverse momenta 8 > pmore » $$trig\\atop{T}$$ > 16 GeV/c and associated charged particles of 0.5 > p $$assoc\\atop{T}$$ > 10 GeV/c versus the azimuthal angle difference Δφ at midrapidity in pp and central Pb–Pb collisions at s NN =2.76 TeV with ALICE. The new measurements exploit associated charged hadrons down to 0.5 GeV/c, which significantly extends our previous measurement that only used charged hadrons above 3 GeV/c. After subtracting the contributions of the flow background, v 2 to v 5 , the per-trigger yields are extracted for |Δφ| > 0.7 on the near and for |Δφ-π| > 1.1 on the away side. The ratio of per-trigger yields in Pb–Pb to those in pp collisions, I AA , is measured on the near and away side for the 0–10% most central Pb–Pb collisions. On the away side, the per-trigger yields in Pb–Pb are strongly suppressed to the level of I AA ≈0.6 for p $$assoc\\atop{T}$$ < 3 GeV/c, while with decreasing momenta an enhancement develops reaching about 5 at low p $$assoc\\atop{T}$$. On the near side, an enhancement of I AA between 1.2 at the highest to 1.8 at the lowest p T assoc is observed. The data are compared to parton-energy-loss predictions of the JEWEL and AMPT event generators, as well as to a perturbative QCD calculation with medium-modified fragmentation functions. All calculations qualitatively describe the away-side suppression at high p $$assoc\\atop{T}$$ . Only AMPT captures the enhancement at low p $$assoc\\atop{T}$$ , both on the near and away side. However, it also underpredicts I AA above 5 GeV/c, in particular on the near-side.« less

Synthesis of amphipathic block copolymers based on polyisobutylene and polyoxyethylene and their application in emulsion polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sar, B.

1992-12-31

Polymer colloids stabilized by polymeric surfactants are of great interest both commercially and academically. It has been found that these materials enhance latex stabilization in a number of applications. The polymeric surfactants are amphipathic block and graft copolymers containing both hydrophilic and hydrophobic moieties. The current study involved the synthesis of a series of amphipathic triblock copolymers, polyisobutylene-block-polyoxyethylene-block-polyisobutylene (PIB-b-POE-b-PIB), for use in the emulsion polymerization of styrene (STY), methyl methacrylate (MMA), and vinyl acetate (VAc). The stabilizing effectiveness of these triblock copolymers was studied as a function of their blocklength. When the molecular weight of the POE center block wasmore » changed from M{sub n} = 2,000 to 20,000 g/mole, stable lattices were obtained in emulsion polymerization with MMA, STY, and VAc as the monomers. In all cases, the polymerization rates remained constant, while the number of particles/volume decreased with increasing POE chain length. When the molecular weight of the PIB end blocks was changed from M{sub n} = 400 to 2,600 g/mole keeping the molecular weight of the POE center block constant at M{sub n} = 20,000 g/mole, the poly(methyl methacrylate) and poly(vinyl acetate) lattices exhibited similar behavior, i.e., the number of particles and particle sizes remained the same, but the rate of polymerization reached a maximum at 87 wt% POE content. In the case of poly(styrene) both the rate of polymerization and the number of particles remained constant. The emulsion polymerization of other monomers such as butadiene, acrylonitrile, methyl acrylate, ethyl acrylate, and butyl acrylate was carried out by using one triblock copolymer, i.e., PIB(400)-b-POE (8,000)-b-PIB-(400). Stable lattices were also formed in all cases.« less

Monodispersed molecularly imprinted polymer for creatinine by modified precipitation polymerization.

PubMed

Haginaka, Jun; Miura, Chitose; Funaya, Noriko; Matsunaga, Hisami

2012-01-01

A monodispersed molecularly imprinted polymer (MIP) for creatinine was prepared by modified precipitation polymerization. The retention and molecular-recognition properties of the prepared MIP were evaluated by the hydrophilic interaction chromatography mode using a mixture of ammonium acetate buffer and acetonitrile as a mobile phase in liquid chromatography. The MIP had a specific recognition ability for creatinine, while other structurally related compounds, such as hydantoin, 1-methylhydantoin, 2-pyrrolidone, N-hydroxysuccinimide and creatine, could not be recognized on the MIP. In addition to shape recognition, hydrophilic interactions could work for the recognition of creatinine on the MIP.

Preparation of molecularly imprinted polymers for strychnine by precipitation polymerization and multistep swelling and polymerization and their application for the selective extraction of strychnine from nux-vomica extract powder.

PubMed

Nakamura, Yukari; Matsunaga, Hisami; Haginaka, Jun

2016-04-01

Monodisperse molecularly imprinted polymers for strychnine were prepared by precipitation polymerization and multistep swelling and polymerization, respectively. In precipitation polymerization, methacrylic acid and divinylbenzene were used as a functional monomer and crosslinker, respectively, while in multistep swelling and polymerization, methacrylic acid and ethylene glycol dimethacrylate were used as a functional monomer and crosslinker, respectively. The retention and molecular recognition properties of the molecularly imprinted polymers prepared by both methods for strychnine were evaluated using a mixture of sodium phosphate buffer and acetonitrile as a mobile phase by liquid chromatography. In addition to shape recognition, ionic and hydrophobic interactions could affect the retention of strychnine in low acetonitrile content. Furthermore, molecularly imprinted polymers prepared by both methods could selectively recognize strychnine among solutes tested. The retention factors and imprinting factors of strychnine on the molecularly imprinted polymer prepared by precipitation polymerization were 220 and 58, respectively, using 20 mM sodium phosphate buffer (pH 6.0)/acetonitrile (50:50, v/v) as a mobile phase, and those on the molecularly imprinted polymer prepared by multistep swelling and polymerization were 73 and 4.5. These results indicate that precipitation polymerization is suitable for the preparation of a molecularly imprinted polymer for strychnine. Furthermore, the molecularly imprinted polymer could be successfully applied for selective extraction of strychnine in nux-vomica extract powder. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

COLLIDE-2: Collisions Into Dust Experiment-2

NASA Technical Reports Server (NTRS)

Colwell, Joshua E.

2002-01-01

The Collisions Into Dust Experimental (COLLIDE-2) was the second flight of the COLLIDE payload. The payload performs six low-velocity impact experiments to study the collisions that are prevalent in planetary ring systems and in the early stages of planet formation. Each impact experiment is into a target of granular material, and the impacts occur at speeds between 1 and 100 cm/s in microgravity and in a vacuum. The experiments are recorded on digital videotape which is later analyzed. During the period of performance a plan was developed to address some of the technical issues that prevented the first flight of COLLIDE from being a complete success, and also to maximize the scientific return based on the science results from the first flight. The experiment was modified following a series of reviews of the design plan, and underwent extensive testing. The data from the experiment show that the primary goal of identifying transition regimes for low-velocity impacts based on cratering versus accretion was achieved. Following a brief period of storage, the experiment flew regimes for low-velocity impacts based on cratering versus accretion was achieved. as a Hitchhiker payload on the MACH-1 Hitchhiker bridge on STS-108 in December 2001. These data have been analyzed and submitted for publication. That manuscript is attached to this report. The experiment was retrieved in January 2002, and all six impact experiments functioned nominally. Preliminary results were reported at the Lunar and Planetary Science Conference.

High-efficiency preparation of poly(2-methacryloyloxyethyl phosphorylcholine) grafting layer on poly(ether ether ketone) by photoinduced and self-initiated graft polymerization in an aqueous solution in the presence of inorganic salt additives.

PubMed

Shiojima, Taro; Inoue, Yuuki; Kyomoto, Masayuki; Ishihara, Kazuhiko

2016-08-01

A highly efficient methodology for preparing a poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) layer on the surface of poly(ether ether ketone) (PEEK) was examined by photoinduced and self-initiated graft polymerization. To enhance the polymerization rate, we demonstrated the effects of inorganic salt additives in the feed monomer solution on thickness of grafted PMPC layer. Photoinduced polymerization occurred and the PMPC graft layer was successfully formed on the PEEK surface, regardless of inorganic salt additives. Moreover, it was clearly observed that the addition of inorganic salt enhanced the grafting thickness of PMPC layer on the surface even when the photoirradiation time was shortened. The addition of inorganic salt additives in the feed monomer solution enhanced the polymerization rate of MPC and resulted in thicker PMPC layers. In particular, we evaluated the effect of NaCl concentration and how this affected the polymerization rate and layer thickness. We considered that this phenomenon was due to the hydration of ions in the feed monomer solution and subsequent apparent increase in the MPC concentration. A PMPC layer with over 100-nm-thick, which was prepared by 5-min photoirradiation in 2.5mol/L inorganic salt aqueous solution, showed good wettability and protein adsorption resistance compared to that of untreated PEEK. Hence, we concluded that the addition of NaCl into the MPC feed solution would be a convenient and efficient method for preparing a graft layer on PEEK. Photoinduced and self-initiated graft polymerization on the PEEK surface is one of the several methodologies available for functionalization. However, in comparison with free-radical polymerization, the efficiency of polymerization at the solid-liquid interface is limited. Enhancement of the polymerization rate for grafting could solve the problem. In this study, we observed the acceleration of the polymerization rate of MPC in an aqueous solution by the addition of inorganic

2-Isopropenyl-2-oxazoline: Well-Defined Homopolymers and Block Copolymers via Living Anionic Polymerization

DOE PAGES

Feng, Hongbo; Changez, Mohammad; Hong, Kunlun; ...

2016-12-23

Poly(2-isopropenyl-2-oxazoline) (PIPOx) has drawn significant attention for numerous applications. However, the successful living anionic polymerization of 2-isopropenyl-2-oxazoline has not been reported previously. In this paper, we describe how well-defined PIPOx with quantitative yields, controlled molecular weights from 6800 to over 100 000 g/mol and low polydispersity indices (PDI ≤ 1.17) were synthesized successfully via living anionic polymerization using diphenylmethylpotassium/diethylzinc (DPM-K/Et 2Zn) in tetrahydrofuran (THF) at 0 °C. In particular, we report the precise synthesis of well-defined PIPOx with the highest molecular weight ever reported (over 100 000 g/mol) and low PDI of 1.17. The resulting polymers were characterized by 1Hmore » and 13C nuclear magnetic resonance spectroscopy (NMR) along with size exclusion chromatography (SEC). Additionally, the reactivity of living PIPOx was investigated by crossover block copolymerization with styrene (St), 2-vinylpyridine (2VP), and methyl methacrylate (MMA). It was found that the nucleophilicity of living PIPOx is of this order: living PS > living P2VP > living PMMA > living PIPOx. The self-assembly behavior in bulk of PIPOx-b-PS-b-PIPOx triblock copolymers having different block ratios of 10:80:10 and 25:50:25 was studied using transmission electron microscopy (TEM). Finally, the formation of spherical and lamellar nanostructures, respectively, was observed.« less

2-Isopropenyl-2-oxazoline: Well-Defined Homopolymers and Block Copolymers via Living Anionic Polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Hongbo; Changez, Mohammad; Hong, Kunlun

Poly(2-isopropenyl-2-oxazoline) (PIPOx) has drawn significant attention for numerous applications. However, the successful living anionic polymerization of 2-isopropenyl-2-oxazoline has not been reported previously. In this paper, we describe how well-defined PIPOx with quantitative yields, controlled molecular weights from 6800 to over 100 000 g/mol and low polydispersity indices (PDI ≤ 1.17) were synthesized successfully via living anionic polymerization using diphenylmethylpotassium/diethylzinc (DPM-K/Et 2Zn) in tetrahydrofuran (THF) at 0 °C. In particular, we report the precise synthesis of well-defined PIPOx with the highest molecular weight ever reported (over 100 000 g/mol) and low PDI of 1.17. The resulting polymers were characterized by 1Hmore » and 13C nuclear magnetic resonance spectroscopy (NMR) along with size exclusion chromatography (SEC). Additionally, the reactivity of living PIPOx was investigated by crossover block copolymerization with styrene (St), 2-vinylpyridine (2VP), and methyl methacrylate (MMA). It was found that the nucleophilicity of living PIPOx is of this order: living PS > living P2VP > living PMMA > living PIPOx. The self-assembly behavior in bulk of PIPOx-b-PS-b-PIPOx triblock copolymers having different block ratios of 10:80:10 and 25:50:25 was studied using transmission electron microscopy (TEM). Finally, the formation of spherical and lamellar nanostructures, respectively, was observed.« less

H{sub 2} dissociation due to collisions with He

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ohlinger, L.; Forrey, R. C.; Lee, Teck-Ghee

2007-10-15

Cross sections for dissociation of H{sub 2} due to collision with He are calculated for highly excited rovibrational states using the quantum-mechanical coupled-states approximation. An L{sup 2} Sturmian basis set with multiple length scales is used to provide a discrete representation of the H{sub 2} continuum which includes orbiting resonances and a nonresonant background. Cross sections are given over a range of translational energies for both resonant and nonresonant dissociation together with the most important bound-state transitions for many different initial states. The results demonstrate that it is possible to compute converged quantum-mechanical cross sections using basis sets of modestmore » size. It is found that collision-induced dissociation competes with inelastic scattering as a depopulation mechanism for the highly excited states. The relevance of the present calculations to astrophysical models is discussed.« less

QCD tests in $$p\\bar{p}$$ collisions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huth, John E.; Mangano, Michelangelo L.

1993-02-01

We review the status of QCD tests in high energy p-pbar collisions. Contents: i) Introduction ii) QCD in Hadronic Collisions iii) Jet Production iv) Heavy Flavour Production v) W and Z Production vi) Direct Photons.

Does a network structure exist in molecular liquid SnI4 and GeI4?

NASA Astrophysics Data System (ADS)

Sakagami, Takahiro; Fuchizaki, Kazuhiro

2017-04-01

The existence of a network structure consisting of electrically neutral tetrahedral molecules in liquid SnI4 and GeI4 at ambient pressure was examined. The liquid structures employed for the examination were obtained from a reverse Monte Carlo analysis. The structures were physically interpreted by introducing an appropriate intermolecular interaction. A ‘bond’ was then defined as an intermolecular connection that minimizes the energy of intermolecular interaction. However, their ‘bond’ energy is too weak for the ‘bond’ and the resulting network structure to be defined statically. The vertex-to-edge orientation between the nearest molecules is so ubiquitous that almost all of the molecules in the system can take part in the network, which is reflected in the appearance of a prepeak in the structure factor.

Development and characterization of a rapid polymerizing collagen for soft tissue augmentation.

PubMed

Devore, Dale; Zhu, Jiaxun; Brooks, Robert; McCrate, Rebecca Rone; Grant, David A; Grant, Sheila A

2016-03-01

A liquid collagen has been developed that fibrilizes upon injection. Rapid polymerizing collagen (RPC) is a type I porcine collagen that undergoes fibrillization upon interaction with ionic solutions, such as physiological solutions. The ability to inject liquid collagen would be beneficial for many soft tissue augmentation applications. In this study, RPC was synthesized and characterized as a possible dermal filler. Transmission electron microscopy, ion induced RPC fibrillogenesis tests, collagenase resistance assay, and injection force studies were performed to assess RPC's physicochemical properties. An in vivo study was performed which consisted of a 1-, 3-, and 6-month study where RPC was injected into the ears of miniature swine. The results demonstrated that the liquid RPC requires low injection force (<7 N); fibrillogenesis and banding of collagen occurs when RPC is injected into ionic solutions, and RPC has enhanced resistance to collagenase breakdown. The in vivo study demonstrated long-term biocompatibility with low irritation scores. In conclusion RPC possesses many of the desirable properties of a soft tissue augmentation material. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 758-767, 2016. © 2015 The authors journal of biomedical materials research part a published by wiley periodicals, inc.

[Theory of V.A. dogiel on polymerization and oligomerization as a general integration concept].

PubMed

Makmaev, Iu V

2010-01-01

The theory of V.A. Dogiel on the significance of polymerization and ligomerization processes in the evolution of Protozoa and Metazoa is compared with the paper of I.I. Schmalhauisen (1972) on factors and steps of aromorph evolution. Dogiel's theory is considered as a general integration conception. Four steps are distinguished in the evolution of biological systems: (1) formation of morphofunctional system by units of the lower structural level, (2) polymerization of morphofunctional units of a system, (3) oligomerization of morphofunctional units of system by means of their reduction, uniting, or differentiation, (4) integration and stabilization of a system owing to development of morphofunctional connections between its parts.

Polymeric Coatings for Combating Biocorrosion

NASA Astrophysics Data System (ADS)

Guo, Jing; Yuan, Shaojun; Jiang, Wei; Lv, Li; Liang, Bin; Pehkonen, Simo O.

2018-03-01

Biocorrosion has been considered as big trouble in many industries and marine environments due to causing great economic loss. The main disadvantages of present approaches to prevent corrosion include being limited by environmental factors, being expensive, inapplicable to field, and sometimes inefficient. Studies show that polymer coatings with anti-corrosion and anti-microbial properties have been widely accepted as a novel and effective approach to preventbiocorrosion. The main purpose of this review is to summarize up the progressive status of polymer coatings used for combating microbially-induced corrosion. Polymers used to synthesize protective coatings are generally divided into three categories: i) traditional polymers incorporated with biocides, ii) antibacterial polymers containing quaternary ammonium compounds, and iii) conductive polymers. The strategies to synthesize polymer coatings resort mainly to grafting anti-bacterial polymers from the metal substrate surface using novel surface-functionalization approaches, such as free radical polymerization, chemically oxidative polymerization and surface-initiated atom transfer radical polymerization, as opposed to the traditional approaches of dip coating or spin coating.

Molecular dynamics and vibrational relaxations in liquid nitromethane.

NASA Astrophysics Data System (ADS)

Grazia Giorgini, Maria; Mariani, Leonardo; Morresi, Assunta; Paliani, Giulio; Cataliotti, Rosario Sergio

The vibrational relaxation processes of totally symmetric v1 (CH stretching and v5 (NO2 bending) motions of liquid nitromethane have been studied as a function of temperature and concentration in CD3NO2 and CCl4 solutions. The experimental vibrational correlation functions of these two modes have shown that relaxation is collision assisted and suitable for modelling with the stochastic Kubo-Rothschild theory.

Quenching of highly vibrationally excited pyrimidine by collisions with CO2

NASA Astrophysics Data System (ADS)

Johnson, Jeremy A.; Duffin, Andrew M.; Hom, Brian J.; Jackson, Karl E.; Sevy, Eric T.

2008-02-01

Relaxation of highly vibrationally excited pyrimidine (C4N2H4) by collisions with carbon dioxide has been investigated using diode laser transient absorption spectroscopy. Vibrationally hot pyrimidine (E'=40635cm-1) was prepared by 248-nm excimer laser excitation, followed by rapid radiationless relaxation to the ground electronic state. The nascent rotational population distribution (J=58-80) of the 0000 ground state of CO2 resulting from collisions with hot pyrimidine was probed at short times following the excimer laser pulse. Doppler spectroscopy was used to measure the CO2 recoil velocity distribution for J =58-80 of the 0000 state. Rate constants and probabilities for collisions populating these CO2 rotational states were determined. The measured energy transfer probabilities, indexed by final bath state, were resorted as a function of ΔE to create the energy transfer distribution function, P(E,E'), from E'-E˜1300-7000cm-1. P(E,E') is fitted to a single exponential and a biexponential function to determine the average energy transferred in a single collision between pyrimidine and CO2 and parameters that can be compared to previously studied systems using this technique, pyrazine/CO2, C6F6/CO2, and methylpyrazine/CO2. P(E,E') parameters for these four systems are also compared to various molecular properties of the donor molecules. Finally, P(E,E') is analyzed in the context of two models, one which suggests that the shape of P(E,E') is primarily determined by the low-frequency out-of-plane donor vibrational modes and one which suggests that the shape of P(E,E') can be determined by how the donor molecule final density of states changes with ΔE.

Effects of hydrogen atom spin exchange collisions on atomic hydrogen maser oscillation frequency

NASA Technical Reports Server (NTRS)

Crampton, S. B.

1979-01-01

Frequency shifts due to collisions between hydrogen atoms in an atomic hydrogen maser frequency standard are studied. Investigations of frequency shifts proportional to the spin exchange frequency shift cross section and those proportional to the duration of exchange collisions are discussed. The feasibility of operating a hydrogen frequency standard at liquid helium temperatures is examined.

Determinations of cloud liquid water in the tropics from the SSM/I

NASA Technical Reports Server (NTRS)

Alishouse, John C.; Swift, Calvin; Ruf, Christopher; Snyder, Sheila; Vongsathorn, Jennifer

1989-01-01

Upward-looking microwave radiometric observations were used to validate the SSM/I determinations, and also as a basis for the determination of new coefficients. Due to insufficiency of the initial four channel algorithm for cloud liquid water, the improved algorithm was derived from the CORRAD (the University of Massachusetts autocorrelation radiometer) measurements of cloud liquid water and the matching SSM/I brightness temperatures using the standard linear regression. The correlation coefficients for the possible four channel combinations, and subsequently the best and the worst combinations were determined.

Cold Collisions in a Molecular Synchrotron

NASA Astrophysics Data System (ADS)

van der Poel, Aernout P. P.; Zieger, Peter C.; van de Meerakker, Sebastiaan Y. T.; Loreau, Jérôme; van der Avoird, Ad; Bethlem, Hendrick L.

2018-01-01

We study collisions between neutral, deuterated ammonia molecules (ND3 ) stored in a 50 cm diameter synchrotron and argon atoms in copropagating supersonic beams. The advantages of using a synchrotron in collision studies are twofold: (i) By storing ammonia molecules many round-trips, the sensitivity to collisions is greatly enhanced; (ii) the collision partners move in the same direction as the stored molecules, resulting in low collision energies. We tune the collision energy in three different ways: by varying the velocity of the stored ammonia packets, by varying the temperature of the pulsed valve that releases the argon atoms, and by varying the timing between the supersonic argon beam and the stored ammonia packets. These give consistent results. We determine the relative, total, integrated cross section for ND3+Ar collisions in the energy range of 40 - 140 cm-1 , with a resolution of 5 - 10 cm-1 and an uncertainty of 7%-15%. Our measurements are in good agreement with theoretical scattering calculations.

TiO2 -enriched polymeric powder coatings support human mesenchymal cell spreading and osteogenic differentiation.

PubMed

Mozumder, Mohammad Sayem; Zhu, Jesse; Perinpanayagam, Hiran

2011-06-01

Novel polymeric powder coatings (PPC) were prepared by ultrafine powder coating technology and shown to support human mesenchymal cell attachment and growth. PPC surfaces enriched with nano-TiO(2) (nTiO(2)) showed enhanced cellular responses, and were compared to commercially pure titanium (cpTi). After cell attachment and growth, osteogenic differentiation and bone matrix formation ensures osseointegration for implantable biomaterials. Therefore, the objective of this study was to determine if mesenchymal cells grown on PPC could undergo osteogenic differentiation by inducing Runx2 and bone matrix proteins, and then initiate mineralization. Atomic force microscopy revealed intricate three-dimensional micro-topographies, and the measures of nano-roughness and porosity were similar for all PPC surfaces. Scanning electron microscopy showed that the cells attached and spread out over all of the surfaces. After 1 week in osteogenic media, RT-PCR analysis showed the induction of Runx2, the up-regulation of type I collagen, and the initial detection of alkaline phosphatase and bone sialoprotein. After 4 weeks, Alizarin Red staining showed mineral deposition. However, cell spreading and osteogenic differentiation were significantly (P < 0.05) higher on the cpTi controls than on the PPC surfaces. Furthermore, spreading and differentiation were consistently higher on the titanium-enriched PPC-2, -3 and -4 than on the titanium-free PPC-1. Therefore, despite the presence of complex micro-topographies and nano-features, titanium-enrichment enhanced the cellular response, and pure titanium still provided the best substrate. These findings confirm the cytocompatibility of these novel polymeric coatings and suggest that titanium-enrichment and nTiO(2) additives may enhance their performance.

Fabricating small-scale, curved, polymeric structures with convex and concave menisci through interfacial free energy equilibrium.

PubMed

Cheng, Chao-Min; Matsuura, Koji; Wang, I-Jan; Kuroda, Yuka; LeDuc, Philip R; Naruse, Keiji

2009-11-21

Polymeric curved structures are widely used in imaging systems including optical fibers and microfluidic channels. Here, we demonstrate that small-scale, poly(dimethylsiloxane) (PDMS)-based, curved structures can be fabricated through controlling interfacial free energy equilibrium. Resultant structures have a smooth, symmetric, curved surface, and may be convex or concave in form based on surface tension balance. Their curvatures are controlled by surface characteristics (i.e., hydrophobicity and hydrophilicity) of the molds and semi-liquid PDMS. In addition, these structures are shown to be biocompatible for cell culture. Our system provides a simple, efficient and economical method for generating integrateable optical components without costly fabrication facilities.

Neutron scattering studies of molecular conformations in liquid crystal polymers

NASA Astrophysics Data System (ADS)

Noirez, L.; Moussa, F.; Cotton, J. P.; Keller, P.; Pépy, G.

1991-03-01

A comblike liquid crystal polymer (LPC) is a polymer on which mesogenic molecules have been grafted. It exhibits a succession of liquid crystal phases. Usually the equilibrium conformation of an ordinary polymeric chain corresponds to a maximum entropy, i.e., to an isotropic spherical coil. How does the backbone of a LCP behave in the nematic and smectic field? Small-angle neutron scattering may answer this question. Such measurements are presented here on four different polymers as a function of temperature. An anisotropy of the backbone conformation is found in all these studied compounds, much more pronounced in the smectic phase than in the nematic phase: the backbone spreads more or less perpendicularly to its hanging cores. A comparison with existing theories and a discussion of these results is outlined.

2D-3D switchable display based on a passive polymeric lenticular lens array and electrically suppressed ferroelectric liquid crystal.

PubMed

Shi, Liangyu; Srivastava, Abhishek Kumar; Wai Tam, Alwin Ming; Chigrinov, Vladimir Grigorievich; Kwok, Hoi Sing

2017-09-01

We reveal a 2D-3D switchable lens unit that is based on a polarization-sensitive microlens array and a polarization selector unit made of an electrically suppressed helix ferroelectric liquid crystal (ESHFLC) cell. The ESHFLCs offer a high contrast ratio (∼10k∶1) between the crossed polarizers at a low applied electric field (∼1.7  V/μm) with a small switching time (<50  μs). A special driving scheme, to switch between a 2D and 3D mode, has been developed to avoid unwanted issues related to DC accumulation in the ferroelectric liquid crystal without affecting its optical quality. The proposed lens unit is characterized by low power consumption, ultrafast response, and 3D crosstalk <5%, and can therefore find application in TVs, cell phones, etc.

Hydrodynamical analysis of centrality dependence of charged particle multiplicity in {radical}(s){sub NN}=2.76 TeV Pb + Pb collisions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chaudhuri, A. K.; Roy, Victor

2011-08-15

In Israel-Stewart's theory of dissipative hydrodynamics, we have analyzed the recent ALICE data for the centrality dependence of charged particle multiplicity, centrality dependence of integrated elliptic flow, and 0%-5% charged particle p{sub T} spectra in {radical}(s){sub NN}= 2.76 TeV Pb+Pb collisions and determined the initial or the thermalization time. Analysis indicates that the ALICE data disfavor very early thermalization {tau}{sub i}= 0.2 fm, or very late thermalization {tau}{sub i} = 4 fm. Data are best explained for thermalization time {tau}{sub i}=0.88{sub +0.68}{sup -0.14} fm.

Chemical Dynamics Simulations of Intermolecular Energy Transfer: Azulene + N2 Collisions.

PubMed

Kim, Hyunsik; Paul, Amit K; Pratihar, Subha; Hase, William L

2016-07-14

Chemical dynamics simulations were performed to investigate collisional energy transfer from highly vibrationally excited azulene (Az*) in a N2 bath. The intermolecular potential between Az and N2, used for the simulations, was determined from MP2/6-31+G* ab initio calculations. Az* is prepared with an 87.5 kcal/mol excitation energy by using quantum microcanonical sampling, including its 95.7 kcal/mol zero-point energy. The average energy of Az* versus time, obtained from the simulations, shows different rates of Az* deactivation depending on the N2 bath density. Using the N2 bath density and Lennard-Jones collision number, the average energy transfer per collision ⟨ΔEc⟩ was obtained for Az* as it is collisionally relaxed. By comparing ⟨ΔEc⟩ versus the bath density, the single collision limiting density was found for energy transfer. The resulting ⟨ΔEc⟩, for an 87.5 kcal/mol excitation energy, is 0.30 ± 0.01 and 0.32 ± 0.01 kcal/mol for harmonic and anharmonic Az potentials, respectively. For comparison, the experimental value is 0.57 ± 0.11 kcal/mol. During Az* relaxation there is no appreciable energy transfer to Az translation and rotation, and the energy transfer is to the N2 bath.

When do particle ratios freeze out in relativistic heavy ion collisions?

NASA Astrophysics Data System (ADS)

Humanic, Thomas; Bellwied, Rene

1999-10-01

The systematics of CERN SPS data for transverse mass distributions have been shown to imply that thermal equilibrium is achieved at freeze out in these collisions. This conclusion is based on the observation that for p+p, S+S, and Pb+Pb collisions freeze out occurs at a single temperature for all particle species measured if one assumes a certain uniform expansion velocity after hadronization for each colliding system [1]. A recent final- state rescattering calculation for SPS Pb+Pb collisions has shown that these systematics can be described as a consequence of particle rescattering where the system is assumed initially (i.e. at hadronization) to have a common temperature for all particles and no initial expansion velocity [2]. In addition to kinetic observables, it is equally interesting to investigate the time dependence of particle abundances through particle ratios in such a calculation. Two questions immediately arise: 1) is chemical equilibrium established in these collisions, and 2) when does chemical freeze out occur with respect to thermal freeze out for different particle ratios? How rescattering influences particle ratios is clearly of interest if one would like to deduce information about the hadronization stage of the collision from particle ratios measured at freeze out. For the present work we will show results for strange and non-strange particle ratios within the context of a version of the dynamic transport code used in Ref. [2]. [1] NA44 colaboration, I.G. Bearden et al., Phys. Rev. Lett. 78,2080(1997), [2] T. J. Humanic, Phys. Rev. C 57,866(1998)

High temperature polymerization monitoring of an epoxy resin using ultrasound

NASA Astrophysics Data System (ADS)

Maréchal, P.; Ghodhbani, N.; Duflo, H.

2018-05-01

In this study, the real time ultrasonic monitoring is investigated to quantify changes in physical and mechanical properties during the manufacture of composite structures. In this context, an experimental transmission was developed with the aim of characterizing a high temperature polymerization reaction and post-curing properties using an ultrasonic method. First, the monitoring of ultrasonic parameters of a thermosetting resin is carried out in a device reproducing the experimental conditions for manufacturing a composite material with a process known as RTM, that is to say an isothermal polymerization at T = 160°C. During this curing, the resin is changing from its initial viscous liquid state to its final viscous solid state. Between those states, a glassy transition stage is observed, during which the physical properties are strongly changing, i.e. an increase of the ultrasonic velocity up to its steady value and a transient increase of the ultrasonic attenuation. Second, the ultrasonic inspection of the thermosetting resin is performed during a heating and cooling process to study the temperature sensitivity after curing. This type of characterization leads to identifying the ultrasonic properties dependence before, during and after the glassy transition temperature Tg . Eventually, this study is composed of two complementary parts: the first is useful for the curing optimization, while the second one is fruitful for the post-processing characterization in a temperature range including the glassy transition temperature Tg .

Polymeric micelles for multi-drug delivery in cancer.

PubMed

Cho, Hyunah; Lai, Tsz Chung; Tomoda, Keishiro; Kwon, Glen S

2015-02-01

Drug combinations are common in cancer treatment and are rapidly evolving, moving beyond chemotherapy combinations to combinations of signal transduction inhibitors. For the delivery of drug combinations, i.e., multi-drug delivery, major considerations are synergy, dose regimen (concurrent versus sequential), pharmacokinetics, toxicity, and safety. In this contribution, we review recent research on polymeric micelles for multi-drug delivery in cancer. In concurrent drug delivery, polymeric micelles deliver multi-poorly water-soluble anticancer agents, satisfying strict requirements in solubility, stability, and safety. In sequential drug delivery, polymeric micelles participate in pretreatment strategies that "prime" solid tumors and enhance the penetration of secondarily administered anticancer agent or nanocarrier. The improved delivery of multiple poorly water-soluble anticancer agents by polymeric micelles via concurrent or sequential regimens offers novel and interesting strategies for drug combinations in cancer treatment.

Equilibrium polymerization on the equivalent-neighbor lattice

NASA Technical Reports Server (NTRS)

Kaufman, Miron

1989-01-01

The equilibrium polymerization problem is solved exactly on the equivalent-neighbor lattice. The Flory-Huggins (Flory, 1986) entropy of mixing is exact for this lattice. The discrete version of the n-vector model is verified when n approaches 0 is equivalent to the equal reactivity polymerization process in the whole parameter space, including the polymerized phase. The polymerization processes for polymers satisfying the Schulz (1939) distribution exhibit nonuniversal critical behavior. A close analogy is found between the polymerization problem of index the Schulz r and the Bose-Einstein ideal gas in d = -2r dimensions, with the critical polymerization corresponding to the Bose-Einstein condensation.

Reporter-free potentiometric sensing of boronic acids and their reactions by using quaternary ammonium salt-functionalized polymeric liquid membranes.

PubMed

Wang, Xuewei; Yue, Dengfeng; Lv, Enguang; Wu, Lei; Qin, Wei

2014-02-18

The tremendous applications of boronic acids (BAs) in chemical sensing, medical chemistry, molecular assembly, and organic synthesis lead to an urgent demand for developing effective sensing methods for BAs. This paper reports a facile and sensitive potentiometric sensor scheme for heterogeneous detection of BAs based on their unexpected potential responses on quaternary ammonium salt-doped polymeric liquid membranes. (11)B NMR data reveal that a quaternary ammonium chloride can trigger the hydrolysis of an electrically neutral BA in an aprotic solvent. Using the quaternary ammonium salt as the receptor, the BA molecules can be extracted from the sample solution into the polymeric membrane phase and undergo the concomitant hydrolysis. Such salt-triggered hydrolysis generates H(+) ions, which can be coejected into the aqueous phase with the counterions (e.g., Cl(-)) owing to their high hydrophilicities. The perturbation on the ionic partition at the sample-membrane interface changes the phase boundary potential and thus enables the potentiometric sensing of BAs. In contrast to other transduction methods for BAs, for which labeled or separate reporters are exclusively required, the present heterogeneous sensing scheme allows the direct detection of BAs without using any reporter molecules. This technique shows superior detection limits for BAs (e.g., 1.0 × 10(-6) M for phenylboronic acid) as compared to previously reported methods based on colorimetry, fluorimetry, and mass spectrometry. The proposed sensing strategy has also been successfully applied to potentiometric indication of the BA reactions with hydrogen peroxide and saccharides, which allows indirect and sensitive detection of these important species.

Development of a polymeric ionic liquid coating for direct-immersion solid-phase microextraction using polyhedral oligomeric silsesquioxane as cross-linker.

PubMed

Chen, Chunyan; Liang, Xiaotong; Wang, Jianping; Zou, Ying; Hu, Huiping; Cai, Qingyun; Yao, Shouzhuo

2014-06-27

A novel solid-phase microextraction (SPME) fiber was developed by chemical binding of a crosslinked polymeric ionic liquid (PIL) on the surface of an anodized Ti wire, and was applied in direct-immersion mode for the extraction of perfluorinated compounds (PFCs) from water samples coupled with high performance liquid chromatography-tandem mass spectrometry analysis. The PIL coatings were synthesized by using 1-vinyl-3-hexylimidazolium hexafluorophosphate as monomer and methylacryloyl-substituted polyhedral oligomeric silsesquioxane (POSS) as cross-linker via free radical reaction. The proposed fiber coating exhibited high mechanical stability due to the chemical bonding between the coating and the Ti wire surface. The integration of POSS reagent enhanced the organic solvent resistance of the coating. The parameters affecting the extraction performance of the fiber coating including extraction time, pH of solution, ionic strength and desorption conditions were optimized. The developed PIL-POSS fiber showed good linearity (R<0.998) between 0.1 and 50ngmL(-1) with method detection limits ranging from 0.005 to 0.08ngmL(-1) depending on the analyte, and with relative standard deviation for single-fiber repeatability and fiber-to-fiber reproducibility less than 8.6% and 9.5%, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

Selected Topics in the Physics of Heavy Ion Collisions (1/3)

ScienceCinema

Wiedemann, Urs Achim

2017-12-15

In these lectures, I discuss some classes of measurements accessible in heavy ion collisions at the LHC. How can these observables be measured, to what extent can they be calculated, and what do they tell us about the dense mesoscopic system created during the collision? In the first lecture, I shall focus in particular on measurements that constrain the spatio-temporal picture of the collisions and that measure centrality, orientations and extensions. In the subsequent lectures, I then discuss on how classes of measurements allow one to characterize collective phenomena, and to what extent these measurements can constrain the properties of matter produced in heavy ion collisions.

A zero-gravity demonstration of the collision and coalescence of water droplets

NASA Technical Reports Server (NTRS)

Hung, R. J.; Vaughan, O. H.; Smith, R. E.

1974-01-01

The mechanics of the collision and coalescence of liquid droplets is one of the main research areas in the fields of nuclear physics, astrophysics, meteorology and fluid mechanics. The crew members on the Skylab 3 and 4 missions were requested to perform demonstrations of the collision and coalescence of water droplets under the low gravity environment at orbital altitude. In Skylab 4 two water droplets with equal volumes, 30 cu cm each, were used. A dark colored droplet (contaminated with grape drink) moving with a velocity of 3.14 cm/sec collided with a stationary pink colored droplet (contaminated with strawberry drink) and coalescence occurred. Theoretical models are proposed to study the various stages of the collision-coalescence processes. Special considerations are concentrated in the investigation of the bounce-coalescence and coalescence-instability processes. The surface tension of the coalesced droplets was calculated to be 52 dynes/cm in perfect agreement with laboratory measurements made after the flight using a reproduction of the liquids.

Synthesis and characterization of polymeric V2O5/AlO(OH) with nanopores on alumina support.

PubMed

Ahmad, A L; Abd Shukor, S R; Leo, C P

2006-12-01

Polymeric vanadium pentoxide gel was formed via the reaction of V2O5 powder with hydrogen peroxide. The polymeric vanadium pentoxide gel was then dispersed in alumina gel. Different vanadium loading composites were coated on alumina support and calcined at 500 degrees C for 1 hr. These composite layers were characterized using TGA, FT-IR, XRD, SEM, and Autosorb. It was found that the lamellar structure of polymerized vanadium pentoxide was retained in the inorganic matrix. Crystalline alumina in gamma phase was formed after calcinations. However, the vanadium-alumina mixed oxides are lack of the well defined PXRD peaks for polycrystalline V2O5. This is possibly because the vanadia species are highly dispersed in the alumina matrix or the vanadia species are dispersed as crystalline which is smaller than 4 nm. In addition, the imbedded polymeric vanadium oxide improved the specific area and average pore diameter of the composite layer.

Vibrational relaxation of I2 in complexing solvents: The role of solvent-solute attractive forces

NASA Astrophysics Data System (ADS)

Shiang, Joseph J.; Liu, Hongjun; Sension, Roseanne J.

1998-12-01

Femtosecond transient absorption studies of I2-arene complexes, with arene=hexamethylbenzene (HMB), mesitylene (MST), or m-xylene (mX), are used to investigate the effect of solvent-solute attractive forces upon the rate of vibrational relaxation in solution. Comparison of measurements on I2-MST complexes in neat mesitylene and I2-MST complexes diluted in carbontetrachloride demonstrate that binary solvent-solute attractive forces control the rate of vibrational relaxation in this prototypical model of diatomic vibrational relaxation. The data obtained for different arenes demonstrate that the rate of I2 relaxation increases with the magnitude of the I2-arene attractive interaction. I2-HMB relaxes much faster than I2 in MST or mX. The results of these experiments are discussed in terms of both isolated binary collision and instantaneous normal mode models for vibrational relaxation.

Efficient simulation of pitch angle collisions in a 2+2-D Eulerian Vlasov code

NASA Astrophysics Data System (ADS)

Banks, Jeff; Berger, R.; Brunner, S.; Tran, T.

2014-10-01

Here we discuss pitch angle scattering collisions in the context of the Eulerian-based kinetic code LOKI that evolves the Vlasov-Poisson system in 2+2-dimensional phase space. The collision operator is discretized using 4th order accurate conservative finite-differencing. The treatment of the Vlasov operator in phase-space uses an approach based on a minimally diffuse, fourth-order-accurate discretization (Banks and Hittinger, IEEE T. Plasma Sci. 39, 2198). The overall scheme is therefore discretely conservative and controls unphysical oscillations. Some details of the numerical scheme will be presented, and the implementation on modern highly concurrent parallel computers will be discussed. We will present results of collisional effects on linear and non-linear Landau damping of electron plasma waves (EPWs). In addition we will present initial results showing the effect of collisions on the evolution of EPWs in two space dimensions. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 and funded by the LDRD program at LLNL under project tracking code 12-ERD-061.

Importance of rotational adiabaticity in collisions of CO2 super rotors with Ar and He

NASA Astrophysics Data System (ADS)

Murray, Matthew J.; Ogden, Hannah M.; Mullin, Amy S.

2018-02-01

The collision dynamics of optically centrifuged CO2 with Ar and He are reported here. The optical centrifuge produces an ensemble of CO2 molecules in high rotational states (with J ˜ 220) with oriented angular momentum. Polarization-dependent high-resolution transient IR absorption spectroscopy was used to measure the relaxation dynamics in the presence of Ar or He by probing the CO2 J = 76 and 100 states with Er o t=2306 and 3979 cm-1, respectively. The data show that He relaxes the CO2 super rotors more quickly than Ar. Doppler-broadened line profiles show that He collisions induce substantially larger rotation-to-translation energy transfer. CO2 super rotors have greater orientational anisotropy with He collisions and the anisotropy from the He collisions persists longer than with Ar. Super rotor relaxation dynamics are discussed in terms of mass effects related to classical gyroscope physics and collisional rotational adiabaticity.

State-to-state, multi-collision, energy transfer in H-H2 gas ensembles.

PubMed

McCaffery, Anthony J; Marsh, Richard J

2013-12-21

We use our recently developed computational model of energy flow in gas ensembles to study translation-to-internal energy conversion in an ensemble consisting of H2(0; 0) in a bath of H atoms. This mixture is found in plasmas of industrial importance and also in interstellar clouds. The storage of energy of relative motion as rovibrational energy of H2 represents a potential mechanism for cooling translation. This may have relevance in astrophysical contexts such as the post-recombination epoch of the early universe when hydrogenic species dominated and cooling was a precondition for the formation of structured objects. We find that conversion of translational motion to H2 vibration and rotation is fast and, in our closed system, is complete within around 100 cycles of ensemble collisions. Large amounts of energy become stored as H2 vibration and a tentative mechanism for this unequal energy distribution is suggested. The "structured dis-equilibrium" we observe is found to persist through many collision cycles. In contrast to the rapidity of excitation, the relaxation of H2(6; 10) in H is very slow and not complete after 10(5) collision cycles. The quasi-equilibrium modal temperatures of translation, rotation, and vibration are found to scale linearly with collision energy but at different rates. This may be useful in estimating the partitioning of energy within a given H + H2 ensemble.

Nonlinear geometries in liquid crystals and liquid crystalline polymers

NASA Astrophysics Data System (ADS)

Dingemans, Theo Jacobus

The thermodynamic properties of thermotropic liquid crystals (LCs), and polymeric LCs are strongly dependent on mesogenic shape and in order to explore the relationships between shape and physical properties new, nonlinear geometries were examined. Symmetric oxadiazole based model compounds were synthesized and despite an internal exocyclic bond angle of 134sp° the model compounds exhibit a variety of mesophases. Conoscopic studies on bis(p-hexyloxyphenyl) 4,4sp'- (1,3,4-oxadiazole-2,5-diyl) dicarboxylate in its phase Ssb{A} phase are not consistent with the uniaxial Ssb{A} phase, but rather a biaxial Ssb{CM} phase. Uniaxial and biaxial mesogenic monomers were incorporated in main-chain polyesters. Transition temperatures of the interfacially prepared polymers were higher than materials that were melt polymerized. sp{13}C NMR showed that all polymers prepared by melt condensation have random monomer sequence distributions at the diad level. Thiophene and 1,3-phenylene modified p-quinquephenyls were synthesized in order to investigate the effects of mesogen nonlinearity and dipole direction on the LC thermodynamic properties. Results indicate that shape asymmetry favors mesophase formation and stability; the thiophene dipole moment appears to have no effect. The 120sp° exocyclic bond angle disrupts liquid crystallinity in 1,3-phenylene derivatives. Additionally the placement of 2,5-thiophene in "p-quinquephenyls" affects a red shift in its UV absorption. This was exploited in single layer light emitting diodes (LEDs) to tune the electroluminescence emission. In double layer LEDs these compounds function as efficient hole transport materials with high light outputs. Ferroelectric LCs derived from isoleucine were synthesized and shown to have spontaneous polarizations that are a strong function of halogen size (F > Cl > Br).

Collision-induced dissociation of protonated water clusters

NASA Astrophysics Data System (ADS)

Berthias, F.; Buridon, V.; Abdoul-Carime, H.; Farizon, B.; Farizon, M.; Dinh, P. M.; Reinhard, P.-G.; Suraud, E.; Märk, T. D.

2014-06-01

Collision-induced dissociation (CID) has been studied for protonated water clusters H+(H2O)n, with n = 2-8, colliding with argon atoms at a laboratory energy of 8 keV. The experimental data have been taken with an apparatus (Device for Irradiation of Molecular Clusters, `Dispositif d'Irradiation d'Agrégats Moléculaire,' DIAM) that has been recently constructed at the Institut de Physique Nucléaire de Lyon. It includes an event-by-event mass spectrometry detection technique, COINTOF (correlated ion and neutral fragment time of flight). The latter device allows, for each collision event, to detect and identify in a correlated manner all produced neutral and charged fragments. For all the studied cluster ions, it has allowed us to identify branching ratios for the loss of i = 1 to i = n water molecules, leading to fragment ions ranging from H+(H2O)i=n-1 all the way down to the production of protons. Using a corresponding calibration technique we determine total charged fragment production cross sections for incident protonated water clusters H+(H2O)n, with n = 2-7. Observed trends for branching ratios and cross sections, and a comparison with earlier data on measured attenuation cross sections for water clusters colliding with other noble gases (He and Xe), give insight into the underlying dissociation mechanisms.

Silver(I) complexes of the weakly coordinating solvents SO(2) and CH(2)Cl(2): crystal structures, bonding, and energetics of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)].

PubMed

Decken, Andreas; Knapp, Carsten; Nikiforov, Grigori B; Passmore, Jack; Rautiainen, J Mikko; Wang, Xinping; Zeng, Xiaoqing

2009-06-22

Pushing the limits of coordination chemistry: The most weakly coordinated silver complexes of the very weakly coordinating solvents dichloromethane and liquid sulfur dioxide were prepared. Special techniques at low temperatures and the use of weakly coordinating anions allowed structural characterization of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(Cl(2)CH(2))(2)][SbF(6)] (see figure). An investigation of the bonding shows that these complexes are mainly stabilized by electrostatic monopole-dipole interactions.The synthetically useful solvent-free silver(I) salt Ag[Al(pftb)(4)] (pftb=--OC(CF(3))(3)) was prepared by metathesis reaction of Li[Al(pftb)(4)] with Ag[SbF(6)] in liquid SO(2). The solvated complexes [Ag(OSO)][Al(pftb)(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)] were prepared and isolated by special techniques at low temperatures and structurally characterized by single-crystal X-ray diffraction. The SO(2) complexes provide the first examples of coordination of the very weak Lewis base SO(2) to silver(I). The SO(2) molecule in [Ag(OSO)][Al(pftb)(4)] is eta(1)-O coordinated to Ag(+), while the SO(2) ligands in [Ag(OSO)(2/2)][SbF(6)] bridge two Ag(+) ions in an eta(2)-O,O' (trans,trans) manner. [Ag(CH(2)Cl(2))(2)][SbF(6)] contains [Ag(CH(2)Cl(2))(2)](+) ions linked through [SbF(6)](-) ions to give a polymeric structure. The solid-state silver(I) ion affinities (SIA) of SO(2) and CH(2)Cl(2), based on bond lengths and corresponding valence units in the corresponding complexes and tensimetric titrations of Ag[Al(pftb)(4)] and Ag[SbF(6)] with SO(2) vapor, show that SO(2) is a weaker ligand to Ag(+) than the commonly used weakly coordinating solvent CH(2)Cl(2) and indicated that binding strength of SO(2) to silver(I) in the silver(I) salts increases with increasing size of the corresponding counteranion ([Al(pftb)(4)](-)>[SbF(6)](-)). The experimental findings are in good agreement with theoretical gas-phase ligand

Radical-Mediated Enzymatic Polymerizations

PubMed Central

Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

2016-01-01

Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

Ionic Liquid Crystals: Versatile Materials.

PubMed

Goossens, Karel; Lava, Kathleen; Bielawski, Christopher W; Binnemans, Koen

2016-04-27

This Review covers the recent developments (2005-2015) in the design, synthesis, characterization, and application of thermotropic ionic liquid crystals. It was designed to give a comprehensive overview of the "state-of-the-art" in the field. The discussion is focused on low molar mass and dendrimeric thermotropic ionic mesogens, as well as selected metal-containing compounds (metallomesogens), but some references to polymeric and/or lyotropic ionic liquid crystals and particularly to ionic liquids will also be provided. Although zwitterionic and mesoionic mesogens are also treated to some extent, emphasis will be directed toward liquid-crystalline materials consisting of organic cations and organic/inorganic anions that are not covalently bound but interact via electrostatic and other noncovalent interactions.

Performance evaluation of microbial electrochemical systems operated with Nafion and supported ionic liquid membranes.

PubMed

Koók, László; Nemestóthy, Nándor; Bakonyi, Péter; Zhen, Guangyin; Kumar, Gopalakrishnan; Lu, Xueqin; Su, Lianghu; Saratale, Ganesh Dattatraya; Kim, Sang-Hyoun; Gubicza, László

2017-05-01

In this work, the performance of dual-chamber microbial fuel cells (MFCs) constructed either with commonly used Nafion ® proton exchange membrane or supported ionic liquid membranes (SILMs) was assessed. The behavior of MFCs was followed and analyzed by taking the polarization curves and besides, their efficiency was characterized by measuring the electricity generation using various substrates such as acetate and glucose. By using the SILMs containing either [C 6 mim][PF 6 ] or [Bmim][NTf 2 ] ionic liquids, the energy production of these MFCs from glucose was comparable to that obtained with the MFC employing polymeric Nafion ® and the same substrate. Furthermore, the MFC operated with [Bmim][NTf 2 ]-based SILM demonstrated higher energy yield in case of low acetate loading (80.1 J g -1 COD in m -2  h -1 ) than the one with the polymeric Nafion ® N115 (59 J g -1 COD in m -2  h -1 ). Significant difference was observed between the two SILM-MFCs, however, the characteristics of the system was similar based on the cell polarization measurements. The results suggest that membrane-engineering applying ionic liquids can be an interesting subject field for bioelectrochemical system research. Copyright © 2017 Elsevier Ltd. All rights reserved.

Near-resonant rotational energy transfer in HCl–H{sub 2} inelastic collisions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lanza, Mathieu; Lique, François, E-mail: francois.lique@univ-lehavre.fr; Kalugina, Yulia

2014-02-14

We present a new four-dimensional (4D) potential energy surface for the HCl–H{sub 2} van der Waals system. Both molecules were treated as rigid rotors. Potential energy surface was obtained from electronic structure calculations using a coupled cluster with single, double, and perturbative triple excitations method. The four atoms were described using the augmented correlation-consistent quadruple zeta basis set and bond functions were placed at mid-distance between the HCl and H{sub 2} centers of mass for a better description of the van der Waals interaction. The global minimum is characterized by the well depth of 213.38 cm{sup −1} corresponding to themore » T-shape structure with H{sub 2} molecule on the H side of the HCl molecule. The dissociation energies D{sub 0} are 34.7 cm{sup −1} and 42.3 cm{sup −1} for the complex with para- and ortho-H{sub 2}, respectively. These theoretical results obtained using our new PES are in good agreement with experimental values [D. T. Anderson, M. Schuder, and D. J. Nesbitt, Chem. Phys. 239, 253 (1998)]. Close coupling calculations of the inelastic integral rotational cross sections of HCl in collisions with para-H{sub 2} and ortho-H{sub 2} were performed at low and intermediate collisional energies. Significant differences exist between para- and ortho-H{sub 2} results. The strongest collision-induced rotational HCl transitions are the transitions with Δj = 1 for collisions with both para-H{sub 2} and ortho-H{sub 2}. Rotational relaxation of HCl in collision with para-H{sub 2} in the rotationally excited states j = 2 is dominated by near-resonant energy transfer.« less

In situ chemical oxidative polymerization preparation of poly(3,4-ethylenedioxythiophene)/graphene nanocomposites with enhanced thermoelectric performance.

PubMed

Xu, Kongli; Chen, Guangming; Qiu, Dong

2015-05-01

Three different in situ chemical oxidative polymerization routes, that is, (A) spin-coating and subsequent liquid layer polymerization, (B) spin-coating followed by vapor phase polymerization, and (C) in situ polymerization and then post-treatment by immersion in ethylene glycol (EG), have been developed to achieve poly(3,4-ethylenedioxythiophene)/reduced graphene oxide (PEDOT/rGO) nanocomposites. As demonstrated by scanning electron microscopic and energy-dispersive X-ray spectroscopic techniques, PEDOT has been successfully coated on the surface of the rGO nanosheets by each of the three preparation routes. Importantly, all of the nanocomposites display a greatly enhanced thermoelectric performance (power factors) relative to those of the corresponding neat PEDOT. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Discrepant Results in a 2-D Marble Collision

ERIC Educational Resources Information Center

Kalajian, Peter

2013-01-01

Video analysis of 2-D collisions is an excellent way to investigate conservation of linear momentum. The often-desired experimental design goal is to minimize the momentum loss in order to demonstrate the conservation law. An air table with colliding pucks is an ideal medium for this experiment, but such equipment is beyond the budget of many…

25th anniversary article: "Cooking carbon with salt": carbon materials and carbonaceous frameworks from ionic liquids and poly(ionic liquid)s.

PubMed

Fellinger, Tim-Patrick; Thomas, Arne; Yuan, Jiayin; Antonietti, Markus

2013-11-06

This review surveys recent work on the use of ionic liquids (ILs) and polymerized ionic liquids (PILs) as precursors to synthesize functional carbon materials. As solvents or educts with negligible vapour pressure, these systems enable simple processing, composition, and structural control of the resulting carbons under rather simple and green synthesis conditions. Recent applications of the resulting nanocarbons across a multitude of fields, such as fuel cells, energy storage in batteries and supercapacitors, catalysis, separation, and sorption materials are highlighted. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The presence of polymeric material in radiolysed aqueous solutions of ammonium bicarbonate

NASA Astrophysics Data System (ADS)

Draganic, Z. D.; Negron-Mendoza, A.; Navarro-Gonzalez, R.; Vujosevic, S. I.

A polymeric material is present in radiolysed aqueous solutions (O 2-free) of ammonium bicarbonate (0.05 mol dm -3) at large doses of cobalt-60 gamma rays (0.15-1.7 MGy). Polymer is a secondary radiolytic product: its measurable amounts appear after about 0.15 MGy and increase with dose to become about 0.1 g dm -3 at 1.7 MGy. Throughout the dose range studied, the HPLC gives for molecular weight 16,000-14,000 dalton, and the i.r. spectra show the presence of characteristic functional groups of CH 2, CH, CO -3, COO - and NH +4. Possible chemical nature of polymeric material and its origin are considered.

Ultra-relativistic Au+Au and d+Au collisions:

NASA Astrophysics Data System (ADS)

Back, B. B.; Baker, M. D.; Ballintijn, M.; Barton, D. S.; Betts, R. R.; Bickley, A. A.; Bindel, R.; Budzanowski, A.; Busza, W.; Carroll, A.; Chai, Z.; Decowski, M. P.; García, E.; Gburek, T.; George, N.; Gulbrandsen, K.; Gushue, S.; Halliwell, C.; Hamblen, J.; Hauer, M.; Heintzelman, G. A.; Henderson, C.; Hofman, D. J.; Hollis, R. S.; Hołyński, R.; Holzman, B.; Iordanova, A.; Johnson, E.; Kane, J. L.; Katzy, J.; Khan, N.; Kucewicz, W.; Kulinich, P.; Kuo, C. M.; Lin, W. T.; Manly, S.; McLeod, D.; Mignerey, A. C.; Nouicer, R.; Olszewski, A.; Pak, R.; Park, I. C.; Pernegger, H.; Reed, C.; Remsberg, L. P.; Reuter, M.; Roland, C.; Roland, G.; Rosenberg, L.; Sagerer, J.; Sarin, P.; Sawicki, P.; Seals, H.; Sedykh, I.; Skulski, W.; Smith, C. E.; Stankiewicz, M. A.; Steinberg, P.; Stephans, G. S. F.; Sukhanov, A.; Tang, J.-L.; Tonjes, M. B.; Trzupek, A.; Vale, C.; van Nieuwenhuizen, G. J.; Vaurynovich, S. S.; Verdier, R.; Veres, G. I.; Wenger, E.; Wolfs, F. L. H.; Wosiek, B.; Woźniak, K.; Wuosmaa, A. H.; Wysłouch, B.

In this talk I will review PHOBOS data on charged particle multiplicities, obtained in Au+Au and d+Au collisions at RHIC. The general features of the Au+Au pseudorapidity distributions results will be discussed and compared to those of /line{p}p collisions. The total charged particle multiplicity, scaled by the number of participant pairs, is observed to be about 40% higher in Au+Au collisions than in /line{p}p and d+Au systems, but, surprisingly at the same level of e+e- collisions. Limiting fragmentation scaling is seen to be obeyed in Au+Au collisions.

Thiolene and SIFEL-based Microfluidic Platforms for Liquid-Liquid Extraction

PubMed Central

Goyal, Sachit; Desai, Amit V.; Lewis, Robert W.; Ranganathan, David R.; Li, Hairong; Zeng, Dexing; Reichert, David E.; Kenis, Paul J.A.

2014-01-01

Microfluidic platforms provide several advantages for liquid-liquid extraction (LLE) processes over conventional methods, for example with respect to lower consumption of solvents and enhanced extraction efficiencies due to the inherent shorter diffusional distances. Here, we report the development of polymer-based parallel-flow microfluidic platforms for LLE. To date, parallel-flow microfluidic platforms have predominantly been made out of silicon or glass due to their compatibility with most organic solvents used for LLE. Fabrication of silicon and glass-based LLE platforms typically requires extensive use of photolithography, plasma or laser-based etching, high temperature (anodic) bonding, and/or wet etching with KOH or HF solutions. In contrast, polymeric microfluidic platforms can be fabricated using less involved processes, typically photolithography in combination with replica molding, hot embossing, and/or bonding at much lower temperatures. Here we report the fabrication and testing of microfluidic LLE platforms comprised of thiolene or a perfluoropolyether-based material, SIFEL, where the choice of materials was mainly guided by the need for solvent compatibility and fabrication amenability. Suitable designs for polymer-based LLE platforms that maximize extraction efficiencies within the constraints of the fabrication methods and feasible operational conditions were obtained using analytical modeling. To optimize the performance of the polymer-based LLE platforms, we systematically studied the effect of surface functionalization and of microstructures on the stability of the liquid-liquid interface and on the ability to separate the phases. As demonstrative examples, we report (i) a thiolene-based platform to determine the lipophilicity of caffeine, and (ii) a SIFEL-based platform to extract radioactive copper from an acidic aqueous solution. PMID:25246730

Do Young Drivers Become Safer After Being Involved in a Collision?

PubMed Central

O’Brien, Fearghal; Bible, Joe; Liu, Danping; Simons-Morton, Bruce G.

2017-01-01

As drivers age, their risk of being involved in a car collision decreases. The present study investigated if this trend is due, in part, to some risky drivers having a collision early in their driving lives and subsequently reducing their risky driving after that negative experience. Accelerometers and video cameras were installed in the vehicles of 16- to 17-year-old drivers (N = 254), allowing coders to measure the number of g-force events (i.e., events in which a threshold acceleration level was exceeded) per 1,000 miles and the number of collisions. Among the 41 participants who experienced a severe collision, the rate of g-force events dropped significantly in the 1st month after the collision, remained unchanged for the 2nd month, and increased significantly in the 3rd month. There were no changes in the rate of g-force events at comparable time points for the drivers not involved in a collision. Being involved in a collision led to a decrease in risky driving, but this may have been a temporary effect. PMID:28406372

Hydrogen Cyanide Polymerization: A Preferred Cosmochemical Pathway

NASA Astrophysics Data System (ADS)

Matthews, Clifford N.

In the presence of a base such as ammonia, liquid HCN polymerizes spontaneously at room temperature to a brown-black solid from which a yellow-brown powder can be extracted by water and further hydrolyzed to yield a-amino acids. Two types of structural units appear to be present in these polymeric products, stable ladder polymers with conjugated -C=N- bonds, and polyamidines, readily converted by water to polypeptides. Several kinds of investigations, including electric discharge experiments which produce HCN from methane and ammonia, give results consistent with the hypothesis that the original polypeptides on Earth were synthesized directly from such HCN polymers and water without the intervening formation of -amino acids. In the absence of water - on land - the intermediate polyamidines could have been the original condensing agents directing the synthesisis of nucleosides and nucleotides from available sugars, phosphates and nitrogen bases. Most significant would have been the parallel synthesis of polypeptides and polynucleotides arising from the dehydrating action of these polyamidines on nucleotides.

The 2.35 year itch of Cygnus OB2 #9. I. Optical and X-ray monitoring

NASA Astrophysics Data System (ADS)

Nazé, Y.; Mahy, L.; Damerdji, Y.; Kobulnicky, H. A.; Pittard, J. M.; Parkin, E. R.; Absil, O.; Blomme, R.

2012-10-01

Context. Nonthermal radio emission in massive stars is expected to arise in wind-wind collisions occurring inside a binary system. One such case, the O-type star Cyg OB2 #9, was proven to be a binary only four years ago, but the orbital parameters remained uncertain. The periastron passage of 2011 was the first one to be observable under good conditions since the discovery of binarity. Aims: In this context, we have organized a large monitoring campaign to refine the orbital solution and to study the wind-wind collision. Methods: This paper presents the analysis of optical spectroscopic data, as well as of a dedicated X-ray monitoring performed with Swift and XMM-Newton. Results: In light of our refined orbital solution, Cyg OB2 #9 appears as a massive O+O binary with a long period and high eccentricity; its components (O5-5.5I for the primary and O3-4III for the secondary) have similar masses and similar luminosities. The new data also provide the first evidence that a wind-wind collision is present in the system. In the optical domain, the broad Hα line varies, displaying enhanced absorption and emission components at periastron. X-ray observations yield the unambiguous signature of an adiabatic collision, because as the stars approach periastron, the X-ray luminosity closely follows the 1/D variation expected in that case. The X-ray spectrum appears, however, slightly softer at periastron, which is probably related to winds colliding at slightly lower speeds at that time. Conclusions: It is the first time that such a variation has been detected in O+O systems, and the first case where the wind-wind collision is found to remain adiabatic even at periastron passage. Based on observations collected at OHP, with Swift, and with XMM-Newton.Tables 1 and 2 are available in electronic form at http://www.aanda.org

Polymeric membrane materials for artificial organs.

PubMed

Kawakami, Hiroyoshi

2008-01-01

Many polymeric materials have already been used in the field of artificial organs. However, the materials used in artificial organs are not necessarily created with the best material selectivity and materials design; therefore, the development of synthesized polymeric membrane materials for artificial organs based on well-defined designs is required. The approaches to the development of biocompatible polymeric materials fall into three categories: (1) control of physicochemical characteristics on material surfaces, (2) modification of material surfaces using biomolecules, and (3) construction of biomimetic membrane surfaces. This review will describe current issues regarding polymeric membrane materials for use in artificial organs.

Rifampicin-loaded 'flower-like' polymeric micelles for enhanced oral bioavailability in an extemporaneous liquid fixed-dose combination with isoniazid.

PubMed

Moretton, Marcela A; Hocht, Christian; Taira, Carlos; Sosnik, Alejandro

2014-08-01

Coadministration of rifampicin (RIF)/isoniazid (INH) is clinically recommended to improve the treatment of tuberculosis. Under gastric conditions, RIF undergoes fast hydrolysis (a pathway hastened by INH) and oral bioavailability loss. We aimed to assess the chemical stabilization and the oral pharmacokinetics of RIF nanoencapsulated within poly(ε-caprolactone)-b-PEG-b-poly(ε-caprolactone) 'flower-like' polymeric micelles. The chemical stability of RIF was evaluated in vitro under acid conditions with and without INH, and the oral pharmacokinetics of RIF-loaded micelles in rats was compared with those of a suspension coded by the US Pharmacopeia. Nanoencapsulation decreased the degradation rate of RIF with respect to the free drug. Moreover, in vivo data showed a statistically significant increase of RIF oral bioavailability (up to 3.3-times) with respect to the free drug in the presence of INH. Overall results highlight the potential of this nanotechnology platform to develop an extemporaneous liquid RIF/INH fixed-dose combination suitable for pediatric administration.

Hydrodynamic collectivity in proton-proton collisions at 13 TeV

NASA Astrophysics Data System (ADS)

Zhao, Wenbin; Zhou, You; Xu, Hao-jie; Deng, Weitian; Song, Huichao

2018-05-01

In this paper, we investigate the hydrodynamic collectivity in proton-proton (p-p) collisions at 13 TeV, using iEBE-VISHNU hybrid model with HIJING initial conditions. With properly tuned parameters, our model simulations can remarkably describe all the measured 2-particle correlations, including integrated and differential elliptic flow coefficients for all charged and identified hadrons (KS0 , Λ). However, our model calculations show positive 4-particle cumulant c2 { 4 } in high multiplicity pp collisions, and can not reproduce the negative c2 { 4 } measured in experiment. Further investigations on the HIJING initial conditions show that the fluctuations of the second order anisotropy coefficient ε2 increases with the increase of its mean value, which leads to a similar trend of the flow fluctuations. For a simultaneous description of the 2- and 4- particle cumulants within the hydrodynamic framework, it is required to have significant improvements on initial condition for pp collisions, which is still lacking of knowledge at the moment.

Ring-Opening Polymerization of rac-Lactide with Aluminum Chiral Anilido-Oxazolinate Complexes

PubMed Central

2015-01-01

A series of dimethylaluminum complexes (L1a–i)AlMe2 (2a–i, where HL1a–i = 2-(2′-ArNH)phenyl-4-R1-oxazoline) bearing chiral, bidentate anilido-oxazolinate ligands have been prepared and characterized. Six of the complexes, in the presence of an alcohol cocatalyst, are shown to be active initiators for the stereoselective ring-opening polymerization of rac-lactide in toluene solution and under bulk conditions, yielding polylactides with a range of tacticity from slightly isotactic to moderately heterotactic. The reactivity and selectivity of these catalysts are discussed on the basis of the effect of their substituents. PMID:24891754

Time-dependent observables in heavy ion collisions. Part I. Setting up the formalism

NASA Astrophysics Data System (ADS)

Wu, Bin; Kovchegov, Yuri V.

2018-03-01

We adapt the Schwinger-Keldysh formalism to study heavy-ion collisions in perturbative QCD. Employing the formalism, we calculate the two-point gluon correlation function G 22 aμ, bν due to the lowest-order classical gluon fields in the McLerran-Venugopalan model of heavy ion collisions and observe an interesting transition from the classical fields to the quasi-particle picture at later times. Motivated by this observation, we push the formalism to higher orders in the coupling and calculate the contribution to G 22 aμ, bν coming from the diagrams representing a single rescattering between two of the produced gluons. We assume that the two gluons go on mass shell both before and after the rescattering. The result of our calculation depends on which region of integration over the proper time of the rescattering τ Z gives the correct correlation function at late proper time τ when the gluon distribution is measured. For (i) τ Z ≫ 1 /Q s and τ - τ Z ≫ 1 /Q s (with Q s the saturation scale) we obtain the same results as from the Boltzmann equation. For (ii) τ - τ Z ≫ τ Z ≫ 1 /Q s we end up with a result very different from kinetic theory and consistent with a picture of "free-streaming" particles. Due to the approximations made, our calculation is too coarse to indicate whether the region (i) or (ii) is the correct one: to resolve this controversy, we shall present a detailed diagrammatic calculation of the rescattering correction in the φ 4 theory in the second paper of this duplex.

Characterization of inclusion complexes of organic ions with hydrophilic hosts by ion transfer voltammetry with solvent polymeric membranes.

PubMed

Olmos, José Manuel; Laborda, Eduardo; Ortuño, Joaquín Ángel; Molina, Ángela

2017-03-01

The quantitative characterization of inclusion complexes formed in aqueous phase between organic ions and hydrophilic hosts by ion-transfer voltammetry with solvent polymeric membrane ion sensors is studied, both in a theoretical and experimental way. Simple analytical solutions are presented for the determination of the binding constant of the complex from the variation with the host concentration of the electrochemical signal. These solutions are valid for any voltammetric technique and for solvent polymeric membrane ion sensors comprising one polarisable interface (1PI) and also, for the first time, two polarisable interfaces (2PIs). Suitable experimental conditions and data analysis procedures are discussed and applied to the study of the interactions of a common ionic liquid cation (1-octyl-3-metyl-imidazolium) and an ionisable drug (clomipramine) with two hydrophilic cyclodextrins: α-cyclodextrin and 2-hydroxypropyl-β-cyclodextrin. The experimental study is performed via square wave voltammetry with 2PIs and 1PI solvent polymeric membranes and in both cases the electrochemical experiments enable the detection of inclusion complexes and the determination of the corresponding binding constant. Copyright © 2016 Elsevier B.V. All rights reserved.

POLYMERIZATION OF /cap alpha/-METHYLSTYRENE BY ELECTRON IRRADIATION (in German)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Braun, D.; Heufer, G.; Seufert, W.

1964-01-01

Ampoules of alpha -methylstyrene sealed under vacuum were irradiated with 1-Mev electrons in a type JS Van de Graaff generator; comparative experiments with gamma rays were carried out with a /sup 60/Co source of 3000 deg C. High doses of electrons (ca. 10/sup 8/ rad) are necessary for polymerization. The conversion is graphed as a function of dose at 0 deg C; it reaches a maximum plateau of 65% at 4 x 10/sup 8/ rad; this may point to radiolysis of the polymer at doses above this. Polymerization conversion increases with decreasing dose rate, when dose and temperature are heldmore » constant; and conversion increases with decreasing temperature (22% at --22 deg C; 10% at 15 deg C; <1% at 60 deg C), as has been found with gamma rays. In the solid state between --40 deg C and --80 deg C the maximum yield is only about 5%. The molecular weights of all poly- alpha -methylstyrenes thus formed lie between 3000 and 12,000, independently of dose rate and temperature. All polymethylstyrenes formed in the liquid state have approximately the same tacticity independent of temperature (isotactic about 20%; syndiotactic about 80%). This corresponds to the tacticity of polymers formed cationically with Lewis acids. In the solid state the tacticity is: isotactic 38%, syndiotactic, 62%, comparable with the tacticity of anionic polymerization. In the liquid state the tacticity and the sensitivity towards water indicate a cationic mechanism for the reaction. NMR studies also indicate a cationic mechanism. (BBB)« less

Evidence for an exotic S= -2, Q= -2 baryon resonance in proton-proton collisions at the CERN SPS.

PubMed

Alt, C; Anticic, T; Baatar, B; Barna, D; Bartke, J; Betev, L; Białkowska, H; Billmeier, A; Blume, C; Boimska, B; Botje, M; Bracinik, J; Bramm, R; Brun, R; Buncić, P; Cerny, V; Christakoglou, P; Chvala, O; Cramer, J G; Csató, P; Darmenov, N; Dimitrov, A; Dinkelaker, P; Eckardt, V; Farantatos, G; Filip, P; Flierl, D; Fodor, Z; Foka, P; Freund, P; Friese, V; Gál, J; Gaździcki, M; Georgopoulos, G; Gładysz, E; Hegyi, S; Höhne, C; Kadija, K; Karev, A; Kniege, S; Kolesnikov, V I; Kollegger, T; Korus, R; Kowalski, M; Kraus, I; Kreps, M; van Leeuwen, M; Lévai, P; Litov, L; Makariev, M; Malakhov, A I; Markert, C; Mateev, M; Mayes, B W; Melkumov, G L; Meurer, C; Mischke, A; Mitrovski, M; Molnár, J; Mrówczyński, St; Pálla, G; Panagiotou, A D; Panayotov, D; Perl, K; Petridis, A; Pikna, M; Pinsky, L; Pühlhofer, F; Reid, J G; Renfordt, R; Retyk, W; Roland, C; Roland, G; Rybczyński, M; Rybicki, A; Sandoval, A; Sann, H; Schmitz, N; Seyboth, P; Siklér, F; Sitar, B; Skrzypczak, E; Stefanek, G; Stock, R; Ströbele, H; Susa, T; Szentpétery, I; Sziklai, J; Trainor, T A; Varga, D; Vassiliou, M; Veres, G I; Vesztergombi, G; Vranić, D; Wetzler, A; Włodarczyk, Z; Yoo, I K; Zaranek, J; Zimányi, J

2004-01-30

Results of resonance searches in the Xi(-)pi(-), Xi(-)pi(+), Xi;(+)pi(-), and Xi;(+)pi(+) invariant mass spectra in proton-proton collisions at sqrt[s]=17.2 GeV are presented. Evidence is shown for the existence of a narrow Xi(-)pi(-) baryon resonance with mass of 1.862+/-0.002 GeV/c(2) and width below the detector resolution of about 0.018 GeV/c(2). The significance is estimated to be above 4.2sigma. This state is a candidate for the hypothetical exotic Xi(--)(3/2) baryon with S=-2, I=3 / 2, and a quark content of (dsdsū). At the same mass, a peak is observed in the Xi(-)pi(+) spectrum which is a candidate for the Xi(0)(3/2) member of this isospin quartet with a quark content of (dsus[-]d). The corresponding antibaryon spectra also show enhancements at the same invariant mass.

Soft Listeria: actin-based propulsion of liquid drops.

PubMed

Boukellal, Hakim; Campás, Otger; Joanny, Jean-François; Prost, Jacques; Sykes, Cécile

2004-06-01

We study the motion of oil drops propelled by actin polymerization in cell extracts. Drops deform and acquire a pearlike shape under the action of the elastic stresses exerted by the actin comet, a tail of cross-linked actin filaments. We solve this free boundary problem and calculate the drop shape taking into account the elasticity of the actin gel and the variation of the polymerization velocity with normal stress. The pressure balance on the liquid drop imposes a zero propulsive force if gradients in surface tension or internal pressure are not taken into account. Quantitative parameters of actin polymerization are obtained by fitting theory to experiment.

Dynamics of the F(-) + CH3I → HF + CH2I(-) Proton Transfer Reaction.

PubMed

Zhang, Jiaxu; Xie, Jing; Hase, William L

2015-12-17

Direct chemical dynamics simulations, at collision energies Erel of 0.32 and 1.53 eV, were performed to obtain an atomistic understanding of the F(-) + CH3I reaction dynamics. There is only the F(-) + CH3I → CH3F + I(-) bimolecular nucleophilic substitution SN2 product channel at 0.32 eV. Increasing Erel to 1.53 eV opens the endothermic F(-) + CH3I → HF + CH2I(-) proton transfer reaction, which is less competitive than the SN2 reaction. The simulations reveal proton transfer occurs by two direct atomic-level mechanisms, rebound and stripping, and indirect mechanisms, involving formation of the F(-)···HCH2I complex and the roundabout. For the indirect trajectories all of the CH2I(-) is formed with zero-point energy (ZPE), while for the direct trajectories 50% form CH2I(-) without ZPE. Without a ZPE constraint for CH2I(-), the reaction cross sections for the rebound, stripping, and indirect mechanisms are 0.2 ± 0.1, 1.2 ± 0.4, and 0.7 ± 0.2 Å(2), respectively. Discarding trajectories that do not form CH2I(-) with ZPE reduces the rebound and stripping cross sections to 0.1 ± 0.1 and 0.7 ± 0.5 Å(2). The HF product is formed rotationally and vibrationally unexcited. The average value of J is 2.6 and with histogram binning n = 0. CH2I(-) is formed rotationally excited. The partitioning between CH2I(-) vibration and HF + CH2I(-) relative translation energy depends on the treatment of CH2I(-) ZPE. Without a CH2I(-) ZPE constraint the energy partitioning is primarily to relative translation with little CH2I(-) vibration. With a ZPE constraint, energy partitioning to CH2I(-) rotation, CH2I(-) vibration, and relative translation are statistically the same. The overall F(-) + CH3I rate constant at Erel of both 0.32 and 1.53 eV is in good agreement with experiment and negligibly affected by the treatment of CH2I(-) ZPE, since the SN2 reaction is the major contributor to the total reaction rate constant. The potential energy surface and reaction dynamics for F

Reverse saturable absorption studies in polymerized indole - Effect of polymerization in the phenomenal enhancement of third order optical nonlinearity

NASA Astrophysics Data System (ADS)

Jayakrishnan, K.; Joseph, Antony; Bhattathiripad, Jayakrishnan; Ramesan, M. T.; Chandrasekharan, K.; Siji Narendran, N. K.

2016-04-01

We report our results on the identification of large order enhancement in nonlinear optical coefficients of polymerized indole and its comparative study with reference to its monomer counterpart. Indole monomer shows virtually little third order effects whereas its polymerized version exhibits phenomenal increase in its third order nonlinear optical parameters such as nonlinear refractive index and nonlinear absorption. Open aperture Z-scan trace of polyindole done with Q-switched Nd:YAG laser source (532 nm, 7 ns), shows β value as high as 89 cm/GW at a beam energy of 0.83 GW/cm2. Closed aperture Z-scan done at identical energies reveals nonlinear refractive index of the order of -3.55 × 10-17 m2/W. Band gap measurement of polyindole was done with UV-Vis absorption spectra and compared with that of Indole. FTIR spectra of the monomer and polymerized versions were recorded and relevant bond formations were confirmed from the characteristic peaks. Photo luminescent spectra were investigated to know the emission features of both molecules. Beam energy (I0) versus nonlinear absorption coefficient (β) plot indicates reverse saturable type of absorption behaviour in polyindole molecules. Degenerate Four Wave Mixing (DFWM) plot of polyindole reveals quite a cubic dependence between probe and phase conjugate signal and the resulting χ(3) is comparable with Z-scan results. Optical limiting efficiency of polyindole is comparable with certain derivatives of porphyrins, phthalocyanines and graphene oxides.

Charged-Particle Multiplicity Density at Midrapidity in Central Pb-Pb Collisions at sNN=2.76TeV

NASA Astrophysics Data System (ADS)

Aamodt, K.; Abelev, B.; Abrahantes Quintana, A.; Adamová, D.; Adare, A. M.; Aggarwal, M. M.; Aglieri Rinella, G.; Agocs, A. G.; Aguilar Salazar, S.; Ahammed, Z.; Ahmad Masoodi, A.; Ahmad, N.; Ahn, S. U.; Akindinov, A.; Aleksandrov, D.; Alessandro, B.; Alfaro Molina, R.; Alici, A.; Alkin, A.; Almaráz Aviña, E.; Alt, T.; Altini, V.; Altinpinar, S.; Altsybeev, I.; Andrei, C.; Andronic, A.; Anguelov, V.; Anson, C.; Antičić, T.; Antinori, F.; Antonioli, P.; Aphecetche, L.; Appelshäuser, H.; Arbor, N.; Arcelli, S.; Arend, A.; Armesto, N.; Arnaldi, R.; Aronsson, T.; Arsene, I. C.; Asryan, A.; Augustinus, A.; Averbeck, R.; Awes, T. C.; Äystö, J.; Azmi, M. D.; Bach, M.; Badalà, A.; Baek, Y. W.; Bagnasco, S.; Bailhache, R.; Bala, R.; Baldini Ferroli, R.; Baldisseri, A.; Baldit, A.; Baltasar Dos Santos Pedrosa, F.; Bán, J.; Barbera, R.; Barile, F.; Barnaföldi, G. G.; Barnby, L. S.; Barret, V.; Bartke, J.; Basile, M.; Bastid, N.; Bathen, B.; Batigne, G.; Batyunya, B.; Baumann, C.; Bearden, I. G.; Beck, H.; Belikov, I.; Bellini, F.; Bellwied, R.; Belmont-Moreno, E.; Beole, S.; Berceanu, I.; Bercuci, A.; Berdermann, E.; Berdnikov, Y.; Bergmann, C.; Betev, L.; Bhasin, A.; Bhati, A. K.; Bianchi, L.; Bianchi, N.; Bianchin, C.; Bielčík, J.; Bielčíková, J.; Bilandzic, A.; Biolcati, E.; Blanc, A.; Blanco, F.; Blanco, F.; Blau, D.; Blume, C.; Boccioli, M.; Bock, N.; Bogdanov, A.; Bøggild, H.; Bogolyubsky, M.; Boldizsár, L.; Bombara, M.; Bombonati, C.; Book, J.; Borel, H.; Borissov, A.; Bortolin, C.; Bose, S.; Bossú, F.; Botje, M.; Böttger, S.; Boyer, B.; Braun-Munzinger, P.; Bravina, L.; Bregant, M.; Breitner, T.; Broz, M.; Brun, R.; Bruna, E.; Bruno, G. E.; Budnikov, D.; Buesching, H.; Bugaiev, K.; Busch, O.; Buthelezi, Z.; Caffarri, D.; Cai, X.; Caines, H.; Calvo Villar, E.; Camerini, P.; Canoa Roman, V.; Cara Romeo, G.; Carena, F.; Carena, W.; Carminati, F.; Casanova Díaz, A.; Caselle, M.; Castillo Castellanos, J.; Catanescu, V.; Cavicchioli, C.; Cepila, J.; Cerello, P.; Chang, B.; Chapeland, S.; Charvet, J. L.; Chattopadhyay, S.; Chattopadhyay, S.; Cherney, M.; Cheshkov, C.; Cheynis, B.; Chiavassa, E.; Chibante Barroso, V.; Chinellato, D. D.; Chochula, P.; Chojnacki, M.; Christakoglou, P.; Christensen, C. H.; Christiansen, P.; Chujo, T.; Cicalo, C.; Cifarelli, L.; Cindolo, F.; Cleymans, J.; Coccetti, F.; Coffin, J.-P.; Coli, S.; Conesa Balbastre, G.; Conesa Del Valle, Z.; Constantin, P.; Contin, G.; Contreras, J. G.; Cormier, T. M.; Corrales Morales, Y.; Cortés Maldonado, I.; Cortese, P.; Cosentino, M. R.; Costa, F.; Cotallo, M. E.; Crescio, E.; Crochet, P.; Cuautle, E.; Cunqueiro, L.; Erasmo, G. D.; Dainese, A.; Dalsgaard, H. H.; Danu, A.; Das, D.; Das, I.; Das, K.; Dash, A.; Dash, S.; de, S.; de Azevedo Moregula, A.; de Barros, G. O. V.; de Caro, A.; de Cataldo, G.; de Cuveland, J.; de Falco, A.; de Gruttola, D.; de Marco, N.; de Pasquale, S.; de Remigis, R.; de Rooij, R.; Debski, P. R.; Del Castillo Sanchez, E.; Delagrange, H.; Delgado Mercado, Y.; Dellacasa, G.; Deloff, A.; Demanov, V.; Dénes, E.; Deppman, A.; di Bari, D.; di Giglio, C.; di Liberto, S.; di Mauro, A.; di Nezza, P.; Dietel, T.; Divià, R.; Djuvsland, Ø.; Dobrin, A.; Dobrowolski, T.; Domínguez, I.; Dönigus, B.; Dordic, O.; Driga, O.; Dubey, A. K.; Dubuisson, J.; Ducroux, L.; Dupieux, P.; Dutta Majumdar, A. K.; Dutta Majumdar, M. R.; Elia, D.; Emschermann, D.; Engel, H.; Erdal, H. A.; Espagnon, B.; Estienne, M.; Esumi, S.; Evans, D.; Evrard, S.; Eyyubova, G.; Fabjan, C. W.; Fabris, D.; Faivre, J.; Falchieri, D.; Fantoni, A.; Fasel, M.; Fearick, R.; Fedunov, A.; Fehlker, D.; Fekete, V.; Felea, D.; Feofilov, G.; Fernández Téllez, A.; Ferretti, A.; Ferretti, R.; Figiel, J.; Figueredo, M. A. S.; Filchagin, S.; Fini, R.; Finogeev, D.; Fionda, F. M.; Fiore, E. M.; Floris, M.; Foertsch, S.; Foka, P.; Fokin, S.; Fragiacomo, E.; Fragkiadakis, M.; Frankenfeld, U.; Fuchs, U.; Furano, F.; Furget, C.; Fusco Girard, M.; Gaardhøje, J. J.; Gadrat, S.; Gagliardi, M.; Gago, A.; Gallio, M.; Gangadharan, D. R.; Ganoti, P.; Ganti, M. S.; Garabatos, C.; Garcia-Solis, E.; Garishvili, I.; Gemme, R.; Gerhard, J.; Germain, M.; Geuna, C.; Gheata, A.; Gheata, M.; Ghidini, B.; Ghosh, P.; Gianotti, P.; Girard, M. R.; Giraudo, G.; Giubellino, P.; Gladysz-Dziadus, E.; Glässel, P.; Gomez, R.; Ferreiro, E. G.; González Santos, H.; González-Trueba, L. H.; González-Zamora, P.; Gorbunov, S.; Gotovac, S.; Grabski, V.; Grajcarek, R.; Grelli, A.; Grigoras, A.; Grigoras, C.; Grigoriev, V.; Grigoryan, A.; Grigoryan, S.; Grinyov, B.; Grion, N.; Gros, P.; Grosse-Oetringhaus, J. F.; Grossiord, J.-Y.; Grosso, R.; Guber, F.; Guernane, R.; Guerra Gutierrez, C.; Guerzoni, B.; Gulbrandsen, K.; Gunji, T.; Gupta, A.; Gupta, R.; Gutbrod, H.; Haaland, Ø.; Hadjidakis, C.; Haiduc, M.; Hamagaki, H.; Hamar, G.; Harris, J. W.; Hartig, M.; Hasch, D.; Hasegan, D.; Hatzifotiadou, D.; Hayrapetyan, A.; Heide, M.; Heinz, M.; Helstrup, H.; Herghelegiu, A.; Hernández, C.; Herrera Corral, G.; Herrmann, N.; Hetland, K. F.; Hicks, B.; Hille, P. T.; Hippolyte, B.; Horaguchi, T.; Hori, Y.; Hristov, P.; Hřivnáčová, I.; Huang, M.; Huber, S.; Humanic, T. J.; Hwang, D. S.; Ichou, R.; Ilkaev, R.; Ilkiv, I.; Inaba, M.; Incani, E.; Innocenti, G. M.; Innocenti, P. G.; Ippolitov, M.; Irfan, M.; Ivan, C.; Ivanov, A.; Ivanov, M.; Ivanov, V.; Jachołkowski, A.; Jacobs, P. M.; Jancurová, L.; Jangal, S.; Janik, R.; Jena, S.; Jirden, L.; Jones, G. T.; Jones, P. G.; Jovanović, P.; Jung, H.; Jung, W.; Jusko, A.; Kalcher, S.; Kaliňák, P.; Kalisky, M.; Kalliokoski, T.; Kalweit, A.; Kamermans, R.; Kanaki, K.; Kang, E.; Kang, J. H.; Kaplin, V.; Karavichev, O.; Karavicheva, T.; Karpechev, E.; Kazantsev, A.; Kebschull, U.; Keidel, R.; Khan, M. M.; Khan, S. A.; Khanzadeev, A.; Kharlov, Y.; Kileng, B.; Kim, D. J.; Kim, D. S.; Kim, D. W.; Kim, H. N.; Kim, J. H.; Kim, J. S.; Kim, M.; Kim, M.; Kim, S.; Kim, S. H.; Kirsch, S.; Kisel, I.; Kiselev, S.; Kisiel, A.; Klay, J. L.; Klein, J.; Klein-Bösing, C.; Kliemant, M.; Klovning, A.; Kluge, A.; Knichel, M. L.; Koch, K.; Köhler, M. K.; Kolevatov, R.; Kolojvari, A.; Kondratiev, V.; Kondratyeva, N.; Konevskih, A.; Kornaś, E.; Kottachchi Kankanamge Don, C.; Kour, R.; Kowalski, M.; Kox, S.; Koyithatta Meethaleveedu, G.; Kozlov, K.; Kral, J.; Králik, I.; Kramer, F.; Kraus, I.; Krawutschke, T.; Kretz, M.; Krivda, M.; Krizek, F.; Krumbhorn, D.; Krus, M.; Kryshen, E.; Krzewicki, M.; Kucheriaev, Y.; Kuhn, C.; Kuijer, P. G.; Kurashvili, P.; Kurepin, A.; Kurepin, A. B.; Kuryakin, A.; Kushpil, S.; Kushpil, V.; Kweon, M. J.; Kwon, Y.; La Rocca, P.; Ladrón de Guevara, P.; Lafage, V.; Lara, C.; Lardeux, A.; Larsen, D. T.; Lazzeroni, C.; Le Bornec, Y.; Lea, R.; Lee, K. S.; Lee, S. C.; Lefèvre, F.; Lehnert, J.; Leistam, L.; Lenhardt, M.; Lenti, V.; León Monzón, I.; León Vargas, H.; Lévai, P.; Li, X.; Lien, J.; Lietava, R.; Lindal, S.; Lindenstruth, V.; Lippmann, C.; Lisa, M. A.; Liu, L.; Loenne, P. I.; Loggins, V. R.; Loginov, V.; Lohn, S.; Loizides, C.; Loo, K. K.; Lopez, X.; López Noriega, M.; López Torres, E.; Løvhøiden, G.; Lu, X.-G.; Luettig, P.; Lunardon, M.; Luparello, G.; Luquin, L.; Luzzi, C.; Ma, K.; Ma, R.; Madagodahettige-Don, D. M.; Maevskaya, A.; Mager, M.; Mahapatra, D. P.; Maire, A.; Mal'Kevich, D.; Malaev, M.; Maldonado Cervantes, I.; Malinina, L.; Malzacher, P.; Mamonov, A.; Manceau, L.; Mangotra, L.; Manko, V.; Manso, F.; Manzari, V.; Mao, Y.; Mareš, J.; Margagliotti, G. V.; Margotti, A.; Marín, A.; Markert, C.; Martashvili, I.; Martinengo, P.; Martínez, M. I.; Martínez Davalos, A.; Martínez García, G.; Martynov, Y.; Masciocchi, S.; Masera, M.; Masoni, A.; Massacrier, L.; Mastromarco, M.; Mastroserio, A.; Matthews, Z. L.; Matyja, A.; Mayani, D.; Mayer, C.; Mazza, G.; Mazzoni, M. A.; Meddi, F.; Menchaca-Rocha, A.; Mendez Lorenzo, P.; Menis, I.; Mercado Pérez, J.; Meres, M.; Mereu, P.; Miake, Y.; Midori, J.; Milano, L.; Milosevic, J.; Mischke, A.; Miśkowiec, D.; Mitu, C.; Mlynarz, J.; Mohanty, A. K.; Mohanty, B.; Molnar, L.; Montaño Zetina, L.; Monteno, M.; Montes, E.; Morando, M.; Moreira de Godoy, D. A.; Moretto, S.; Morsch, A.; Muccifora, V.; Mudnic, E.; Muhuri, S.; Müller, H.; Munhoz, M. G.; Munoz, J.; Musa, L.; Musso, A.; Nandi, B. K.; Nania, R.; Nappi, E.; Nattrass, C.; Navach, F.; Navin, S.; Nayak, T. K.; Nazarenko, S.; Nazarov, G.; Nedosekin, A.; Nendaz, F.; Newby, J.; Nicassio, M.; Nielsen, B. S.; Niida, T.; Nikolaev, S.; Nikolic, V.; Nikulin, S.; Nikulin, V.; Nilsen, B. S.; Nilsson, M. S.; Noferini, F.; Nooren, G.; Novitzky, N.; Nyanin, A.; Nyatha, A.; Nygaard, C.; Nystrand, J.; Obayashi, H.; Ochirov, A.; Oeschler, H.; Oh, S. K.; Oleniacz, J.; Oppedisano, C.; Ortiz Velasquez, A.; Ortona, G.; Oskarsson, A.; Ostrowski, P.; Otterlund, I.; Otwinowski, J.; Oyama, K.; Ozawa, K.; Pachmayer, Y.; Pachr, M.; Padilla, F.; Pagano, P.; Jayarathna, S. P.; Paić, G.; Painke, F.; Pajares, C.; Pal, S.; Pal, S. K.; Palaha, A.; Palmeri, A.; Pappalardo, G. S.; Park, W. J.; Patalakha, D. I.; Paticchio, V.; Pavlinov, A.; Pawlak, T.; Peitzmann, T.; Peresunko, D.; Pérez Lara, C. E.; Perini, D.; Perrino, D.; Peryt, W.; Pesci, A.; Peskov, V.; Pestov, Y.; Peters, A. J.; Petráček, V.; Petran, M.; Petris, M.; Petrov, P.; Petrovici, M.; Petta, C.; Piano, S.; Piccotti, A.; Pikna, M.; Pillot, P.; Pinazza, O.; Pinsky, L.; Pitz, N.; Piuz, F.; Piyarathna, D. B.; Platt, R.; Płoskoń, M.; Pluta, J.; Pocheptsov, T.; Pochybova, S.; Podesta-Lerma, P. L. M.; Poghosyan, M. G.; Polák, K.; Polichtchouk, B.; Pop, A.; Porteboeuf, S.; Pospíšil, V.; Potukuchi, B.; Prasad, S. K.; Preghenella, R.; Prino, F.; Pruneau, C. A.; Pshenichnov, I.; Puddu, G.; Pulvirenti, A.; Punin, V.; Putiš, M.; Putschke, J.; Quercigh, E.; Qvigstad, H.; Rachevski, A.; Rademakers, A.; Rademakers, O.; Radomski, S.; Räihä, T. S.; Rak, J.; Rakotozafindrabe, A.; Ramello, L.; Ramírez Reyes, A.; Rammler, M.; Raniwala, R.; Raniwala, S.; Räsänen, S. S.; Read, K. F.; Real, J.; Redlich, K.; Renfordt, R.; Reolon, A. R.; Reshetin, A.; Rettig, F.; Revol, J.-P.; Reygers, K.; Ricaud, H.; Riccati, L.; Ricci, R. A.; Richter, M.; Riedler, P.; Riegler, W.; Riggi, F.; Rodríguez Cahuantzi, M.; Rohr, D.; Röhrich, D.; Romita, R.; Ronchetti, F.; Rosinský, P.; Rosnet, P.; Rossegger, S.; Rossi, A.; Roukoutakis, F.; Rousseau, S.; Roy, C.; Roy, P.; Rubio Montero, A. J.; Rui, R.; Rivetti, A.; Rusanov, I.; Ryabinkin, E.; Rybicki, A.; Sadovsky, S.; Šafařík, K.; Sahoo, R.; Sahu, P. K.; Saini, J.; Saiz, P.; Sakai, S.; Sakata, D.; Salgado, C. A.; Samanta, T.; Sambyal, S.; Samsonov, V.; Sanchez Castro, X.; Šándor, L.; Sandoval, A.; Sano, M.; Sano, S.; Santo, R.; Santoro, R.; Sarkamo, J.; Saturnini, P.; Scapparone, E.; Scarlassara, F.; Scharenberg, R. P.; Schiaua, C.; Schicker, R.; Schmidt, C.; Schmidt, H. R.; Schreiner, S.; Schuchmann, S.; Schukraft, J.; Schutz, Y.; Schwarz, K.; Schweda, K.; Scioli, G.; Scomparin, E.; Scott, P. A.; Scott, R.; Segato, G.; Selyuzhenkov, I.; Senyukov, S.; Seo, J.; Serci, S.; Serradilla, E.; Sevcenco, A.; Sgura, I.; Shabratova, G.; Shahoyan, R.; Sharma, N.; Sharma, S.; Shigaki, K.; Shimomura, M.; Shtejer, K.; Sibiriak, Y.; Siciliano, M.; Sicking, E.; Siemiarczuk, T.; Silenzi, A.; Silvermyr, D.; Simonetti, G.; Singaraju, R.; Singh, R.; Singhal, V.; Sinha, B. C.; Sinha, T.; Sitar, B.; Sitta, M.; Skaali, T. B.; Skjerdal, K.; Smakal, R.; Smirnov, N.; Snellings, R.; Søgaard, C.; Soloviev, A.; Soltz, R.; Son, H.; Song, J.; Song, M.; Soos, C.; Soramel, F.; Spyropoulou-Stassinaki, M.; Srivastava, B. K.; Stachel, J.; Stan, I.; Stefanek, G.; Stefanini, G.; Steinbeck, T.; Steinpreis, M.; Stenlund, E.; Steyn, G.; Stocco, D.; Stock, R.; Stokkevag, C. H.; Stolpovskiy, M.; Strmen, P.; Suaide, A. A. P.; Subieta Vásquez, M. A.; Sugitate, T.; Suire, C.; Sukhorukov, M.; Šumbera, M.; Susa, T.; Swoboda, D.; Symons, T. J. M.; Szanto de Toledo, A.; Szarka, I.; Szostak, A.; Tagridis, C.; Takahashi, J.; Tapia Takaki, J. D.; Tauro, A.; Tavlet, M.; Tejeda Muñoz, G.; Telesca, A.; Terrevoli, C.; Thäder, J.; Thomas, D.; Thomas, J. H.; Tieulent, R.; Timmins, A. R.; Tlusty, D.; Toia, A.; Torii, H.; Toscano, L.; Tosello, F.; Traczyk, T.; Truesdale, D.; Trzaska, W. H.; Tsuji, T.; Tumkin, A.; Turrisi, R.; Turvey, A. J.; Tveter, T. S.; Ulery, J.; Ullaland, K.; Uras, A.; Urbán, J.; Urciuoli, G. M.; Usai, G. L.; Vacchi, A.; Vajzer, M.; Vala, M.; Valencia Palomo, L.; Vallero, S.; van der Kolk, N.; van Leeuwen, M.; Vande Vyvre, P.; Vannucci, L.; Vargas, A.; Varma, R.; Vasileiou, M.; Vasiliev, A.; Vechernin, V.; Veldhoen, M.; Venaruzzo, M.; Vercellin, E.; Vergara, S.; Vernekohl, D. C.; Vernet, R.; Verweij, M.; Vickovic, L.; Viesti, G.; Vikhlyantsev, O.; Vilakazi, Z.; Villalobos Baillie, O.; Vinogradov, A.; Vinogradov, L.; Vinogradov, Y.; Virgili, T.; Viyogi, Y. P.; Vodopyanov, A.; Voloshin, K.; Voloshin, S.; Volpe, G.; von Haller, B.; Vranic, D.; Øvrebekk, G.; Vrláková, J.; Vulpescu, B.; Vyushin, A.; Wagner, B.; Wagner, V.; Wan, R.; Wang, D.; Wang, Y.; Wang, Y.; Watanabe, K.; Wessels, J. P.; Westerhoff, U.; Wiechula, J.; Wikne, J.; Wilde, M.; Wilk, A.; Wilk, G.; Williams, M. C. S.; Windelband, B.; Xaplanteris Karampatsos, L.; Yang, H.; Yang, S.; Yasnopolskiy, S.; Yi, J.; Yin, Z.; Yokoyama, H.; Yoo, I.-K.; Yu, W.; Yuan, X.; Yushmanov, I.; Zabrodin, E.; Zach, C.; Zampolli, C.; Zaporozhets, S.; Zarochentsev, A.; Závada, P.; Zaviyalov, N.; Zbroszczyk, H.; Zelnicek, P.; Zenin, A.; Zgura, I.; Zhalov, M.; Zhang, X.; Zhou, D.; Zichichi, A.; Zinovjev, G.; Zoccarato, Y.; Zynovyev, M.

2010-12-01

The first measurement of the charged-particle multiplicity density at midrapidity in Pb-Pb collisions at a center-of-mass energy per nucleon pair sNN=2.76TeV is presented. For an event sample corresponding to the most central 5% of the hadronic cross section, the pseudorapidity density of primary charged particles at midrapidity is 1584±4(stat)±76(syst), which corresponds to 8.3±0.4(syst) per participating nucleon pair. This represents an increase of about a factor 1.9 relative to pp collisions at similar collision energies, and about a factor 2.2 to central Au-Au collisions at sNN=0.2TeV. This measurement provides the first experimental constraint for models of nucleus-nucleus collisions at LHC energies.

Pressure induced polymerization of acetylide anions in CaC2 and 107 fold enhancement of electrical conductivity.

PubMed

Zheng, Haiyan; Wang, Lijuan; Li, Kuo; Yang, Youyou; Wang, Yajie; Wu, Jiajia; Dong, Xiao; Wang, Chun-Hai; Tulk, Christopher A; Molaison, Jamie J; Ivanov, Ilia N; Feygenson, Mikhail; Yang, Wenge; Guthrie, Malcolm; Zhao, Yusheng; Mao, Ho-Kwang; Jin, Changqing

2017-01-01

Transformation between different types of carbon-carbon bonding in carbides often results in a dramatic change of physical and chemical properties. Under external pressure, unsaturated carbon atoms form new covalent bonds regardless of the electrostatic repulsion. It was predicted that calcium acetylide (also known as calcium carbide, CaC 2 ) polymerizes to form calcium polyacetylide, calcium polyacenide and calcium graphenide under high pressure. In this work, the phase transitions of CaC 2 under external pressure were systematically investigated, and the amorphous phase was studied in detail for the first time. Polycarbide anions like C 6 6- are identified with gas chromatography-mass spectrometry and several other techniques, which evidences the pressure induced polymerization of the acetylide anions and suggests the existence of the polyacenide fragment. Additionally, the process of polymerization is accompanied with a 10 7 fold enhancement of the electrical conductivity. The polymerization of acetylide anions demonstrates that high pressure compression is a viable route to synthesize novel metal polycarbides and materials with extended carbon networks, while shedding light on the synthesis of more complicated metal organics.

Dynamics of droplet collision and flame-front motion

NASA Astrophysics Data System (ADS)

Pan, Kuo-Long

Three physical phenomena were experimentally and computationally investigated in this research, namely the dynamics of head-on droplet-droplet collision, head-on droplet-film collision, and laminar premixed flames, with emphasis on the transition between bouncing and merging of the liquid surfaces for the droplet collision studies, and on the susceptibility to exhibit hydrodynamic instability for the flame dynamics. All three problems share the common feature of having an active deformable interface separating two flow regions of disparate densities, and as such can be computationally described using the adopted immersed boundary technique. Experimentally, the droplets (˜300 mum diameter) were generated using the ink jet printing technique, and imaged using stroboscopy for the droplet-droplet collision events and high-speed cine-photography for the droplet-film collision events. For the study of droplet-droplet collision, the instant of merging was experimentally determined and then used as an input in the computational simulation of the entire collision event. The simulation identified the differences between collision and merging at small and large Weber numbers, and satisfactorily described the dynamics of the inter-droplet gap including the role of the van der Waals force in effecting surface rupture. For the study of droplet-film collision, extensive experimental mapping showed that the collision dynamics is primarily affected by the droplet Weber number (We) and the film thickness scaled by the droplet radius (H), that while droplet absorption by the film is facilitated with increasing droplet Weber number, the boundary of transition is punctuated by an absorption peninsula, in the We-H space, within which absorption is further facilitated for smaller Weber numbers. Results from computation simulation revealed the essential dependence of the collision dynamics on the restraining nature of the solid surface, the energy exchange between the droplet and the

Translational Entanglement and Teleportation of Matter Wavepackets by Collisions and Half-Collisions

NASA Astrophysics Data System (ADS)

Fisch, L.; Tal, A.; Kurizki, G.

To date, the translationally-entangled state originally proposed by Einstein, Podolsky and Rosen (EPR) in 1935 has not been experimentally realized for massive particles. Opatrný and Kurizki [Phys. Rev. Lett. 86, 3180 (2000)] have suggested the creation of a position- and momentum-correlated, i.e., translationally-entangled, pair of particles approximating the EPR state by dissociation of cold diatomic molecules, and further manipulation of the EPR pair effecting matter-wave teleportation. Here we aim at setting the principles of and quantifying translational entanglement by collisions and half-collisions. In collisions, the resonance width s and the initial phase-space distributions are shown to determine the degree of post-collisional momentum entanglement. Half-collisions (dissociation) are shown to yield different types of approximate EPR states. We analyse a feasible realization of translational EPR entanglement and teleportation via cold-molecule Raman dissociation and subsequent collisions, resolving both practical and conceptual difficulties it has faced so far: How to avoid entanglement loss due to the wavepacket spreading of the dissociation fragments? How to measure both position and momentum correlations of the dissociation fragments with sufficient accuracy to verify their EPR correlations? How to reliably perform two-particle (Bell) position and momentum measurements on one of the fragments and the wavepacket to be teleported?

Initial angular momentum and flow in high energy nuclear collisions

NASA Astrophysics Data System (ADS)

Fries, Rainer J.; Chen, Guangyao; Somanathan, Sidharth

2018-03-01

We study the transfer of angular momentum in high energy nuclear collisions from the colliding nuclei to the region around midrapidity, using the classical approximation of the color glass condensate (CGC) picture. We find that the angular momentum shortly after the collision (up to times ˜1 /Qs , where Qs is the saturation scale) is carried by the "β -type" flow of the initial classical gluon field, introduced by some of us earlier. βi˜μ1∇iμ2-μ2∇iμ1 (i =1 ,2 ) describes the rapidity-odd transverse energy flow and emerges from Gauss's law for gluon fields. Here μ1 and μ2 are the averaged color charge fluctuation densities in the two nuclei, respectively. Interestingly, strong coupling calculations using anti-de Sitter/conformal field theory (AdS/CFT) techniques also find an energy flow term featuring this particular combination of nuclear densities. In classical CGC the order of magnitude of the initial angular momentum per rapidity in the reaction plane, at a time 1 /Qs , is |d L2/d η |≈ RAQs-3ɛ¯0/2 at midrapidity, where RA is the nuclear radius, and ɛ¯0 is the average initial energy density. This result emerges as a cancellation between a vortex of energy flow in the reaction plane aligned with the total angular momentum, and energy shear flow opposed to it. We discuss in detail the process of matching classical Yang-Mills results to fluid dynamics. We will argue that dissipative corrections should not be discarded to ensure that macroscopic conservation laws, e.g., for angular momentum, hold. Viscous fluid dynamics tends to dissipate the shear flow contribution that carries angular momentum in boost-invariant fluid systems. This leads to small residual angular momentum around midrapidity at late times for collisions at high energies.

Enhanced amplified spontaneous emission in a quantum dot-doped polymer-dispersed liquid crystal

NASA Astrophysics Data System (ADS)

Cao, Mingxuan; Zhang, Yating; Song, Xiaoxian; Che, Yongli; Zhang, Haiting; Yan, Chao; Dai, Haitao; Liu, Guang; Zhang, Guizhong; Yao, Jianquan

2016-07-01

Quantum dot-doped polymer-dispersed liquid crystals (QD-PDLCs) were prepared by photoinitiated polymerization and sealed in capillary tubes. The concentration of QDs in the PDLC was 1 wt%. Amplified spontaneous emission (ASE) of the quantum dot-doped polymer-dispersed liquid crystals was observed with 532 nm wavelength laser excitation. The threshold for ASE was 6 mJ cm-2, which is much lower than that for homogeneous quantum dot-doped polymer (25 mJ cm-2). The threshold for ASE was dramatically enhanced when the working temperature exceeded the clearing point of the liquid crystal; this result demonstrates that multi-scattering caused by the liquid crystals effectively improved the path length or dwell time of light in the gain region, which played a key role in decreasing the threshold for ASE.

Collisional Quenching of Highly-Excited H2 due to H2 Collisions

NASA Astrophysics Data System (ADS)

Wan, Yier; Yang, Benhui H.; Stancil, Phillip C.; Naduvalath, Balakrishnan; Forrey, Robert C.; This work was partially support by Hubble grant HST-AT-13899. We thank Kyle Walkerassistance with vrrmm.

2017-06-01

Collision-induced energy transfer involving H2 molecules are of significant interest, since H2 is the most abundant molecular species in the universe. Collisional de-excitation rate coefficients of the H2-H2 system are necessary to produce accurate models of astrophysical environments. However, accurate calculations of collisional energy transfer are still a challenging problem, especially for highly-excited H2 because a large number of levels must be included in the calculation.Currently, most data are limited to initial rotational levels j up to 8 or initial vibrational levels up to 3. The vast majority of these results involve some form of a reduced-dimensional approach which may be of questionable accuracy. A reliable and accurate four-dimensional PES computed by Patkowski et al. is used in this work along with two quantum scattering programs (MOLSCAT and vrrmm). Another accurate full-dimensional PES has been reported for the H2-H2 system by Hinde.Not all transitions will be explicitly calculated. A zero-energy scaling technique (ZEST) is used to estimate some intermediate transitions from calculated rate coefficients. New inelastic quenching cross section for para-H2+para-H2 collisions with initial level j= 10, 12, 14, 18, 24 are calculated. Calculations for other de-excitation transitions from higher initial levels and collisions involving other spin isomer of hydrogen, ortho-H2+para-H2, ortho-H2+ortho-H2 and para-H2+ortho-H2 are in progress. The coupled- states approximation is also applied to obtain cross sections at high energy.K. Patkowski, et al., J. Chem. Phys. 129, 094304 (2008).J. M. Hutson and S. Green, MOLSCAT Computer code, v14 (1994).K. Walker, 2013, VRRMM: Vibrational/Rotational Rich Man’s MOLSCAT v3.1.K. Walker, Song, L., Yang, B. H.,et al. 2015, ApJ, \\811,27.S. Green, J. Chem. Phys. 62, 2271 (1975).Flower, D. R., Roueff, E. 1998, J. Phys. B, 31, 2935.T. -G. Lee, N. Balakrishnan, R. C. Forrey, P. C. Stancil, G. Shaw, D. R. Schultz, and G. J

Structural properties of Y2O3–Al2O3 liquids and glasses: An overview

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilding, Martin C.; Wilson, Mark; McMillan, Paul F.

2015-01-01

Liquids in the system Y2O3- Al2O3 have been the subject of considerable study because of the reported occurrence of a first-order density and entropy-driven liquid-liquid phase transition (LLPT) in the supercooled liquid state. The observations have become controversial because of the presence of crystalline material that can be formed simultaneously and that can mask the nucleation and growth of the lower density liquid. The previous work is summarized here along with arguments for and against the different viewpoints. Also two studies have been undertaken to investigate the LLPT in this refractory system with emphasis on determining the structure of unequivocallymore » amorphous materials. These include the in situ high energy X-ray diffraction (HEXRD) of supercooled Y2O3 - Al2O3 liquids and the low frequency vibrational dynamics of recovered glasses. Manybody molecular dynamics simulations are also used to interpret the results of both studies. The HEXRD measurements, combined with aerodynamic levitation and rapid data acquisition techniques, show that for the 20 mol% Y2O3 (i.e. AlY20) liquid there is a shift in the position of the first peak in the diffraction pattern over a narrow temperature range (2100-1800 K) prior to crystallization. Microbeam Raman spectroscopy measurements made on AlY20 glasses clearly show contrasting spectra in the low frequency part of the spectrum for low(LDA) and high-density (HDA) glassy regions. The molecular dynamics simulations identify contrasting coordination environments around oxygen anions for the high- (HDL) and low-density (LDL) liquids. (C) 2014 Elsevier B.V. All rights reserved.« less

Structural properties of Y 2O 3–Al 2O 3 liquids and glasses: An overview